# Patent

## Title
Use of a copolymer having at least one grafted alkoxy or hydroxy polyalkylene glycol function as an agent for improving optical brightening activation, and products obtained

## Abstract

The invention relates to a water-soluble copolymer having at least one alkoxy or hydroxyl polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, as an agent to improve the activation of the optical brightness of the end product, in the fields of paper, textile, detergents and paint.

## Background
The present invention relates to the technical sector of paper, textile, detergents, paint, and, in particular, the field of fillers and paper coating colours, with a view to improving the activation of optical brightness at the level of the end product.
The invention first of all relates to the use of a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, as agent improving the activation of the optical brightness of the end product.
The invention also relates to the agent improving the activation of the optical brightness of the end product.
The invention also relates to the use of a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, as agent designed to improve the activation of the optical brightness of the end product, and implemented in a dispersion method of pigments and/or mineral fillers in aqueous suspension. It also relates to the dispersion method that implements said copolymer and the aqueous suspensions thus obtained.
It also relates to the use of said aqueous suspensions for the manufacture of fillers and/or coating colours. It also relates to the coating colours and fillers thus obtained. Finally, it relates to the use of said fillers and said coating colours for manufacturing and/or coating the papers. It also relates to the papers thus obtained.
The invention also relates to the use of a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, as agent improving the activation of the optical brightness of the end product, and implemented in grinding fillers and/or mineral pigments in aqueous suspension. It also relates to the grinding method that implements said copolymer and the aqueous suspensions thus obtained.
It also relates to the use of said aqueous suspensions for the manufacture of fillers and/or coating colours. It also relates to the coating colours and fillers thus obtained. Finally, it relates to the use of said fillers and said coating colours for manufacturing and/or coating the papers. It also relates to the papers thus obtained.
The invention also relates to the use of a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, as agent improving the activation of the optical brightness of the end product, and implemented in a filler manufacturing method. It also relates to the filler manufacturing method that implements said copolymer and the fillers thus obtained. It also relates to the use of said fillers for the manufacture of coating colours. Finally, it relates to the papers thus obtained.
The invention also relates to the use of a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, as agent improving the activation of the optical brightness of the end product, and implemented in a coating colour manufacturing method. It also relates to the coating colour manufacturing method that implements said copolymer and the coating colours thus obtained. It also relates to the use of the coating colours thus obtained for coating the papers. Finally, it relates to the papers thus obtained.
Moreover, the invention relates to the use of water-soluble copolymers according to the invention as additives in the manufacture of suspensions of previously dispersed and/or ground mineral matter. It also relates to the use of the suspensions thus obtained in the manufacture of paper coating colours.
Finally, the invention relates to the use of water-soluble copolymers according to the invention as additives to improve the activation of optical brightness in textile, detergent or paint compositions and also relates to the textile, detergent or paint compositions that contain them.
The paper manufacturing method comprises several stages, including: the slurrying of the pigments and/or mineral fillers; the use of said suspensions or slurries to manufacture fillers and/or coating colours; the use of said coating colours and said fillers to manufacture and/or coat the papers. Throughout this method, the skilled man in the art will keep in mind the need to obtain a final product presenting a strong activation of optical brightness, and, consequently, to obtain as white a colour as possible; the increase in the degree of whiteness of the end product is a matter of major concern to the paper manufacturers. This property of activating the optical brightness, together with the known means for enhancing said brightness during the course of the method described above, are subsequently illustrated via documents accessible to the skilled man in the art in the prior art.
During the course of said method, the mineral fillers and/or pigments, such as calcium carbonate, dolomites, kaolin, talc, gypsum, titanium oxide, satin white or aluminium trihydroxide, are initially slurried, alone or in mixtures. To do this, use is made of dispersing and/or grinding aid agents of these pigments and/or mineral fillers still referred to as mineral matter.
It is to be noted that, throughout the description, we speak of mineral matter, fillers and/or pigments, as these terms have the same meaning for the Applicant.
These dispersing and/or grinding aid agents behave as rheology modifiers in so far as they fluidify the suspensions. The mechanical action of grinding, facilitated by the use of grinding agents, also contributes to reducing the size of the particles. Use can also be made of additives that make it possible to regulate the viscosity of said suspensions of mineral matter.
Thus, the skilled man in the art knows document EP 0 610 534 which describes how to prepare polymers obtained by the copolymerization of an isocyanate monomer and aprotic monomers and by functionization using glycol polyalkylene monoalkyl amines or ethers. Such agents are particularly effective for grinding organic pigments.
He also knows document WO 00/77058 which describes copolymers based on an unsaturated derivative of a mono- or dicarboxylic acid, of an unsaturated derivative of polyalkylene glycol, of an unsaturated polysiloxane compound or of an unsaturated ester. These copolymers are used as dispersing agents in mineral filler suspensions, notably in the cement industry.
He also knows document WO 01/96007 which describes an ionic, water-soluble copolymer, having a grafted alkoxy or hydroxy polyalkylene glycol function, the role of which is to disperse and/or facilitate the grinding of the pigments and/or mineral fillers.
Similarly, the skilled man in the art knows document FR 2 707 182 which explains how to use a polymeric compound based on polyacrylic acid salts and phosphonates to fluidify suspensions of inorganic pigments.
However, neither these documents, nor the others that appear in the prior art, teach that the grafting of an alkoxy or hydroxy polyalkylene glycol group improves the activation of the optical brightness.
Said aqueous suspensions of pigments and/or of mineral fillers then enter into the composition of the fillers and/or coating colours.
In the case of fillers, said fillers are added to the fibres before manufacture of the paper sheet; we speak of fillers added to the mass, or fillers, during the manufacture of the fibrous suspension which feeds the paper machine, as indicated in document WO 99/42657. Said fillers can be added to the fibres in the form of suspensions of pigments and/or of mineral fillers. Optical brighteners can also be added to the fibres. These are fluorescent substances “added to the detergents or used to treat textiles or papers, in order to increase their whiteness” (A Dictionary of Science, Oxford University Press, Market House Books 1999), this whiteness being a matter of fundamental importance for the end user. Optical brighteners are generally stylbenic molecules having the property of absorbing part of the luminous radiation in the UV wavelengths, in order to re-emit it in the visible spectrum, thus improving the whiteness of the end product. This whiteness is characterized by the diffuse reflectance factors of the paper for a wavelength of 457 nm, measured with and without UV, noted respectively R457+UV and R457−UV; the difference ΔUV=R457+UV−R457−UV is then calculated. These factors are measured according to French standard NF Q 03-039 using a spectrocolorimeter which meets the specifications of experimental standard NF Q 03-038. The whiteness can also be characterized by the factor W(CIE) measured in accordance with standard ISO/FDIS 11475.
In the case of coating colours, said coating colours are made by adding a certain number of additives to the aqueous suspensions of pigments and/or of mineral fillers. Use is made in particular of latexes which act as binders, and of optical brightness agents. Finally, it is possible to add to these substances compounds known as “carriers” or “activators” of optical brighteners, in the sense that they develop the activity of said brighteners, thus improving the whiteness of the end product.
In this manner, in order to activate the optical brightness, a well known approach is to incorporate, in the paper coating colours a certain number of compounds such as, for example polyvinyl alcohol (PVA), carboxymethylcellulose (CMC), polyvinylpyrrolidone (PVP), casein or starch, which are described in the document “Optical Brightening of Coated Papers” (Allg. Papier-Rundschau, Nov. 5, 1982, No. 44, p. 1242.). Similarly, the document “Effect of Polyethylene Glycols on the Properties of Coating Colors and Coating Quality” (Wochbl. Papierfabr., Feb. 15, 1978, Vol. 106, No. 3, pp. 109-112.) teaches the skilled man in the art how to use polyethylene glycol as carrier for optical brightness in paper coating colours.
The skilled man in the art also knows document JP 60 134096 which describes how to coat papers using a coating colour containing an acrylic or styrene-butadiene copolymer based latex binder, fillers such as, for example calcium carbonate, chalk, talc, kaolin, or a stylbenic or polyethylene glycol compound. This enhances the whiteness of the papers. Finally, the skilled man in the art knows document EP 1 001 083 which describes a polymeric composition containing at least one polyvinyl alcohol and at least one water-soluble polymer at neutral or alkaline pH, used in paper coating colours to improve water retention and activate the optical brightness of the end product.
Pursuing its research with a view to increasing the activation of the optical brightness of papers, the Applicant has surprisingly found that the use in pigment and/or mineral filler grinding methods, in pigment and/or mineral filler dispersion methods, in filler manufacturing methods, in coating colour manufacturing methods, of a water-soluble copolymer having at least one grafted alkoxy or hydroxy polyalkylene glycol function on at least one ethylenically unsaturated monomer, made it possible to improve the activation of the optical brightness of the papers, thereby improving the whiteness of the end product.
In this way, the use according to the invention of a water-soluble copolymer as optical brightness activator is characterized in that the copolymer has at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer.
More specifically, the Applicant found that the presence in said copolymer of at least one monomer of formula (I):




where

    
    
        m and p represent a number of alkylene oxide units less than or equal to 150
        n represents a number of ethylene oxide units less than or equal to 150
        q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150,
        R1 represents hydrogen or the methyl or ethyl radical
        R2 represents hydrogen or the methyl or ethyl radical
        R represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
        R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms,

made it possible to develop copolymers having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, thereby improving the activation of the optical brightness of the papers.

    
    


Thus, according to the invention, said water-soluble copolymer comprises:

    
    
        a) at least one anionic monomer with a carboxylic or dicarboxylic or phosphoric or phosphonic or sulfonic function or a mixture thereof,
        b) at least one non-ionic monomer, the non-ionic monomer consisting of at least one monomer of formula (I):
    
    






    
    
        
        
            where
            
                m and p represent a number of allylene oxide units less than or equal to 150
                n represents a number of ethylene oxide units less than or equal to 150
                q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150, and preferably such that 15≦(m+n+p)q≦120,
                R1 represents hydrogen or the methyl or ethyl radical,
                R2 represents hydrogen or the methyl or ethyl radical,
                R represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as for example acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
                R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having from 1 to 12 carbon atoms and even more preferably a hydrocarbon radical having from 1 to 4 carbon atoms,
            
            
            or a mixture of several monomers of formula (I),
        
        
        c) possibly, at least one monomer of the acrylamide or methacrylamide type or their derivatives such as N-[3-(dimethylamino) propyl]acrylamide or N-[3-(dimethylamino) propyl]methacrylamide, and mixtures thereof, or at least one non water-soluble monomer such as the alkyl acrylates or methacrylates, unsaturated esters such as N-[2-(dimethylamino) ethyl]methacrylate, or N-[2-(dimethylamino) ethyl]acrylate, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or at least one cationic monomer or quaternary ammonium such as [2-(methacryloyloxy) ethyl]trimethyl ammonium chloride or sulfate, [2-(acryloyloxy) ethyl]trimethyl ammonium chloride or sulfate, [3-(acrylamido) propyl]trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, [3-(methacrylamido) propyl]trimethyl ammonium chloride or sulfate, or at least one organofluorinated or organosilylated monomer, or a mixture of several of these monomers,
        d) possibly at least one monomer having at least two ethylenic insaturations referred to as the crosslinking monomer in the rest of the application,

the total of the proportions of components a), b), c) and d) being equal to 100%.

    
    


Said copolymer brought about an improvement in the activation of the optical brightness of the papers.
This goal is attained thanks to the use of a water-soluble copolymer comprising:

    
    
        a) at least one ethylenically unsaturated anionic monomer with a monocarboxylic or dicarboxylic or sulfonic or phosphoric or phosphonic function or a mixture thereof,
        b) at least one non-ionic monomer of formula (I),
        c) possibly, at least one monomer of the acrylamide or methacrylamide type or their derivatives such as N-[3-(dimethylamino) propyl]acrylamide or N-[3-(dimethylamino) propyl]methacrylamide, and mixtures thereof, or at least one non water-soluble monomer such as the alkyl acrylates or methacrylates, unsaturated esters such as N-[2-(dimethylamino) ethyl]methacrylate, or N-[2-(dimethylamino) ethyl]acrylate, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or at least one cationic monomer or quaternary ammonium such as [2-(methacryloyloxy) ethyl]trimethyl ammonium chloride or sulfate, [2-(acryloyloxy) ethyl]trimethyl ammonium chloride or sulfate, [3-(acrylamido) propyl]trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, [3-(methacrylamido) propyl]trimethyl ammonium chloride or sulfate, or at least one organofluorinated or organosilylated monomer, or a mixture of several of these monomers,
        d) possibly, at least one crosslinking monomer,

the total of the proportions of components a), b), c) and d) being equal to 100%.

    
    


The use, according to the invention, of a water-soluble copolymer, having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer leading to an improvement in the activation of the optical brightness of the papers, is characterized in that said water-soluble copolymer consists of:

    
    
        a) at least one ethylenically unsaturated anionic monomer having a monocarboxylic function selected from among the ethylenically unsaturated monomers having a monocarboxylic function such as acrylic or methacrylic acid or hemiesters of diacids such as C1 to C4 monoesters of maleic or itaconic acid, or mixtures thereof, or selected from among the ethylenically unsaturated monomers having a dicarboxylic function such as crotonic, isocrotonic, cinnamic, itaconic, maleic acid, or anhydrides of carboxylic acids, such as maleic anhydride or selected from among the ethylenically unsaturated monomers having a sulfonic function such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, vinylsulfonic acid and styrenesulfonic acid or selected from among the ethylenically unsaturated monomers having a phosphoric function such as vinylphosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate and their ethoxylates or selected from among the ethylenically unsaturated monomers having a phosphonic function such as vinylphosphonic acid, or mixtures thereof,
        b) at least one non-ionic ethylenically unsaturated monomer of formula (I):
    
    






    
    
        
        
            where
            
                m and p represent a number of alkylene oxide units less than or equal to 150
                n represents a number of ethylene oxide units less than or equal to 150
                q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150, and preferably such that 15≦(m+n+p)q≦120,
                R1 represents hydrogen or the methyl or ethyl radical,
                R2 represents hydrogen or the methyl or ethyl radical,
                R represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as for example acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
                R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having from 1 to 12 carbon atoms and even more preferably a hydrocarbon radical having from 1 to 4 carbon atoms,
            
            
            or a mixture of several monomers of formula (I),
        
        
        c) possibly, at least one monomer of the acrylamide or methacrylamide type or their derivatives such as N-[3-(dimethylamino) propyl]acrylamide or N-[3-(dimethylamino) propyl]methacrylamide, and mixtures thereof, or at least one non water-soluble monomer such as the alkyl acrylates or methacrylates, unsaturated esters such as N-[2-(dimethylamino) ethyl]methacrylate, or N-[2-(dimethylamino) ethyl]acrylate, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or at least one cationic monomer or quaternary ammonium such as [2-(methacryloyloxy) ethyl]trimethyl ammonium chloride or sulfate, [2-(acryloyloxy) ethyl]trimethyl ammonium chloride or sulfate, [3-(acrylamido) propyl]trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, [3-(methacrylamido) propyl]trimethyl ammonium chloride or sulfate, or at least one organofluorinated or at least one organosilylated monomer, selected preferably from among molecules of formula (IIa) or (IIb), with formula (IIa)
    
    






    
    
        
        
            where
            
                m1, p1, m2 and p2 represent a number of alkylene oxide units less than or equal to 150
                n1 and n2 represent a number of ethylene oxide units less than or equal to 150
                q1 and q2 represent an integer equal to at least 1 and such that 0≦(m1+n1+p1)q1≦150 and 0≦(m2+n2+p2)q2≦150,
                r represents a number such that 1≦r≦200
                R3 represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as for example acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
                R4, R5, R10 and R11 represent hydrogen or the methyl or ethyl radical,
                R6, R7, R8 and R9 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof,
                R12 represents a hydrocarbon radical having from 1 to 40 carbon atoms,
                A and B are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,
            
            
            with formula (IIb)

R-A-Si(OB)3 

            where
            
                R represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as for example acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
                A is a group which may be present, in which case it represents a hydrocarbon radical having from 1 to 4 carbon atoms
                B represents a hydrocarbon radical having from 1 to 4 carbon atoms
            
            
            or a mixture of several of said monomers,
        
        
        d) possibly, at least one crosslinking monomer selected, but not exclusively, from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, the allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers prepared from polyols such as pentaerythritol, sorbitol, sucrose or others, or selected from the molecules of formula (III):
    
    






    
    
        
        
            where
            
                m3, p3, m4 and p4 represent a number of alkylene oxide units less than or equal to 150,
                n3 and n4 represent a number of ethylene oxide units less than or equal to 150,
                q3 and q4 represent an integer equal to at least 1 and such that 0≦(m3+n3+p3)q3≦150 and 0≦(m4+n4+p4)q4≦150,
                r′ represents a number such that 1≦r′≦200,
                R13 represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as for example acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
                R14, R15, R20 and R21 represent hydrogen or the methyl or ethyl radical,
                R16, R17, R18 and R19 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof,
                D and E are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,
            
            
            or a mixture of several of said monomers,

the total of the proportions of components a), b), c) and d) being equal to 100%.

        
        
    
    


More particularly, the use of the above-mentioned copolymer is characterized in that said water-soluble copolymer consists, in terms of weight, of:

    
    
        a) from 2% to 95%, and more particularly from 5% to 90% of at least one ethylenically unsaturated anionic monomer having a monocarboxylic function selected from among the ethylenically unsaturated monomers having a monocarboxylic function such as acrylic or methacrylic acid or hemiesters of diacids such as C1 to C4 monoesters of maleic or itaconic acid, or mixtures thereof, or selected from among the ethylenically unsaturated monomers having a dicarboxylic function such as crotonic, isocrotonic, cinnamic, itaconic, maleic acid, or anhydrides of carboxylic acids, such as maleic anhydride or selected from among the ethylenically unsaturated monomers having a sulfonic function such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, vinylsulfonic acid and styrenesulfonic acid or selected from among the ethylenically unsaturated monomers having a phosphoric function such as vinylphosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate and their ethoxylates or selected from among the ethylenically unsaturated monomers having a phosphonic function such as vinylphosphonic acid, or mixtures thereof,
        b) from 2 to 95% and, more particularly, from 5% to 90%, of at least one non-ionic ethylenically unsaturated monomer of formula (I):
    
    






    
    
        
        
            where
            
                m and p represent a number of alkylene oxide units less than or equal to 150,
                n represents a number of ethylene oxide units less than or equal to 150,
                q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150, and preferably such that 15≦(m+n+p)q≦120,
                R1 represents hydrogen or the methyl or ethyl radical
                R2 represents hydrogen or the methyl or ethyl radical
                R represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as for example acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
                R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having from 1 to 12 carbon atoms and even more preferably a hydrocarbon radical having from 1 to 4 carbon atoms,
            
            
            or a mixture of several monomers of formula (I),
        
        
        c) from 0% to 50% of at least one monomer of the acrylamide or methacrylamide type or their derivatives such as N-[3-(dimethylamino) propyl]acrylamide or N-[3-(dimethylamino) propyl]methacrylamide, and mixtures thereof, or at least one non water-soluble monomer such as the alkyl acrylates or methacrylates, unsaturated esters such as N-[2-(dimethylamino) ethyl]methacrylate, or N-[2-(dimethylamino) ethyl]acrylate, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or at least one cationic monomer or quaternary ammonium such as [2-(methacryloyloxy) ethyl]trimethyl ammonium chloride or sulfate, [2-(acryloyloxy) ethyl]trimethyl ammonium chloride or sulfate, [3-(acrylamido) propyl]trimethyl ammonium chloride or sulfate, dimethyl diallyl ammonium chloride or sulfate, [3-(methacrylamido) propyl]trimethyl ammonium chloride or sulfate, or an organofluorinated monomer or a organosilylated monomer, selected preferably from among the molecules of formula (IIa) or (IIb),
        
            with formula (IIa)
        
        
    
    






    
    
        
        
            where
            
                m1, p1, m2 and p2 represent a number of alkylene oxide units less than or equal to 150,
                n1 and n2 represent a number of ethylene oxide units less than or equal to 150,
                q1 and q2 represent an integer equal to at least 1 and such that 0≦(m1+n1+p1)q1≦150 and 0≦(m2+n2+p2)q2≦150,
                r represents a number such that 1≦r≦200,
                R3 represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as for example acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
                R4, R5, R10 and R11 represent hydrogen or the methyl or ethyl radical,
                R6, R7, R8 and R9 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof,
                R12 represents a hydrocarbon radical having from 1 to 40 carbon atoms,
                A and B are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,
            
            
            with formula (IIb)

R-A-Si(OB)3 

            where
            
                R represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as for example acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
                A is a group which may be present, in which case it represents a hydrocarbon radical having from 1 to 4 carbon atoms,
                B represents a hydrocarbon radical having from 1 to 4 carbon atoms,
            
            
            or a mixture of several of said monomers,
        
        
        d) from 0% to 3% of at least one crosslinking monomer selected, but not exclusively, from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, the allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers prepared from polyols such as pentaerythritol, sorbitol, sucrose or others from among the molecules of formula (III):
    
    






    
    
        
        
            where
            
                m3, p3, m4 and p4 represent a number of alkylene oxide units less than or equal to 150,
                n3 and n4 represent a number of ethylene oxide units less than or equal to 150,
                q3 and q4 represent an integer equal to at least 1 and such that 0≦(m3+n3+p3)q3≦150 and 0≦(m4+n4+p4)q4≦150,
                r′ represents a number such that 1≦r′≦200,
                R13 represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates such as acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane and allylurethane, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
                R14, R15, R20 and R21 represent hydrogen or the methyl or ethyl radical,
                R16, R17, R18 and R19 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof,
                D and E are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,
            
            
            or a mixture of several of said monomers,

the total of the proportions of components a), b), c) and d) being equal to 100%.

        
        
    
    


The copolymer used according to the invention is obtained by known radical copolymerization methods in solution, in direct or inverse emulsion, in suspension or precipitation in appropriate solvents, in the presence of known catalytic systems and transfer agents, or by means of controlled radical polymerization methods such as the method known as Reversible Addition Fragmentation Transfer (RAFT), the method known as Atom Transfer Radical Polymerization (ATRP), the method known as Nitroxide Mediated Polymerization (NMP), or the method known as Cobaloxime Mediated Free Radical Polymerization.
This copolymer obtained in acid form and possibly distilled may also be fully or partially neutralized by one or more neutralization agents having a monovalent neutralizing function or a polyvalent neutralizing function such as, for example, for the monovalent function those selected from the group consisting of the alkaline cations, in particular sodium, potassium, lithium, ammonium or the primary, secondary or tertiary aliphatic and/or cyclic amines such as for example stearylamine, the ethanolamines (mono-, di-, triethanolamine), mono and diethylamine, cyclohexylamine, methylcyclohexylamine, aminomethylpropanol, morpholine or, for the polyvalent function those selected from the group consisting of alkaline earth divalent cations, in particular magnesium and calcium, or zinc, and of the trivalent cations, including in particular aluminium, or of certain cations of higher valency. Each neutralization agent then operates according to neutralization rates proper to each valency function.
According to another variant, the copolymer obtained from the copolymerization reaction may, before or after the total or partial neutralization reaction, be treated and separated into several phases, according to statistical or dynamic methods known to the skilled man in the art, by one or more polar solvents belonging to the group consisting of water, methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofurane or mixtures thereof.
One of the phases then corresponds to the copolymer used according to the invention as agent whose role is to improve the activation of the optical brightness of the paper.
The invention also relates to said copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, by means of which it is possible to improve the activation of the optical brightness of the papers, detergents, textiles and paints.
Thus, according to the invention, the agent whose role it is to improve the activation of the optical brightness is characterized in that it is the above-mentioned water-soluble copolymer.
The specific viscosity of the copolymer is symbolized by the symbol ηspe and is determined as follows.
A solution of polymerizate is taken so as to obtain a solution corresponding to 2.5 g of dry polymer neutralized with soda and 50 ml of demineralised water. Then, using a capillary viscometer of Baume constant equal to 0.000105 placed in a thermostat controlled bath at 25° C., we measure the runoff time of a given volume of the above-mentioned solution containing the copolymer, and the runoff time of the same volume of demineralized water without said copolymer. It is then possible to define the specific viscosity ηspe thanks to the following relation:




  
    η
    spe
  
  =
  
    
      
        
          
            
              (
              
                runoff
                ⁢
                
                  
                
                ⁢
                time
                ⁢
                
                  
                
                ⁢
                of
              
            
          
        
        
          
            
              
                solution
                ⁢
                
                  
                
                ⁢
                of
                ⁢
                
                  
                
                ⁢
                polymer
              
              )
            
          
        
      
      -
      
        
          
            
              (
              
                runoff
                ⁢
                
                  
                
                ⁢
                time
                ⁢
                
                  
                
                ⁢
                of
              
            
          
        
        
          
            
              
                of
                ⁢
                
                  
                
                ⁢
                demineralized
                ⁢
                
                  
                
                ⁢
                water
              
              )
            
          
        
      
    
    
      runoff
      ⁢
      
        
      
      ⁢
      time
      ⁢
      
        
      
      ⁢
      of
      ⁢
      
        
      
      ⁢
      demineralized
      ⁢
      
        
      
      ⁢
      water
    
  




The capillary tube is generally selected in such a way that the runoff time of the pure demineralized water is approximately 60 to 100 seconds, thus giving highly accurate specific viscosity measurements.
The invention also relates to the dispersion method that implements said copolymer.
This dispersion method according to the invention is characterized in that use is made of said copolymer, and, in particular, in that use is made of 0.05% to 5% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments, and, more particularly, in that use is made of 0.1% to 3% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments.
This dispersion method in aqueous suspension of mineral matter according to the invention is characterized in that the mineral matter is selected from among calcium carbonate, dolomites, kaolin, talc, gypsum, titanium oxide, satin white or aluminium trihydroxide, mica and the mixture of these fillers, such as talc-calcium carbonate or calcium carbonate-kaolin mixtures, or mixtures of calcium carbonate with aluminium trihydroxide, or mixtures with synthetic or natural fibres or co-structures of minerals such as talc-calcium carbonate or talc-titanium dioxide co-structures, and consists more particularly of calcium carbonate such as natural calcium carbonate selected from among marble, calcite, chalk or mixtures thereof.
The invention also relates to the grinding method that implements said copolymer.
This grinding method in aqueous suspension of mineral matter according to the invention is characterized in that use is made of said copolymer, and, in particular, in that use is made of 0.05% to 5% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments, and, more particularly, in that use is made of 0.1% to 3% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments.
This grinding method in aqueous suspension of mineral matter according to the invention is characterized in that the mineral matter is selected from among calcium carbonate, dolomites, kaolin, talc, gypsum, titanium oxide, satin white or aluminium trihydroxide, mica and the mixture of these fillers, such as talc-calcium carbonate or calcium carbonate-kaolin mixtures, or mixtures of calcium carbonate with aluminium trihydroxide, or mixtures with synthetic or natural fibres or co-structures of minerals such as talc-calcium carbonate or talc-titanium dioxide co-structures, and consists more particularly of calcium carbonate such as natural calcium carbonate selected from among marble, calcite, chalk or mixtures thereof.
The invention also relates to the filler manufacturing method that implements said copolymer.
This filler manufacturing method according to the invention is characterized in that use is made of said copolymer, and, in particular, in that use is made of 0.05% to 5% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments, and, more particularly, in that use is made of 0.1% to 1% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments.
The invention also relates to the coating colour manufacturing method that implements said copolymer.
This coating colour manufacturing method according to the invention is characterized in that use is made of said copolymer, and, in particular, in that use is made of 0.05% to 5% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments, and, more particularly, in that use is made of 0.1% to 3% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments. The aqueous suspensions of fillers and/or pigments still referred to as mineral matter, dispersed, and/or ground, and/or with additives of the copolymer according to the invention, are characterized in that they contain said copolymer and more particularly in that they contain from 0.05% to 5% by dry weight of said copolymer with respect to the total dry weight of the fillers and/or pigments, and yet more particularly 0.1% to 3.0% by dry weight of said copolymer with respect to the dry weight of the fillers and/or pigments.
They are also characterized in that the filler and/or pigment is selected from among calcium carbonate, dolomites, kaolin, talc, gypsum, titanium oxide, satin white or aluminium trihydroxide, mica and the mixture of these fillers, such as talc-calcium carbonate or calcium carbonate-kaolin mixtures, or mixtures of calcium carbonate with aluminium trihydroxide, or mixtures with synthetic or natural fibres or co-structures of minerals such as talc-calcium carbonate or talc-titanium dioxide co-structures, or any other filler and/or pigment habitually implemented in the paper industry and mixtures thereof.
Preferably, the aqueous suspensions of mineral matter according to the invention are characterized in that the mineral matter is calcium carbonate such as natural calcium carbonate selected from among marble, calcite, chalk or mixtures thereof.
The fillers according to the invention are characterized in that they contain said copolymer and more particularly in that they contain 0.05% to 5% by dry weight of said copolymer with respect to the total dry weight of the fillers and/or pigments, and more particularly still 0.1% to 1% by dry weight of said copolymer with respect to the total dry weight of the fillers and/or pigments.
The coating colours according to the invention are characterized in that they contain said copolymer and more particularly in that they contain 0.05% to 5% by dry weight of said copolymer with respect to the total dry weight of the fillers and/or pigments, and more particularly still 0.1% to 2% by dry weight of said copolymer with respect to the total dry weight of the fillers and/or pigments.
The manufactured and/or coated papers according to the invention are characterized in that they contain said copolymer.
The textile compositions according to the invention are characterized in that they contain said copolymer.
The detergent compositions according to the invention are characterized in that they contain said copolymer.
The paint compositions according to the invention are characterized in that they contain said copolymer.
The scope and interest of the invention will be better perceived thanks to the following examples which are not of a comprehensive nature.


EXAMPLE 1
This example relates to the use of copolymers according to the invention in a mineral filler dispersion method. It also relates to the use of the suspensions thus obtained in the manufacture of coating colours, said coating colours being used to coat papers. This example also relates to measurements of the optical brightness and whiteness of the papers thus obtained. More precisely, the aim of this example is to demonstrate the efficiency of a water-soluble copolymer according to the invention containing at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, as compared with polymers of the prior art that lack this grafted function.
In the tests corresponding to this example, the first step is to disperse a suspension of mineral matter, in accordance with one of the methods familiar to the skilled man in the art.
The BrookfieldTM viscosity of said suspensions is determined as follows.
The BrookfieldTM viscosity of the suspension is measured using a model RVT BrookfieldTM viscometer, in the unstirred beaker, at a temperature of 23° C. and two speeds of rotation of 10 and 100 rpm with the appropriate spindle. The reading is taken after 1 minute of rotation. This gives 2 BrookfieldTM viscosity measurements respectively noted μ10 and μ100.
Having left this sample lie in the beaker for 8 days, the BrookfieldTM viscosity of the suspension is measured by introducing the appropriate spindle of the RVT model BrookfieldTM viscometer into the unstirred beaker, at a temperature of 23° C. and at 2 speeds of rotation of 10 and 100 rpm (μ10 and μ100). The reading is taken after 1 minute of rotation (BrookfieldTM viscosity before stirring). The same BrookfieldTM viscosity measurements (μ10 and μ100) are also made after the beaker has been stirred for 5 minutes (BrookfieldTM viscosity after stirring).
Said suspensions then enter into the composition of the coating colours.
In this example, each of the coating colours is prepared by incorporating, for 100 parts by weight of dry pigment of said ground suspension of calcium carbonate, 15 parts by dry weight of styrene-butadiene latex marketed by DOW CHEMICAL under the name DL920TM, and 1 part by weight as is of optical brightener marketed by BAYER under the name Blancophor PTM.
The initial viscosity of said coating colours can be determined using the same method as that applied to aqueous suspensions of mineral matter.
Said coating colours are used to coat sheets of support board manufactured by CASCADES LA ROCHETTE, the whiteness of which is characterized by the parameters R457+UV, R457−UV, ΔUV and W(CIE) respectively equal to 70.3−70.0−0.3 and 49.4. Each coating test uses a 21×29.7 cm sheet of board with a specific weight of 223 g/m2 which is coated with the coating colour to be tested. Said coating is performed using a laboratory coater with interchangeable rollers marketed by ERICHSEN under the name Mod. KCC 202TM. Each board sheet is thus coated to 21 g/m2 and then dried in a non-ventilated oven for 5 minutes at 50° C.
Test No. 1
This test illustrates the prior art and implements 0.75% by dry weight, measured with respect to the dry weight of mineral filler of a copolymer according to the prior art to disperse a suspension of calcium carbonate, of which 75% by weight of the particles have a diameter of less than 1 μm determined using a SedigraphTM 5100 grain size analyzer, having a dry matter content of 72%.
Said copolymer consists (by weight) of 70% acrylic acid and 30% maleic anhydride. It has a specific viscosity of 1.4 and is neutralized by means of soda.
Test No. 2
This test illustrates the invention and implements 0.75% by dry weight, measured with respect to the dry weight of mineral filler of a copolymer according to the invention to disperse a suspension of calcium carbonate, of which 75% by weight of the particles have a diameter of less than 1 μm determined using a SedigraphTM 5100 grain size analyzer, having a dry matter content of 72%.
Said copolymer, which has a specific viscosity of 1.2 is neutralized by potash and consists of:

    
    
        a) 13.5% acrylic acid and 3.5% methacrylic acid
        b) 83% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=45
        
        
    
    


For tests No. 1 and 2, the dry matter content of the coating colours, their pH, and the BrookfieldTM viscosities are determined at 10 and 100 rpm (μ10 and μ100).
Finally the parameters R457+UV and R457−UV are measured for coated boards according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
The results corresponding to tests No. 1 and 2 are summed up in table I.









TABLE I








Characteristics of coating



Tests
colours
Whiteness of coated boards
















Prior art/

NVM






W


Invention
No.
(%)
pH
μ10
μ100
R457+UV
R457+UV
ΔUV
(CIE)



















Prior art
1
64.8
8.1
1780
325
88.9
83.7
5.2
92.4


Invention
2
65.1
8.1
5360
860
91.6
82.9
8.7
103.9









Table I shows that the use of the copolymer according to the invention containing a grafted methoxypolyethylene glycol methacrylate function of molecular weight 2000, as indicated in test No. 2 via the description of the monomer b), makes a significant improvement to the activation of the optical brightness and the whiteness of the coated boards.
Furthermore, it is noted that the BrookfieldTM viscosities of the coating colours obtained according to the invention are compatible with the normal industrial application.
EXAMPLE 2
This example relates to the use of copolymers according to the invention in a mineral filler grinding method. It also relates to the use of the suspensions thus obtained in the manufacture of coating colours, said coating colours being used to coat papers. This example also relates to measurements of the optical brightness and whiteness of the papers thus obtained. Finally, the aim of this example is to illustrate the influence of the rate of monomer b) on the whiteness of the coated papers.
In the tests corresponding to this example, the first step is to grind a suspension of mineral matter, in accordance with the following method.

    
    
        Use is made of a Dyno-MillTM type fixed-cylinder grinder with rotating impeller, the grinding body consisting of zirconium based beads with a diameter between 0.6 millimeters and 1 millimeter.
        The total volume occupied by the grinding body is 1000 cubic centimeters while its mass is 2700 g.
        The grinding chamber has a volume of 1400 cubic centimeters.
        The circumferential speed of the grinder is 10 meters per second.
        The pigment suspension is recycled at a rate of 40 liters per hour.
        The output of the Dyno-MillTM is fitted with a 200-micron grade separator by means of which it is possible to separate the suspension resulting from the grinding and the grinding body.
        The temperature during each grinding test is maintained at approximately 60° C.
    
    


The granulometry of said suspensions is determined as follows.
One hour after grinding is completed, a sample of the pigmentary suspension the granulometry of which (expressed in % weight of the particles less than 2 micrometers) is measured using a SedigraphTM 5100 particle size analyzer is recovered in a beaker.
The BrookfieldTM viscosity of said suspensions is determined in accordance with the method described in example 1.
Said suspensions then enter into the composition of the coating colours.
In this example, each of the coating colours is prepared by incorporating, for 100 parts by weight of dry pigment of said ground suspension of calcium carbonate, 10 parts by dry weight of styrene-butadiene latex marketed by DOW CHEMICAL under the name DL920TM, and 1 part by weight as is of optical brightener marketed by BAYER under the name Blancophor PTM.
Said coating colours are used to coat precoated sheets of paper. Their whiteness is characterized by the parameters R457+UV, R457−UV, ΔUV and W(CIE) respectively equal to 88.4−85.8−2.6 and 89.5.
Each coating test uses a 21×29.7 cm sheet with a specific weight of 96 g/m2 which is coated with the coating colour to be tested. Said coating is performed using a laboratory coater with interchangeable rollers marketed by ERICHSEN under the name Mod. KCC 202TM. Each paper sheet is thus coated to 15 g/m2 and then dried in an unaired oven for 5 minutes at 50° C.
Test No. 3
This test illustrates the prior art and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a homopolymer of acrylic acid according to the prior art to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
This homopolymer of acrylic acid has a specific viscosity of 0.64 and is neutralized by means of calcium and sodium hydroxides.
Test No. 4
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.08, is neutralized by soda and consists of:

    
    
        a) 89.8% acrylic acid and 0.2% methacrylic acid
        b) 10% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 5

        
        
    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.01, is neutralized by soda and consists of:

    
    
        a) 79.6% acrylic acid and 0.4% methacrylic acid
        b) 20% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 6

        
        
    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.08, is neutralized by soda and consists of:

    
    
        a) 69.5% acrylic acid and 0.5% methacrylic acid
        b) 30% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 7

        
        
    
    


This test illustrates the invention and implements 0.70% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.56, is neutralized by soda and consists of:

    
    
        a) 8.5% acrylic acid and 1.5% methacrylic acid
        b) 90% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 8

        
        
    
    


This test illustrates the prior art and implements 1% by dry weight, measured with respect to the dry weight of mineral filler, of a homopolymer of acrylic acid according to the prior art to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
This homopolymer of acrylic acid has a specific viscosity of 0.64 and is neutralized by means of calcium and sodium hydroxides.
Test No. 9
This test illustrates the invention and implements 1% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 0.64, is neutralized by soda and consists of:

    
    
        a) 94.5% acrylic acid and 0.5% methacrylic acid
        b) 5% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
    
    


For all the tests 3 to 9, the dry matter content of the suspensions of mineral matter, their pH, their granulometry characterized by the percentage by weight of particles smaller than 1 and 2 μm, their BrookfieldTM viscosities at 10 and 100 rpm (μ10 and μ100) determined at t=0, and then at t=8 days, are determined before and after stirring. Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 3 to 9 are summed up in table II.
























Brookfield TM
Brookfield TM









viscosities
viscosities







Brookfield TM
(mPa · s)
(mPa · s)




Dry

Grain
viscosities
at t = 8
at t = 8


Tests
Composition
Mat.

size
(mPa · s)
days before
days after
Whiteness






















Prior art/
of

Cont.

% <
% <
at t = 0
stirring
stirring



W
























No.
Invention
polymer
ηspe
(%)
pH
2 μm
1 μm
μ10
μ100
μ10
μ100
μ10
μ100
R457+UV
R457+UV
Δ UV
(CIE)



























3
Prior art
100% AA
0.64
75.7
9.5
89.8
60.5
510
200
3000
800
470
190
91.4
85.2
6.2
95.5


4
Invention
89.8% AA
1.08
75.9
9.9
85.9
53.3
350
170
2510
640
450
200
92.8
85.2
7.6
97.4




0.2% AMA




10% M




MePEG5000


5
Invention
79.6% AA
1.01
76.2
9.8
90.1
60.5
1710
610
20400
2720
2110
700
93.1
85.1
8
98.4




0.4% AMA




20% M




MePEG5000


6
Invention
69.5% AA
1.08
75.3
9.9
85.7
55.5
1080
410
9560
1760
1170
430
93.4
84.9
8.5
100.2




0.5% AMA




30% M




MePEG5000


7
Invention
8.5% AA
1.56
75.4
8.4
76.1
44.8
1880
740
5000
2020
1660
690
92.8
85.5
7.3
101.2




1.5% AMA




90% M




MePEG5000


8
Prior art
100% AA
0.64
75.8
9.6
90.4
61.3
320
110
1210
510
400
130
91.2
85.4
5.8
95.4


9
Invention
94.5% AA
0.96
75.9
9.4
89.3
58.8
540
220
4440
1110
790
340
93.2
85.3
7.9
98.0




0.5% AMA




5% M




MePEG5000





AA designates: acrylic acid


AMA designates: methacrylic acid


M MePEG5000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 5000






Table II shows that the copolymers according to the invention, used in a mineral filler grinding method, make it possible to significantly improve the activation of the optical brightness of the coated papers, and make a significant improvement to their whiteness, irrespective of the rate of the monomer b) as described in tests No. 4, 5, 6, 7 and 9.
Moreover, these results also demonstrate that the copolymers according to the invention make it possible to obtain suspensions of mineral fillers that can be handled after storage without stirring.
EXAMPLE 3
This example relates to the use of copolymers according to the invention in a mineral filler grinding method. It also relates to the use of the suspensions thus obtained in the manufacture of coating colours, said coating colours being used to coat papers. This example also relates to the measurement of the optical brightness and of the whiteness of the papers thus obtained. Finally, the aim of this example is to illustrate the influence of the length of the grafted alkoxy polyalkylene glycol chain (i.e. the value of (m+n+p)q in formula (I) which enters into the description of the monomer b), and the influence of the chemical nature of the molecule grafting said alkoxy polyalkylene glycol group to the main chain of the polymer.
In this example, the first step is to grind suspensions of mineral matter as per the method described for example 2. Their granulometry and their BrookfieldTM viscosity are determined as per the methods described for example 2. Said suspensions then enter into the composition of coating colours formulated as per the method described for example 2. Finally, said coating colours are used to coat paper sheets as per the method described for example 2, with a coating weight equal to 15 g/m2. Said sheets are 21×29.7 cm precoated paper sheets with a specific weight of 96 g/m2. Their whiteness is characterized by the parameters R457+UV, R457−UV, ΔUV and W(CEE) respectively equal to 88.4−85.8−2.6 and 89.5.
Test No. 10
This test illustrates the prior art and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a homopolymer of acrylic acid according to the prior art to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
This homopolymer of acrylic acid has a specific viscosity of 0.64 and is neutralized by means of calcium and sodium hydroxides.
Test No. 11
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 0.84, is neutralized by soda and consists of:

    
    
        a) 18% methacrylic acid
        b) 82% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=8

Test No. 12

        
        
    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 0.78, is neutralized by soda and consists of:

    
    
        a) 8.3% acrylic acid and 8.7% methacrylic acid
        b) 83% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=17

Test No. 13

        
        
    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.47, is neutralized by soda and consists of:

    
    
        a) 17% acrylic acid
        b) 77.6% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylurethane group, a product of the reaction of ethylene glycol methacrylate and diisocyanate toluene
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
        c) 5.4% ethyl acrylate

Test No. 14

    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 3.66, is neutralized by sodium and consists of:

    
    
        a) 10% methacrylic acid
        b) 90% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the 3 isopropenyl α, α dimethylbenzyl urethane group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
    
    


For all the tests 10 to 14, the dry matter content of the suspensions of mineral matter, their pH, their granulometry identified by the percentage by weight of particles smaller than 1 and 2 μm, their BrookfieldTM viscosities at 10 and 100 rpm (μ10 and μ100) determined at t=0, and then at t=8 days, are determined before and after stirring. Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 10 to 14 are summed up in table III.
























Brookfield TM
Brookfield TM









viscosities
viscosities







Brookfield TM
(mPa · s)
(mPa · s)




Dry

Grain
viscosities
at t = 8
at t = 8


Tests
Composition
Mat.

size
(mPa · s)
days before
days after
Whiteness






















Prior art/
of

Cont.

% <
% <
at t = 0
stirring
stirring



W
























No.
Invention
polymer
ηspe
(%)
pH
2 μm
1 μm
μ10
μ100
μ10
μ100
μ10
μ100
R457+UV
R457+UV
Δ UV
(CIE)



























10
Prior art
100% AA
0.64
76.0
9.4
60.2
37
400
140
670
320
330
130
91.4
84.9
6.5
95.7


11
Invention
18% AMA
0.84
75.3
8.8
60.4
35.4
390
290
18750
2030
7540
890
96.5
85.5
11
110.9




82% M




MePEG350


12
Invention
8.3% AA
0.78
75.9
9.0
60.5
32.7
190
150
1440
460
220
160
95.6
85.0
10.6
109.5




8.7% AMA




83% M




MePEG350


13
Invention
17% AA
1.47
75.7
9.3
63.4
36.9
300
190
3800
820
590
280
96.1
85.0
11.1
112.6




77.6% 




MAEG-TDI-




MePEG5000




5.4% AE


14
Invention
10% AA
3.66
75.3
8.6
60.6
33.5
1630
460
12300
1500
2960
740
95.0
85.3
9.7
109.0




90% IDMBI




MePEG5000





AA designates: acrylic acid


AMA designates: methacrylic acid


AE designates: ethyl acrylate


M MePEG350 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 350


M MePEG5000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 750


MAEG-TDI-MePEG5000 designates: methacrylurethane, a product of the reaction of ethylene glycol methacrylate and diisocyanate toluene and of methoxypolyethylene glycol with a molecular weight of 5000


M MePEG5000 designates: the product of the reaction of methoxypolyethylene glycol of molecular weight 5000 with 3 isopropenyl α,α dimethylbenzyl isocyanate






Table III shows that the copolymers according to the invention, used in a mineral filler grinding method, make a significant improvement to the activation of the optical brightness of the coated papers and to their whiteness, for different natures of the monomer b) containing the alkoxy polyalkylene glycol group, on the one hand, and, on the other hand, for a value of (m+n+p)q between 5 and 150, in the definition of the monomer b) as described via formula (I).
Moreover, these results also demonstrate that the copolymers according to the invention make it possible to obtain suspensions of mineral fillers that can be handled after storage without stirring.
EXAMPLE 4
This example relates to the use of copolymers according to the invention in a mineral filler grinding method. It also relates to the use of the suspensions thus obtained in the manufacture of coating colours, said coating colours being used to coat papers. This example also relates to the measurement of the optical brightness and of the whiteness of the papers thus obtained. Finally, the aim of this example is to illustrate the influence of the nature of the monomer selected from among components c) and d) of the copolymer according to the invention.
In this example, the first step is to grind suspensions of mineral matter as per the method described for example 2. Their granulometry and their BrookfieldTM viscosity are determined as per the methods described for example 2. Said suspensions then enter into the composition of coating colours formulated as per the method described for example 2. Finally, said coating colours are used to coat paper sheets as per the method described for example 2, with a coating weight equal to 15 g/m2. Said sheets are 21×29.7 cm precoated paper sheets with a specific weight of 96 g/m2. Their whiteness is characterized by the parameters R457+UV, R457−UV, ΔUV and W(CEE) respectively equal to 88.4−85.8−2.6 and 89.5.
Test No. 15
This test illustrates the prior art and implements 0.70% by dry weight, measured with respect to the dry weight of mineral filler, of a homopolymer of acrylic acid according to the prior art to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
This homopolymer of acrylic acid has a specific viscosity of 0.64 and is neutralized by means of calcium and sodium hydroxides.
Test No. 16
This test illustrates the invention and implements 0.70% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 2.74, is neutralized by soda and consists of:

    
    
        a) 11.8% acrylic acid and 16% methacrylic acid
        b) 69.2% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
        c) 3% of a monomer of formula (IIb) in which
        
            R represents the vinyl group
            B represents the methyl radical

Test No. 17

        
        
    
    


This test illustrates the invention and implements 0.70% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 2.88, is neutralized by soda and consists of:

    
    
        a) 11.8% acrylic acid and 16% methacrylic acid
        b) 69.2% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
        c) 3% of a monomer of formula (IIb) in which
        
            R represents the methacrylate group
            A represents the propyl chain
            B represents the methyl radical

Test No. 18

        
        
    
    


This test illustrates the invention and implements 0.70% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 3.52, is neutralized by soda and consists of:

    
    
        a) 11.8% acrylic acid and 16% methacrylic acid
        b) 69.2% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
        c) 3% of a monomer of formula (IIb) in which
        
            R represents the methacrylate group
            A represents the propyl chain
            B represents the methyl radical

Test No. 19

        
        
    
    


This test illustrates the invention and implements 0.70% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.99, is neutralized by soda and consists of:

    
    
        a) 11.8% acrylic acid and 16% methacrylic acid
        b) 69.2% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
        c) 3% of a monomer of formula (IIb) in which
        
            R represents the methacrylate group
            A represents the propyl chain
            B represents the methyl radical

Test No. 20

        
        
    
    


This test illustrates the invention and implements 0.70% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 2.74, is neutralized by soda and consists of:

    
    
        a) 11.8% acrylic acid and 16% methacrylic acid
        b) 69.2% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
        c) 3% of 2 perfluoro alkyl ethyl acrylate consisting of a unit containing 21 fluorine atoms and 10 carbon atoms

Test No. 21

    
    


This test illustrates the invention and implements 0.70% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 2.78, is neutralized by soda and consists of:

    
    
        a) 11.8% acrylic acid and 16% methacrylic acid
        b) 68.9% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
         and 3% of a monomer of formula (I) in which
        
            R1 represents the methyl radical
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the buthyl radical
            with (m+n+p)q=32
        
        
        d) 0.3% of ethylene glycol dimethacrylate.

Test No. 22

    
    


This test illustrates the invention and implements 0.70% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 2.80, is neutralized by soda and consists of:

    
    
        a) 11.8% acrylic acid and 16% methacrylic acid
        b) 68.9% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
         and 3% of a monomer of formula (I) in which
        
            R1 represents the methyl radical
            R2 represents hydrogen
            R represents the methacrylamido group
            R′ represents the methyl radical
            with (m+n+p)q=22
        
        
        d) 0.3% of a monomer of formula (III) in which:
        
            R13 represents the propyl methacrylate radical
            R16, R17, R18 and R19 represent the methyl group
            D and E are not present
            m3=n3=p3=m4=n4=p4=0
            r′=14
        
        
    
    


For all the tests 15 to 22, the dry matter content of the suspensions of mineral matter, their pH, their granulometry characterized by the percentage by weight of particles smaller than 1 and 2 μm, their BrookfieldTM viscosities at 10 and 100 rpm (μ10 and μ100) determined at t=0, and then at t=8 days, are determined before and after stirring. Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 15 to 22 are summed up in table IV.






















Brook-
Brook-








field TM
field TM






Brook-
viscosities
viscosities


Tests



field TM
(mPa · s)
(mPa · s)

















Prior

Dry

Grain
viscosities
at t = 8
at t = 8




art/
Composition
Mat.

size
(mPa · s)
days before
days after
Whiteness





















Inven-
of
Cont.

% <
% <
at t = 0
stirring
stirring



W
























No.
tion
polymer
ηspe
(%)
pH
2 μm
1 μm
10
μ100
μ10
μ100
μ10
μ100
R457+UV
R457+UV
Δ UV
(CIE)



























15
Prior art
100% AA
0.64
76.0
9.0
90.1
59.6
390
150
1000
360
310
140
91.1
85.0
6
93


16
Inven-
11.8% AA
2.74
76.5
9.3
79.1
46.1
1930
560
16000
2030
1670
570
94.8
85.4
9.4
107.1



tion
16% AMA




69.2% M




MePEG 5000




3% 




vinyltriethoxy




silane


17
Inven-
11.8% AA
2.88
75.4
9.1
78.3
45.3
810
320
8480
1340
940
380
95.0
85.4
9.6
107.6



tion
16% AMA




69.2% M




MePEG 5000




3% 




3-methacryloxy




propyl




trimethyl




silane


18
Inven-
11.8% AA
3.52
76.1
9.2
75.8
44.1
1890
560
13980
1850
1120
420
94.8
85.2
9.4
107



tion
16% AMA




69.2% M




MePEG 5000




3% 3-




methacryloxypropyl




trimethylsilane


19
Inven-
11.8% AA
1.99
75.3
9.0
81.1
48.3
750
290
8080
1430
1340
430
95
85.6
9.6
107.3



tion
16% AMA




72.2% M




MePEG 5000




3% 3-




methacryloxypropyl




trimethylsilane


20
Inven-
11.8% AA
2.74
76.2
9.3
80.5
47.8
2390
680
14880
1900
1960
610
94.8
85.4
9.4
107.1



tion
16% AMA




69.2% M




MePEG 5000




3% of 




2-ethyl perfluoro




alkyl acrylate





AA designates: acrylic acid


AMA designates: methacrylic acid


M MePEG5000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 5000































Brook-









Brookfield TM
field TM







Brook-
viscosities
viscosities


Tests




field TM
(mPa · s)
(mPa · s)

















Prior

Dry

Grain
viscosities
at t = 8
at t = 8




art/
Composition
Mat.

size
(mPa · s)
days before
days after
Whiteness






















Inven-
of

Cont.

% <
% <
at t = 0
stirring
stirring



W
























No.
tion
polymer
ηspe
(%)
pH
2 μm
1 μm
μ10
μ100
μ10
μ100
μ10
μ100
R457+UV
R457+UV
Δ UV
(CIE)



























21
Inven-
11.8% AA
2.78
76.3
9.2
82.6
49.9
3460
820
15560
2210
4160
1020
93.8
85.4
8.4
104.4



tion
16% AMA




68.9% M




MePEG 5000




3% butoxy




methacrylate




16 OE 16




OP 1700




0.3% ethylene




glycol




dimethacrylate


22
Inven-
11.8% AA
2.80
76.4
9.4
78.6
46.5
1980
570
11520
1840
1760
580
94.5
85.4
9.1
106.5



tion
16% AMA




68.9% M




MePEG 5000




3%




methacrylamido




methoxy




OE 19 OP3




0.3% siloxane




dimethacrylate




with a




molecular




weight of 1100





AA designates: acrylic acid


AMA designates: methacrylic acid


M MePEG5000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 5000


butoxy methacrylate 16 OE 16 OP 1700 designates: the b) monomer of the copolymer according to the invention as described in test 21


methacrylamido methoxy OE 19 OP3 designates: the b) monomer of the copolymer according to the invention as described in test 22


siloxane dimethacrylate with a molecular weight of 1100 designates: the d) monomer of the copolymer according to the invention as described in test 22






Table IV shows that the copolymers according to the invention, used in a mineral filler grinding method make a significant improvement to the optical brightness of the coated papers and to their whiteness, for different monomers c) or d) of the copolymer according to the invention.
Moreover, these results also demonstrate that the copolymers according to the invention make it possible to obtain suspensions of mineral fillers that can be handled after storage without stirring.
EXAMPLE 5
This example relates to the use of copolymers according to the invention in a mineral filler grinding method. It also relates to the use of the suspensions thus obtained in the manufacture of coating colours, said coating colours being used to coat papers. This example also relates to the measurement of the optical brightness and of the whiteness of the papers thus obtained. Finally, the aim of this example is to illustrate the influence of the specific viscosity of the copolymer according to the invention, at constant monomeric composition.
In this example, the first step is to grind suspensions of mineral matter as per the method described for example 2. Their granulometry and their BrookfieldTM viscosity are determined as per the methods described for example 2. Said suspensions then enter into the composition of coating colours formulated as per the method described for example 2. Finally, said coating colours are used to coat paper sheets as per the method described for example 2, with a coating weight equal to 15 g/m2. Said sheets are 21×29.7 cm precoated paper sheets with a specific weight of 96 g/m2. Their whiteness is characterized by the parameters R457+UV, R457−UV, ΔUV and W(CIE) respectively equal to 88.4−85.8−2.6 and 89.5.
For tests 23 to 28, the composition by weight of the copolymer according to the invention is constant and equal to:

    
    
        a) 18.6% acrylic acid and 1.4% methacrylic acid
        b) 80% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 23

        
        
    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 0.77 is neutralized by soda.
Test No. 24
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.00 is neutralized by soda.
Test No. 25
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.40 is neutralized by soda.
Test No. 26
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 2.72 is neutralized by soda.
Test No. 27
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 4.79 is neutralized by soda.
Test No. 28
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 7.85 is neutralized by soda.
The copolymers according to the invention as described in tests 23 to 28 are compared in this example to the polymer of the prior art described in test No. 10 of example 3. For all the tests 23 to 28, the dry matter content of the suspensions of mineral matter, their pH, their granulometry characterized by the percentage by weight of particles smaller than 1 and 2 μm, their BrookfieldTM viscosities at 10 and 100 rpm (μ10 and μ100) determined at t=0, and then at t=8 days, are determined before and after stirring. Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 23 to 28 are summed up in table V.
























Brookfield TM
Brookfield TM








Brook-
viscosities
viscosities







field TM
(mPa · s)
(mPa · s)




Dry


viscosities
at t = 8
at t = 8


Tests
Composition
Mat.

Grain size
(mPa · s)
days before
days after
Whiteness






















Prior art/
of

Cont.

% <
% <
at t = 0
stirring
stirring



W
























No.
Invention
polymer
ηspe
(%)
pH
2 μm
1 μm
μ10
μ100
μ10
μ100
μ10
μ100
R457+UV
R457+UV
Δ UV
(CIE)



























10
Prior art
100% AA
0.64
76.0
9.4
60.2
37
400
140
670
320
330
130
91.4
84.9
6.5
95.7


23
Invention
18.6% AA
0.77
75.5
8.8
47.5
25.5
6380
1220
10800
2090
6680
1320
96.7
84.9
11.8
113.8


24
Invention

1.00
75.0
9.1
59.4
34.4
160
140
1880
600
250
190
96.2
84.8
11.4
112.7


25
Invention
1.4% AMA
1.40
75.2
9.2
65.3
37.9
270
160
1880
580
320
180
96.9
84.9
12
114.9


26
Invention

2.72
75.4
9.4
57.2
30.4
810
310
5200
1150
990
350
96.9
84.8
12.1
115.1


27
Invention
80% M
4.79
54.7
9.2
54.7
28.9
1270
360
8600
1220
990
330
97.3
85.9
11.4
114.7


28
Invention
MePEG5000
7.85
75.5
9.7
52.6
27.4
380
190
4660
970
530
240
97.8
85.8
12
114.9





AA designates: acrylic acid


AMA designates: methacrylic acid


M MePEG5000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 5000






Table V shows that the copolymers according to the invention, used in a mineral filler grinding method, make a significant improvement to the activation of the optical brightness of the coated papers and to their whiteness, for a broad range of specific viscosities ranging from 0.5 to 8.
Moreover, these results also demonstrate that the copolymers according to the invention make it possible to obtain suspensions of mineral fillers that can be handled after storage without stirring.
EXAMPLE 6
This example relates to the use of copolymers according to the invention in a mineral filler grinding method. It also relates to the use of the suspensions thus obtained in the manufacture of coating colours, said coating colours being used to coat papers. This example also relates to the measurement of the optical brightness and of the whiteness of the papers thus obtained. Finally, this example is designed to illustrate the influence of the monomeric composition of a copolymer according to the invention, for a constant rate of methoxy polyethylene glycol methacrylate of molecular weight 5000.
In this example, the first step is to grind suspensions of mineral matter as per the method described for example 2. Their granulometry and their BrookfieldTM viscosity are determined as per the methods described for example 2. Said suspensions then enter into the composition of coating colours formulated as per the method described for example 2. Finally, said coating colours are used to coat paper sheets as per the method described for example 2, with a coating weight equal to 15 g/m2. Said sheets are 21×29.7 cm precoated paper sheets with a specific weight of 96 g/m2. Their whiteness is characterized by the parameters R457+UV, R457−UV, ΔUV and W(CIE) respectively equal to 88.4−85.8−2.6 and 89.5.
Test No. 29
This test illustrates the prior art and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a homopolymer of acrylic acid according to the prior art to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
This homopolymer of acrylic acid has a specific viscosity of 0.64 and is neutralized by means of calcium and sodium hydroxides.
Test No. 30
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.34, is neutralized by soda and consists of:

    
    
        a) 8.6% acrylic acid and 1.4% methacrylic acid
        b) 80% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
        c) 10% of acrylamide

Test No. 31

    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.24 is neutralized by soda and consists of:

    
    
        a) 8.6% acrylic acid, 1.4% methacrylic acid and 10% itaconic acid
        b) 80% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 32

        
        
    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.38, is neutralized by soda and consists of:

    
    
        a) 8.6% acrylic acid, 1.4% methacrylic acid and 10% of ethylene glycol methacrylate phosphate
        b) 80% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 33

        
        
    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.24, is neutralized by soda and consists of:

    
    
        a) 8.6% acrylic acid, 1.4% methacrylic acid and 10% of acrylamidomethylpropane sulfonic acid
        b) 80% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 34

        
        
    
    


This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.92, is neutralized by soda and consists of:

    
    
        a) 20% methacrylic acid
        b) 80% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
    
    


The copolymers according to the invention as described in tests 30 to 33 are compared in this example to the polymer of the prior art described in test No. 10 of example 3. The copolymer according to the invention as described in test No. 34 is compared in this example to the polymer of the prior art described in test No. 29 of this example. In fact, as can be seen in the corresponding table of values, the polymers that made it possible to obtain suspensions of mineral matter of similar granulometry are compared.
For all the tests 30 to 34, the dry matter content of the suspensions of mineral matter, their pH, their granulometry characterized by the percentage by weight of particles smaller than 1 and 2 μm, their BrookfieldTM viscosities at 10 and 100 rpm (μ10 and μ100) determined at t=0, and then at t=8 days, are determined before and after stirring.
Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 30 to 34 are summed up in table VI.
























Brookfield TM
Brookfield TM








Brook-
viscosities
viscosities







field TM
(mPa · s)
(mPa · s)




Dry

Grain
viscosities
at t = 8
at t = 8


Tests
Composition
Mat.

size
(mPa · s)
days before
days after
Whiteness






















Prior art/
of

Cont.

% <
% <
at t = 0
stirring
stirring



W
























No.
Invention
polymer
ηspe
(%)
pH
2 μm
1 μm
μ10
μ100
μ10
μ100
μ10
μ100
R457+UV
R457+UV
Δ UV
(CIE)



























10
Prior art
100% AA
0.64
76.0
9.4
60.2
37
400
140
670
320
330
130
91.4
84.9
6.5
95.7


30
Invention
8.6% AA
1.34
75.4
8.6
62.2
35.9
240
170
2000
720
390
230
97.1
85.1
12
114.9




1.4% AMA




10%




Acrylamide




80% M




MePEG350


31
Invention
8.6% AA
1.24
75.9
9.0
61.6
34
260
150
1320
570
370
180
97.2
84.7
12.5
115.6




1.4% AMA




10% 




Itaconic acid




80% M




MePEG5000


32
Invention
8.6% AA
1.38
75.6
9.0
58.7
31.8
300
170
1480
420
280
170
97.0
84.8
12.2
115.0




1.4% AMA




10% MAEG




Phosphate




80% M




MePEG5000


33
Invention
8.6% AA
1.24
75.4
8.7
58.7
31.6
210
180
1380
610
350
220
97.1
85.1
12
111.5




1.4% AMA




10% AMPS




80% M




MePEG5000


29
Prior art
100% AA
0.64
75.7
9.5
82.8
50.0
450
180
2700
600
410
150
91.0
85.0
6.0
95.2


34
Invention
20% AMA
1.92
75.8
8.9
81.2
48.7
1220
450
12900
2040
2920
780
96.8
85.5
11.3
113.8




80% M




MePEG5000





AA designates: acrylic acid


AMA designates: methacrylic acid


MAEG phosphate designates: ethyleneglycol methacrylate phosphate


AE designates: acrylamido methyl sulfonic propane acid


M MePEG5000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 5000






Table VI shows that the copolymers according to the invention, used in a mineral filler grinding method, make a significant improvement to the activation of the optical brightness of the coated papers and to their whiteness, for a constant rate of methoxypolyethylene glycol methacrylate of molecular weight 5000, for a wide variety of monomeric compositions.
Moreover, these results also demonstrate that the copolymers according to the invention make it possible to obtain suspensions of mineral fillers that can be handled after storage without stirring.
EXAMPLE 7
This example relates to the use of copolymers according to the invention in a mineral filler grinding method. It also relates to the use of the suspensions thus obtained in the manufacture of coating colours, said coating colours being used to coat papers. This example also relates to the measurement of the optical brightness and of the whiteness of the papers thus obtained. Finally, the aim of this example is to illustrate the influence of the rate and of the nature of the neutralization of the copolymer according to the invention, at constant monomeric composition.
In this example, the first step is to grind suspensions of mineral matter as per the method described for example 2. Their granulometry and their BrookfieldTM viscosity are determined as per the methods described for example 2. Said suspensions then enter into the composition of coating colours formulated as per the method described for example 2. Finally, said coating colours are used to coat paper sheets as per the method described for example 2, with a coating weight equal to 15 g/m2. Said sheets are 21×29.7 cm pigmented paper sheets with a specific weight of 76 g/m2. Their whiteness is characterized by the parameters R457+UV, R457−UV, ΔUV and W(CIE) respectively equal to 90.9−83.8−7.1 and 103.6.
For tests 36 to 39 and 41 to 44, the composition of the copolymer according to the invention is fixed, in weight terms, at:

    
    
        a) 11.8% acrylic acid and 16% methacrylic acid
        b) 72.2% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=8

Test No. 35

        
        
    
    


This test illustrates the prior art and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a homopolymer of acrylic acid according to the prior art to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said homopolymer, which has a specific viscosity of 0.64 when it is neutralized by soda, is neutralized by a system consisting of moles of 70% sodium ions and 30% calcium ions for this test.
Test No. 36
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
This copolymer, which has a specific viscosity of 1.08 when it is neutralized by soda, is totally neutralized by the potassium ion for this test.
Test No. 37
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.08 when it is neutralized by soda, is neutralized by a system consisting of moles of 70% sodium ions and 30% calcium ions for this test.
Test No. 38
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said copolymer, which has a specific viscosity of 1.08 when it is neutralized by soda, is neutralized by a system consisting of moles of 50% sodium ions and 50% magnesium ions for this test.
Test No. 39
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
This copolymer, which has a specific viscosity of 1.08 when it is neutralized by soda, is totally neutralized by aminomethylpropanol for this test.
Test No. 40
This test illustrates the prior art and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a homopolymer of acrylic acid according to the prior art to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
Said homopolymer, which has a specific viscosity of 0.64 when it is neutralized by soda, is neutralized by a system consisting of moles of 70% sodium ions and 30% calcium ions for this test.
Test No. 41
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
This copolymer, which has a specific viscosity of 1.08 when it is neutralized by soda, is not neutralized for this test (all its carboxylic functions remain acid).
Test No. 42
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76%.
This copolymer, which has a specific viscosity of 1.08 when it is neutralized by soda, is totally neutralized by triethanolamine for this test.
Test No. 43
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76% by weight.
This copolymer, which has a specific viscosity of 1.08 when it is neutralized by soda, is totally neutralized by the ammonium ion for this test.
Test No. 44
This test illustrates the invention and implements 0.65% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 76% by weight.
This copolymer, which has a specific viscosity of 1.08 when it is neutralized by soda, is totally 50% neutralized by the potassium ion, 50% of its functions remaining acid.
For all the tests 35 to 44, the dry matter content of the suspensions of mineral matter, their pH, their granulometry characterized by the percentage by weight of particles smaller than 1 and 2 μm, their BrookfieldTM viscosities at 10 and 100 rpm (μ10 and μ100) determined at t=0, and then at t=8 days, are determined before and after stirring. Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 35 to 44 are summed up in table VII.



























Brook-










Brookfield TM
field TM


Tests





Brook-
viscosities
viscosities



















Prior






field TM
(mPa · s)
(mPa · s)




art/

Neu-

Dry

Grain
viscosities
at t = 8
at t = 8



In
Composition
tral

Mat.

size
(mPa · s)
days before
days after
Whiteness























ven-
of
iza-

Cont.

% <
% <
at t = 0
stirring
stirring



W

























No.
tion
polymer
tion
ηspe
(%)
pH
2 μm
1 μm
μ10
μ100
μ10
μ100
μ10
μ100
R457+UV
R457+UV
Δ UV
(CIE)




























35
Prior
100%
70%
0.64
75.5
9.5
90.6
60.4
310
120
2690
600
290
130
94.0
85.4
8.536
107.7



art
AA
Na





30%





Ca


36
In-
11.8% AA
100%
1.08
75.9
9.1
78.0
49.4
2330
890
18000
4300
7500
1070
95.6
85.1
10.5
110.7



ven-

K



tion


37
In-
16%
70%
1.08
76.0
8.7
81.9
50
2090
560
10200
1470
1690
580
96.0
85.4
10.6
111.2



ven-
AMA
Na



tion

30%





Ca


38
In-
72.2% M
50%
1.08
76.7
8.9
79.4
47.9
660
280
8440
1340
1220
460
96.0
85.2
10.8
111.9



ven-
MePEG350
Na



tion

50%





Mg


39
In-

100%
1.08
75.8
9.2
76.2
45.6
5500
1350
15000
3240
7800
1850
96.3
85.3
11.0
114.5



ven-

AMP



tion


40
Prior
100% AA
70%
0.64
75.1
9.5
61.6
36.0
330
120
420
220
230
110
95.0
85.9
10.1
111.2



art

Na





30%





Ca


41
In-
11.8% AA
Not
1.08
75.1
7.7
61.7
34.8
1830
410
3480
780
970
280
96.2
84.8
11.4
113.8



ven-

neu-



tion

trali-





zed


42
In-
16% AMA
100%
1.08
75.2
8.3
55.2
31.5
550
220
2900
680
970
290
97.0
84.7
11.3
112.0



ven-

TEA



tion


43
In-
72.2% M
100%
1.08
75.5
8.6
66
38.5
1340
500
5800
1490
3140
780
96.2
85.1
11.1
112.2



ven-

NH4



tion


44
In-
MePEG350
50%
1.08
76.3
8.5
66.7
37.6
670
270
3880
830
660
270
96.3
84.9
11.4
112.7



ven-

K



tion





AA designates: acrylic acid


AMA designates: methacrylic acid


M MePEG350 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 350


AMP designates: aminomethylpropanol


TEA designates: triethanolamine






Table VII shows that the copolymers according to the invention, used in a mineral filler grinding method, make a significant improvement to the activation of the optical brightness of the coated papers and to their whiteness, for a constant monomeric composition and for different rates and natures of the neutralization system envisaged. Moreover, these results also demonstrate that the copolymers according to the invention make it possible to obtain suspensions of mineral fillers that that can be handled after storage without stirring.
EXAMPLE 8
This example relates to the use of copolymers according to the invention in a mineral filler grinding method. It also relates to the use of the suspensions thus obtained in the manufacture of coating colours, said coating colours being used to coat papers. This example also relates to the measurement of the optical brightness and of the whiteness of the papers thus obtained. Finally, the aim of this example is to illustrate the different monomeric compositions of a copolymer according to the invention.
In this example, the first step is to grind suspensions of mineral matter as per the method described for example 2. Their granulometry and their BrookfieldTM viscosity are determined as per the methods described for example 2. Said suspensions then enter into the composition of coating colours made by incorporating, for 100 parts by weight of dry pigment of said ground suspension of calcium carbonate, 10 parts by dry weight of a styrene-butadiene latex marketed by DOW CHEMICAL under the name DL950TM, 0.2 parts of a co-binder marketed by COATEX under the name RheocoatTM 35, and 1 part by weight as is of optical brightener marketed by BAYER under the name Blancophor PTM.
Finally, said coating colours are used to coat paper sheets as per the method described for example 2, with a coating weight equal to 15 g/m2. Said sheets are 21×29.7 cm precoated paper sheets with a specific weight of 96 g/m2.
Test No. 45
This test illustrates the prior art and implements 0.65% by dry weight measured with respect to the dry weight of mineral filler, of a homopolymer of acrylic acid according to the prior art to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 78.2%.
This homopolymer of acrylic acid has a specific viscosity of 0.64 and is neutralized by means of calcium and sodium hydroxides.
Test No. 46
This test illustrates the invention and implements 1.50% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 78.3%.
Said copolymer is neutralized by soda and consists of:

    
    
        a) 13.3% acrylic acid and 3.3% methacrylic acid
        b) 78.4% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            With m=p=0; n=45; q=1 and (m+n+p)q=45
        
        
        c) 5% of vinylpyrrolidone.

Test No. 47

    
    


This test illustrates the invention and implements 1.20% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 78.6%.
Said copolymer is neutralized by soda and consists of:

    
    
        a) 94% acrylic acid and 1% maleic anhydride
        b) 5% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the vinyl group
            R′ represents hydrogen
            With m=p=0; n=113; q=1 and (m+n+p)q=113

Test No. 48

        
        
    
    


This test illustrates the invention and implements 1.50% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 75%.
Said copolymer is neutralized by soda and consists of:

    
    
        a) 94% acrylic acid and 1% maleic anhydride
        b) 2% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the vinyl group
            R′ represents hydrogen
            With m=p=0; n=113; q=1 and (m+n+p)q=113
        
        
        c) 3% of a monomer of formula (IIb) in which:
        
            R represents the methacrylate group
            A represents the propyl chain
            B represents the methyl radical
        
        
    
    


For all the tests 45 to 48, the dry matter content of the suspensions of mineral matter, their pH, their granulometry characterized by the percentage by weight of particles smaller than 1 and 2 μm, their BrookfieldTM viscosities at 10 et 100 rpm (μ10 et μ100) determined at t=0, and then at t=8 days, are determined before and after stirring.
Finally the parameters R457+UV et R457−UV are measured for coated papers according to standards NF Q 03-038 et NF Q 03-039 then the difference ΔUV=R457+UV−R457−UV, is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 45 to 48 are summed up in table VIII.






















Brookfield TM
Brookfield TM








viscosities
viscosities






Brookfield TM
(mPa · s)
(mPa · s)




Dry

viscosities
at t = 8
at t = 8


Tests
Composition
Mat.
Grain
(mPa · s)
days before
days after
















Prior art/
of
Cont.
size
at t = 0 
stirring
stirring
Whiteness






















No
Invention
polymer
(%)
% < 2 μm
% < 1 μm
μ10
μ100
μ10
μ100
μ10
μ100
R457+UV
R457−UV
Δ UV
W(CIE)

























45
Prior Art
100% AA
78.2
89.3
61.2
730
244
7100
1580
1800
610
89.5
85.2
4.3
90.4


46
Invention
13.3% AA
78.3
95.1
66.9
1820
570
18000
3730
2300
720
92.4
85.3
7.1
108.2




3.3% AMA




5% VP




78.4% M




MePEG2000


47
Invention
94% AA
78.6
90.8
62
2150
750
28000
4120
6600
1790
90.6
85.0
5.6
93.4




1% Maleic




anhydrid




5% Vinyl




PEG5000


48
Invention
94% AA
75.0
93.8
62
1950
600
19000
3880
2560
850
90.8
84.9
5.9
92.5




1% Maleic




anhydrid




2% Vinyl




PEG5000




3% formula




(IIb)





AA designates: acrylic acid


AMA designates: methacrylic acid


VP designates: vinyl pyrrolidone


M MePEG2000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 2000






Table VIII shows that the copolymers according to the invention of different monomeric compositions, used in a mineral filler grinding method make a significant improvement to the activation of the optical brightness of the coated papers and to their whiteness.
EXAMPLE 9
This example relates to the use of copolymers according to the invention in a mineral filler manufacturing method. It also relates to the use of the fillers thus obtained in the manufacture of paper. This example also relates to the measurement of the optical brightness and of the whiteness of the papers thus obtained. Finally, this example is designed to illustrate the effectiveness of the copolymers according to the invention in improving the activation of the optical brightness and the whiteness of the papers manufactured.
In the tests corresponding to this example, the first step is to grind a suspension of mineral matter, according to the method described for example 2. The mineral filler is calcium carbonate. For each test, use is made of a constant quantity of grinding agent which is either a copolymer according to the invention, or a grinding agent of the prior art; this quantity is equal to 0.35% by dry weight of copolymer measured with respect to the dry weight of mineral filler. The granulometry of said suspension is determined using a SedigraphTM 5100 grain size analyzer. Its BrookfieldTM viscosity at 10 and 100 rpm (μ10 and μ100) is also measured at t=0, and after 8 days before and after stirring, according to the operating procedure described in example 2.
Following the measurement of BrookfieldTM viscosity at t=0, the filler is used to manufacture a sheet of paper in accordance with the following method.
This gives a pulp which is a mixture of 30% by weight of resinous fibres and 70% by weight of eucalyptus fibres. This pulp is refined in a Valley stack at 30° SR, the refining concentration being 16 g/l. Said pulp is contained in a Franck type former bowl. 1% by weight (with respect to the total dry weight of fibres) of the Blancophor P 01TM optical brightener market by BAYER is incorporated in this pulp. Then 0.6% by weight, with respect to the total dry weight of fibres, of the KeydimeTM C222 glue marketed by EKA CHEMICAL is introduced. Then the filler in the form of an aqueous suspension is added at a rate of 30% by weight with respect to the total weight of fibres. The result is diluted to obtain a sheet with a final grammage of 80 g/m2. A retention system of the cationic/polyacrylamide starch type is also introduced. The cationic starch is Hi-CatTM 5283 marketed by ROQUETTE and the polyacrylamide is PercolTM 178 marketed by CIBA. The quantity of retention agent is adjusted so as to obtain a percentage of residual fillers of 20% by weight in the sheet obtained.
Finally the parameters R457+UV and R457−UV are measured for the manufactured papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
Test No. 49
This test illustrates the prior art and implements 0.35% by dry weight, measured with respect to the dry weight of mineral filler, of a homopolymer of acrylic acid according to the prior art to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 65% by weight.
This homopolymer of acrylic acid has a specific viscosity of 0.64 and is neutralized by means of calcium and sodium hydroxides.
Test No. 50
This test illustrates the invention and implements 0.35% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 65% by weight.
Said copolymer, which has a specific viscosity of 1.10, is neutralized by soda and consists of:

    
    
        a) 14.1% acrylic acid and 3.4% methacrylic acid
        b) 82.5% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=45

Test No. 51

        
        
    
    


This test illustrates the invention and implements 0.35% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 65% by weight.
Said copolymer, which has a specific viscosity of 1.49, is neutralized by soda and consists of:

    
    
        a) 13.7% acrylic acid and 3.3% methacrylic acid
        b) 83% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 52

        
        
    
    


This test illustrates the invention and implements 0.35% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 65% by weight.
Said copolymer, which has a specific viscosity of 1.27, is neutralized by soda and consists of:

    
    
        a) 8.5% acrylic acid and 1.5% methacrylic acid
        b) 90% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 53

        
        
    
    


This test illustrates the invention and implements 0.35% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to grind a suspension of calcium carbonate. The suspension of calcium carbonate contains, before grinding, 20% by weight of particles with a diameter of less than 2 μm determined using a SedigraphTM 5100 grain size analyzer, and has a dry matter content of 65% by weight.
Said copolymer, which has a specific viscosity of 1.56, is neutralized by soda and consists of:

    
    
        a) 8.5% acrylic acid and 1.5% methacrylic acid
        b) 90% of a monomer of formula (D) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
    
    


For all the tests 9 to 53, the granulometry of the ground suspensions of mineral filler, identified by the percentage by weight of particles smaller than 1 and 2 μm, their BrookfieldTM viscosities at 10 and 100 rpm (μ10 and μ100) determined at t=0, and then at t=8 days, are determined before and after stirring.
Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CEE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 49 to 53 are summed up in table IX.





















Brookfield TM
Brookfield TM







Brookfield TM
viscosities
viscosities





viscosities
(mPa · s)
(mPa · s)


Tests
Composition
Grain
(mPa · s)
at t = 8 days
at t = 8 days
Optical

















Prior art/
of

size
at t = 0
before stirring
after stirring
brightener
Whiteness




















No.
Invention
polymer
ηspe
% < 2 μm
% < 1 μm
μ10
μ100
μ10
μ100
μ10
μ100
Δ UV
W (CIE)






















49
Prior art
100% AA
0.64
59.0
29.1
120
110
sedimentation
130
110
8.0
98.5




















50
Invention
14.1% AA
1.10
58.4
28.3
450
110
1380
220
540
120
8.6
102.0




3.4% AMA




82.5% M MePEG2000


51
Invention
13.7% AA
1.49
59.0
28.5
4440
580
4640
620
3250
490
8.8
101.8




3.3% AMA




83% M MePEG5000


52
Invention
8.5% AA
1.27
59.1
29.5
1160
230
1560
280
480
160
8.5
99.8




1.5% AMA




90% M MePEG5000


53
Invention
8.5% AA
1.56
59.4
29.3
2500
490
2880
430
1620
340
8.4
99.5




1.5% AMA




90% M MePEG5000





AA designates: acrylic acid


AMA designates: methacrylic acid


M MePEG2000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 2000


M MePEG5000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 5000






Table IX shows that the copolymers according to the invention, used in a filler manufacturing method, make a significant improvement to the activation of optical brightness of manufactured papers and their whiteness.
Moreover, these results also demonstrate that the copolymers according to the invention make it possible to obtain suspensions of mineral fillers that can be handled after storage without stirring.
EXAMPLE 10
This example relates to the use of copolymers according to the invention as additives in a coating colour manufacturing method. It also relates to the use of the coating colours thus obtained in the manufacture of coated paper. This example also relates to the measurement of the optical brightness and of the whiteness of the coated papers thus obtained. Finally, this example is designed to illustrate the effectiveness of the copolymers according to the invention in improving the activation of the optical brightness and the whiteness of the coated papers.
In the tests corresponding to this example, the first step is to mix, in accordance with methods with which the skilled man in the art is familiar, a suspension of calcium carbonate marketed by OMYA under the name SetacarbTM, and a suspension of kaolin marketed by HUBER under the name HydraglossTM 90. The mix is then made by incorporating, for 100 parts by weight of dry pigment, 10 parts by dry weight of a styrene-butadiene latex marketed by DOW CHEMICAL under the name DL950TM and 1 part by weight as is of the optical brightener Blancophor PTM marketed by BAYER. Then, possibly, 1 half part by dry weight of an optical brightness support known to the skilled man in the art, i.e. polyvinyl alcohol marketed under the name MowiolTM 4-98 by CLARIANT, is added. A copolymer according to the invention in proportions which will be specified for each of the tests may or may not be added.
These mixes are then used to coat paper sheets according to the method described in example 2, with a coating weight equal to 15 g/m2. Said sheets are 21×29.7 cm pigmented paper sheets with a specific weight of 76 g/m2. Their whiteness is characterized by the parameters R457+UV, R457−UV, ΔUV and W(CIE) respectively equal to 90.9-83.8-7.1 and 103.6.
Test No. 54
This test illustrates the prior art and implements, for the production of the mix, the above-mentioned mixture of mineral fillers, the above-mentioned latex and the above-mentioned optical brightener, in the proportions defined at the beginning of example 9.
Test No. 55
This test illustrates the invention and implements, for the production of the mix, the above-mentioned mixture of mineral fillers, the above-mentioned latex and the above-mentioned optical brightener, in the proportions defined at the beginning of example 9. It also implements, in the formulation of the mix, 1.5 parts by dry weight of a copolymer according to the invention.
Said copolymer, which has a specific viscosity of 14.2, is neutralized by soda and consists of:

    
    
        a) 13.6% acrylic acid and 3.4% methacrylic acid
        b) 83% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=45

Test No. 56

        
        
    
    


This test illustrates the invention and implements, for the production of the coating colour, the above-mentioned mixture of mineral fillers, the above-mentioned latex and the above-mentioned optical brightener, in the proportions defined at the beginning of example 9.
It also implements, in the formulation of the coating colour, 1 part by dry weight of a copolymer according to the invention.
Said copolymer, which has a specific viscosity of 4.83, is neutralized by soda and consists of:

    
    
        a) 13.6% acrylic acid and 3.4% methacrylic acid
        b) 83% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=45

Test No. 57

        
        
    
    


This test illustrates the prior art and implements, for the production of the coating colour, the above-mentioned mixture of mineral fillers, the above-mentioned latex and the above-mentioned optical brightener, in the proportions defined at the beginning of example 9.
It also implements 0.5 parts by dry weight of polyvinyl alcohol as optical brightness support.
Test No. 58
This test illustrates the invention and implements, for the production of the coating colour, the above-mentioned mixture of mineral fillers, the above-mentioned latex and the above-mentioned optical brightener, in the proportions defined at the beginning of example 9.
It also implements, in the formulation of the mix, 0.5 parts by dry weight of polyvinyl alcohol as optical brightness medium, and 0.9 parts by dry weight of a copolymer according to the invention.
Said copolymer, which has a specific viscosity of 14.2, is neutralized by soda and consists of:

    
    
        a) 13.6% acrylic acid and 3.4% methacrylic acid
        b) 83% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=45

Test No. 59

        
        
    
    


This test illustrates the invention and implements, for the production of the coating colour, the above-mentioned mixture of mineral fillers, the above-mentioned latex and the above-mentioned optical brightener, in the proportions defined at the beginning of example 9.
It also implements, in the formulation of the mix, 0.5 parts by dry weight of polyvinyl alcohol as optical brightness medium, and 1 part by dry weight of a copolymer according to the invention.
Said copolymer, which has a specific viscosity of 4.83, is neutralized by soda and consists of:

    
    
        a) 13.6% acrylic acid and 3.4% methacrylic acid
        b) 83% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=45
        
        
    
    


For tests 54 to 59, the viscosity of the coating colours obtained at t=0 are determined at 10 and 100 rpm (μ10 and μ100).
Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
The water retention value is also determined for each coating colour, in accordance with the method described in EP 1 001 083.
The coating colour is subjected to a pressure of 7 bar in a standardized cylinder, and fitted with a filter paper type surface capable of letting the water through. The volume of filtrate of mix collected after 20 minutes (V20 min in milliliters) and the time from which the first drop crosses the filter paper (t1st drop in minutes) are then determined. The retention is better the lower the value of V20 min and the higher the value of t1st drop.
All the results corresponding to tests No. 54 to 59 are summed up in table X.













Tests














Formulation of
Chemical
Prior art
Invention
Invention
Prior art
Invention
Invention


mix
compounds
54
55
56
57
58
59

















Fillers
Setacarb TM
80
80
80
80
80
80



Hydragloss TM 90
20
20
20
20
20
20


Latex
DL950 TM
10
10
10
10
10
10


Optical brightener
Blancophor P TM
1
1
1
1
1
1


Optical brightener
PVA 4-98 TM
0
0
0
0.5
0.5
0.5


medium


Polymer
13.6% AA
0
1.5
0
0
0.9
0


according to
3.4% AMA


invention
83% M MePEG2000



(ηspe = 14.2)



13.6% AA
0
0
1.0
0
0
1.0



3.4% AMA



83% M MePEG2000



(ηspe = 4.83)


Properties
pH
8.6
8.6
8.6
8.6
8.6
8.6


of
Dry Mat.Cont. (%)
67.3
66.8
66.8
66.7
66.9
66.9


mix
μ10 mPa · s
2920
8700
11380
1780
6160
8040



μ100 mPa · s
550
1610
1880
430
1390
1620



V20 min (ml)
6.4
2.3
2.7
3.3
1.5
1.3



t1st drop (min)
1′26
3′25
2′05
2′01
5′00
4′54


Whiteness
R457+UV
92.8
95.4
95.1
96.7
98.2
98.1


of
R457+UV
85.0
84.9
84.9
84.7
84.6
84.6


coated
ΔUV
7.8
10.5
10.2
12.0
13.6
13.5


paper
W (CIE)
103.3
112.2
111.2
115.1
121.7
121.8





AA designates: acrylic acid


AMA designates: methacrylic acid


M MePEG2000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 2000






Table X shows that, independently of the presence of polyvinyl alcohol as optical brightness agent, the copolymers according to the invention make a significant improvement to the activation of optical brightness for coated papers, and an improvement in their whiteness.
It is also noted that the use of a copolymer according to the invention makes a significant improvement to the water retention of the coating colour.
Furthermore, it is noted that the BrookfieldTM viscosities of the coating colours obtained according to the invention are compatible with the normal industrial application.
EXAMPLE 11
This example relates to the use of copolymers according to the invention as additives in the manufacture of suspensions of previously dispersed and/or ground mineral matter. It also relates to the use of the suspensions thus obtained in the manufacture of coating colour, said coating colour being used to coat papers. This example also relates to the measurement of the optical brightness and whiteness of the papers thus obtained. Finally, this example is designed to illustrate the effectiveness of the copolymers according to the invention in improving the activation of the optical brightness and the whiteness of the coated papers.
In the tests corresponding to this example, use is made of a suspension of calcium carbonate marketed under the name HydrocarbTM 90 by OMYA.
The next step then is to incorporate a copolymer according to the invention in these suspensions, in a proportion of 1% by dry weight, measured with respect to the dry weight of mineral fillers.
Said suspensions then enter into the composition of the coating colours.
The coating colour is prepared by incorporating, for 100 parts by weight of dry pigment, 10 parts by dry weight of styrene-butadiene latex marketed by DOW CHEMICAL under the name DL920TM, and 1 part by weight as is of optical brightener marketed by BAYER under the name Blancophor PTM.
These coating colours are then used to coat paper sheets according to the method described in example 2, with a coating weight equal to 15 g/m2. Said sheets are 21×29.7 cm precoated paper sheets with a specific weight of 96 g/m2. Their whiteness is characterized by the parameters R457+UV, R457−UV, ΔUV and W(CEE) respectively equal to 88.4−85.8−2.6 and 89.5.
Their viscosity is determined according to the same method as that applied to the aqueous suspensions of mineral matter.
The paper sheets are coated as per the method described in example 2.
Test No. 60
This test illustrates the prior art and implements, in the manufacture of the coating colour the Hydrocarb 90TM calcium carbonate suspension.
Test No. 61
This test illustrates the invention and implements 1% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention as additive in the Hydrocarb 90TM calcium carbonate suspension.
Said copolymer, which has a specific viscosity of 1.52, is neutralized by soda and consists of:

    
    
        a) 8.5% acrylic acid and 1.5% methacrylic acid
        b) 90% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113

Test No. 62

        
        
    
    


This test illustrates the prior art and implements the Hydrocarb 90TM calcium carbonate suspension in the manufacture of the coating colour. It also implements, in the manufacture of the coating colour, 1 part (for 100 parts by weight of dry pigment) by dry weight of an optical brightness carrier of the prior art, i.e. polyvinylpyrrolidone marketed by BASF under the name K30TM.
Test No. 63
This test illustrates the invention and implements 1% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention to as additive in the Hydrocarb 90TM calcium carbonate suspension.
Said copolymer, which has a specific viscosity of 1.52, is neutralized by soda and consists of:

    
    
        a) 8.5% acrylic acid and 1.5% methacrylic acid
        b) 90% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
    
    


It also implements, in the manufacture of the coating colour, 1 part (for 100 parts by weight of dry pigment) by dry weight of an optical brightness carrier of the prior art, i.e. polyvinylpyrrolidone marketed by BASF under the name K30TM.
Test No. 64
This test illustrates the prior art and implements the Hydrocarb 90TM calcium carbonate suspension in the manufacture of the coating colour. It also implements, in the manufacture of the coating colour, 1 part (for 100 parts by weight of dry pigment) by dry weight of an optical brightness carrier of the prior art, i.e. methoxypolyethylene glycol of molecular weight 5000.
Test No. 65
This test illustrates the invention and implements 1% by dry weight, measured with respect to the dry weight of mineral filler, of a copolymer according to the invention as additive in the Hydrocarb 90TM calcium carbonate suspension.
Said copolymer, which has a specific viscosity of 1.52, is neutralized by soda and consists of:

    
    
        a) 8.5% acrylic acid and 1.5% methacrylic acid
        b) 90% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            with (m+n+p)q=113
        
        
    
    


It also implements, in the manufacture of the coating colour, 1 part (for 100 parts by weight of dry pigment) by dry weight of an optical brightness carrier of the prior art, i.e. methoxypolyethylene glycol of molecular weight 5000.
For tests 60 to 65, the viscosity of the mixes obtained at t=0 are determined at 10 and 100 rpm (μ10 and μ100).
Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 60 to 65 are summed up in table XI.













Tests














Prior art
Invention
Prior art
Invention
Prior art
Invention



60
61
62
63
64
65



















Formulation
Suspension
Hydragloss TM 90
100
100
100
100
100
100


of
of


coating
filler


mix
Latex
DL920 TM
10
10
10
10
10
10



Optical
Blancophor P TM
1
1
1
1
1
1



brightener



Copolymer
8.5% AA
0
1
0
1
0
1



according to
1.5% AMA



invention
90% M




MePEG5000



Other
K30 TM
0
0
1
1
0
0



additive
M MePEG5000:
0
0
0
0
1
1














Properties
pHpH
8.6
8.7
8.6
8.7
8.6
8.9


of
Dry Mat.Cont.
67.1
67.0
67.1
67.0
66.9
67.0


mix
(%)



μ10 mPa · s
640
650
750
2650
650
1750



μ100 mPa · s
180
230
200
550
310
360


Properties
R457+UV
90.8
95.5
96.6
98.3
95.3
96.3


of
R457−UV
85.3
85.6
85.2
85.5
85.5
85.5


coated
ΔUV
5.5
9.9
11.4
12.7
9.8
10.7


paper
W (CIE)
92.6
110.7
114.7
119.8
110.0
114.2





AA designates: acrylic acid


AMA designates: methacrylic acid


M MePEG5000 designates: methoxypolyethylene glycol methacrylate with a molecular weight of 5000






Table XI shows that the introduction as additive in the suspension of mineral matter of a copolymer according to the invention significantly improves the activation of the optical brightness of the end product and its whiteness.
Furthermore, it is noted that the BrookfieldTM viscosities of the coating colours obtained according to the invention are compatible with the normal industrial application.
EXAMPLE 12
This example relates to the use of copolymers according to the invention as additives in a coating colour manufacturing method and more precisely as co-binder. This example also relates to the measurement of the optical brightness and of the whiteness of the coated papers thus obtained. Finally, this example is designed to illustrate the effectiveness of the copolymers according to the invention in improving the activation of the optical brightness and the whiteness of the coated papers.
In the tests corresponding to this example, use is made of a suspension of calcium carbonate marketed under the name HydrocarbTM 90 by OMYA which enter into the composition of the coating colours.
The coating colour is prepared by incorporating for 100 parts by weight of dry pigment, 10 parts by dry weight of styrene-butadiene latex marketed by DOW CHEMICAL under the name DL950TM, the quantity of co-binder to be tested and 1 part by weight as is of optical brightener marketed by BAYER under the name Blancophor PTM.
Said coating colours are then used to coat paper sheets according to the method described in example 2, with a coating weight equal to 15 g/m2. Said sheets are 21×29.7 cm precoated paper sheets with a specific weight of 96 g/m2.
Their viscosity is determined according to the same method as that applied to the aqueous suspensions of mineral matter.
The paper sheets are coated as per the method described in example 2.
Test No. 66
This test illustrates the prior art and implements in the manufacture of the coating colour, 0.2 parts of a co-binder of the prior art marketed by COATEX under the name RheocoatTM 35.
Test No. 67
This test illustrates the invention and implements in the manufacture of the coating colour, 0.2 parts of a copolymer according to the invention as additive co-binder.
Said copolymer is neutralized by soda and consists of:

    
    
        a) 5.9% acrylic acid and 1.6% methacrylic acid
        b) 92.5% of a monomer of formula (I) in which:
        
            R1 represents hydrogen
            R2 represents hydrogen
            R represents the methacrylate group
            R′ represents the methyl radical
            With m=p=0; n=113; q=1 and (m+n+p)q=113.

Test No. 68

        
        
    
    


This test illustrates the invention and implements as additive co-binder in the manufacture of the coating colour, 0.8 parts of the same copolymer according to the invention as the one implemented in the test No. 67.
Test No. 69
This test illustrates the invention and implements as additive co-binder in the manufacture of the coating colour, 3 parts of the same copolymer according to the invention as the one implemented in the test No. 67.
Test No. 70
This test illustrates the invention and implements as additive co-binder in the manufacture of the coating colour, 4 parts of the same copolymer according to the invention as that implemented in test No. 67.
For tests 66 to 70, the viscosity of the coating colours obtained at t=0 are determined at 10 and 100 rpm (μ10 and μ100).
Finally the parameters R457+UV and R457−UV are measured for coated papers according to standards NF Q 03-038 and NF Q 03-039, then the difference ΔUV=R457+UV−R457−UV is calculated, and the W(CIE) parameter is also measured according to standard ISO/FDIS 11475.
All the results corresponding to tests No. 66 to 70 are summed up in table XII.
















Formulation of

Prior Art
Invention
Invention
Invention
Invention


coating colour
Chemical compounds
66
67
68
69
70





















Fillers
Hydrocarb TM 90
100
100
100
100
100


Latex
DL950 TM
10
10
10
10
10


Optical brightener
Blancophor P TM
1
1
1
1
1


Co-binder
Rheocoat TM35
0.2
0
0
0
0



Polymer according to
0
0.2
0.8
3.0
4.0



invention


Properties of
pH
8.5
8.5
8.5
8.6
8.6


coating colour
Dry Mat. Cont. (%)
66.8
67.0
67.0
67.0
65.0



μ10 mPa · s
25200
8030
16000
34600
43200



μ100 mPa · s
3700
1470
2510
6430
6300


Whiteness of
R457+UV
89.7
91.3
91.5
92.2
92.5


coated paper
R457−UV
85.5
85.3
85.2
85.1
85.3



ΔUV
4.2
6.0
6.3
7.1
7.2



W(CIE)
88.6
94.2
97.2
101.3
101.1









Table XII shows that the use of copolymers according to the invention as additives in the coating colour makes a significant improvement to the activation of the optical brightness and the whiteness of the coated papers.

## Claims

1. An agent for improving the activation of optical brightness, comprising a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer.

2. The agent for improving the activation of optical brightness according to claim 1, wherein the agent is a water-soluble copolymer consisting of at least one monomer of formula (I):



wherein
m and p represent a number of alkylene oxide units less than or equal to 150,
n represents a number of ethylene oxide units less than or equal to 150,
q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150,
R1 represents hydrogen or the methyl or ethyl radical,
R2 represents hydrogen or the methyl or ethyl radical,
R represents a radical comprising a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides, and
R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms.

3. The agent for improving the activation of optical brightness according to claim 1, wherein said agent is a water-soluble copolymer consisting of:
a) at least one anionic monomer with a carboxylic or dicarboxylic or phosphoric or phosphonic or sulfonic function or a mixture thereof,
b) at least one non-ionic monomer, the non-ionic monomer consisting of at least one monomer of formula (I):




wherein
m and p represent a number of alkylene oxide units less than or equal to 150,
n represents a number of ethylene oxide units less than or equal to 150,
q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150,
R1 represents hydrogen or the methyl or ethyl radical,
R2 represents hydrogen or the methyl or ethyl radical,
R represents a radical comprising a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides, and
R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms,

or a mixture of several monomers of formula (I),
c) optionally, at least one monomer of the acrylamide or methacrylamide type or their derivatives and mixtures thereof, at least one non water-soluble monomer and their derivatives, at least one cationic monomer or quaternary ammonium at least one organofluorinated or organosilylated monomer, or a mixture of several of these monomers, and
d) optionally, at least one monomer having at least two ethylenic insaturations referred to as a crosslinking monomer,
the total of the proportions of components a), b), c) and d) being equal to 100%.

4. The agent improving the activation of optical brightness according to claim 3, wherein the organosilylated monomer is selected from the group consisting of molecules of formulae (IIa) and (IIb),
with formula (IIa)




wherein
m1, p1, m2 and p2 represent a number of alkylene oxide units less than or equal to 150,
n1 and n2 represent a number of ethylene oxide units less than or equal to 150,
q1 and q2 represent an integer equal to at least 1 and such that 0≦(m1+n1+p1)q1≦150 and 0≦(m2+n2+p2)q2≦150,
r represents a number such that 1≦r≦200,
R3 represents a radical comprising a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
R4, R5, R10 and R11 represent hydrogen or the methyl or ethyl radical,
R6, R7, R8 and R9 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof,
R12 represents a hydrocarbon radical having from 1 to 40 carbon atoms, and
A and B are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,

with formula (IIb)


R—A—Si(OB)3 


wherein
R represents a radical comprising a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
A is a group which may be present, in which case it represents a hydrocarbon radical having from 1 to 4 carbon atoms,
B represents a hydrocarbon radical having from 1 to 4 carbon atoms,

or a mixture of several of said monomers,
and wherein the crosslinking monomer is selected from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, the allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, and allyl ethers prepared from polyols, or selected from the group consisting of molecules of formula (III):




wherein
m3, p3, m4 and p4 represent a number of alkylene oxide units less than or equal to 150,
n3 and n4 represent a number of ethylene oxide units less than or equal to 150
q3 and q4 represent an integer equal to at least 1 and such that 0≦(m3+n3+p3)q3≦150 and 0≦(m4+n4+p4)q4≦150,
r′ represents a number such that 1≦r′≦200,
R13 represents a radical comprising a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
R14, R15, R20 and R21 represent hydrogen or the methyl or ethyl radical,
R16, R17, R18 and R19 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof, and
D and E are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms, or a mixture of several of said monomers.

5. The agent for improving the activation of optical brightness according to claim 1, wherein the agent is a water-soluble copolymer consisting, by weight, of:
a) from 2% to 95% of at least one ethylenically unsaturated anionic monomer having a monocarboxylic function selected from the group consisting of ethylenically unsaturated monomers having a monocarboxylic function, ethylenically unsaturated monomers having a dicarboxylic function, ethylenically unsaturated monomers having a sulfonic function, ethylenically unsaturated monomers having a phosphoric function, ethylenically unsaturated monomers having a phosphonic function and mixtures thereof,
b) from 2 to 95% of at least one non-ionic ethylenically unsaturated monomer of formula (I):




wherein
m and p represent a number of alkylene oxide units less than or equal to 150,
n represents a number of ethylene oxide units less than or equal to 150,
q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150,
R1 represents hydrogen or the methyl or ethyl radical,
R2 represents hydrogen or the methyl or ethyl radical,
R represents a radical comprising a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides, and
R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms,

or a mixture of several monomers of formula (I),
c) from 0% to 5% of at least one monomer of the acrylamide or methacrylamide type or their derivatives and mixtures thereof, at least one non water-soluble monomer, unsaturated esters, vinyls and their derivatives, at least one cationic monomer or quaternary ammonium, at least one organofluorinated monomer, or at least one organosilylated monomer selected from the group consisting of molecules of formulae (IIa) and (IIb),

with formula (IIa)




wherein
m1, p1, m2 and p2 represent a number of alkylene oxide units less than or equal to 150,
n1 and n2 represent a number of ethylene oxide units less than or equal to 150,
q1 and q2 represent an integer equal to at least 1 and such that 0≦(m1+n1+p1)q1≦150 and 0≦(m2+n2+p2)q2≦150,
r represents a number such that 1≦r≦200,
—R3 represents a radical comprising a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
R4, R5, R10 and R11 represent hydrogen or the methyl or ethyl radical,
R6, R7, R8 and R9 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof,
R12 represents a hydrocarbon radical having from 1 to 40 carbon atoms, and
A and B are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms,


with formula (IIb)


R—A—Si(OB)3 

wherein
R represents a radical comprising a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
A is a group which may be present, in which case it represents a hydrocarbon radical having from 1 to 4 carbon atoms, and
B represents a hydrocarbon radical having from 1 to 4 carbon atoms, or a mixture of several of said monomers,

d) from 0% to 3% of at least one crosslinking monomer selected from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, the allyl maleates, methylene-bis-acrylamide, methylene-bis methacrylamide, tetrallyloxyethane, triallylcyanurates, and allyl ethers prepared from polyols, or selected from the group consisting of molecules of formula (III):




wherein
m3, p3, m4 and p4 represent a number of alkylene oxide units less than or equal to 150,
n3 and n4 represent a number of ethylene oxide units less than or equal to 150,
q3 and q4 represent an integer equal to at least 1 and such that 0≦(m3+n3+p3)q3≦150 and 0≦(m4+n4+p4)q4≦150,
r′ represents a number such that 1≦r′≦200,
R13 represents a radical comprising a polymerizable unsaturated function, belonging to the vinyl group and to the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphtalic esters and to the group of urethane unsaturates, and to the group of allyl or vinyl ethers, whether or not substituted, or to the group of ethylenically unsaturated amides or imides,
R14, R15, R20 and R21 represent hydrogen or the methyl or ethyl radical,
R16, R17, R18 and R19 represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof, and
D and E are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms

or a mixture of several of said monomers,
the total of the proportions of components a), b), c) and d) being equal to 100%.

6. The agent for improving the activation of optical brightness according to claim 1, wherein the agent is a copolymer in acid form or fully or partially neutralized by one or more neutralization agents having a monovalent neutralizing function or a polyvalent neutralizing function.