Lubricating insolubiliser for paper coating compositions

Abstract: Paper coating compositions contain at least one pigment, at least one binder, and as an insolubiliser for the binder, the product of reacting glyoxal with a polyhydroxyl substituted ester of a fatty acid and then with a polyol.

Description: This invention relates to glyoxal reaction products and primarily to paper coating compositions containing them. More particularly it relates to the preparation of novel products for use as insolubilisers for the binders in coatings for paper. Paper coating compositions are generally a fluid suspension of pigments, such as clay with or without titanium dioxide and/or calcium carbonate, or the like, in an aqueous medium which includes a binder such as starch, modified starch, styrene-butadiene copolymer, acrylic polymer, or protein to adhere the pigment to paper. The hydrophilic nature of the binder requires the presence of an insolubilising material which crosslinks the binder, making it hydrophobic and thus improving the characterisitics of the surface of the coated paper. The most widely-used crosslinking materials are glyoxal, blocked glyoxal resins and formaldehyde-donor agents such as melamineformaldehyde, urea-melamineformaldehyde, and partially or wholly methylated derivatives thereof. Glyoxal is a highly reactive monomer which cures quickly and has excellent insolubilising properties. As a result of this rapid crosslinking of glyoxal and binder, however, the viscosity of the coating composition increases so rapidly and is so great that the composition cannot be used. Frequently glyoxal-insolubilised coatings gel completely, particularly in high solids formulations; gelling can occur also in moderate or low solids formulations if they are not used promptly. Thus in situations where it is required that viscosity remain stable for many hours, for example when high-solids coatings are to be applied by blade coating techniques, a glyoxal system is unsuitable. Melamineformaldehyde resins do not build viscosity in the coating compositions, but they have the disadvantage of having an unpleasant odor and of releasing free formaldehyde. Curing with such resins involves the crosslinking of the binder molecule with the methylol or methylated methylol group of the melamine resin, usually in an acid or neutral coating, and full insolubilisation of the binder takes place slowly over a period of several days. Free formaldehyde can be released either directly from the coating mixture or when the coating is cured on the drying machine. The presence of even less than one percent of free formaldehyde, based on the total weight of the product, is undesirable, not only because of its objectionable odor, but because it is an allergen and an irritant, causing severe reactions in the operators who manufacture the coatings and who treat and handle the coated paper. The use of the reaction product of urea and glyoxal as an insolubiliser is disclosed in US-A-3,869,296. Treating agents formed by the reaction of ethylene urea with glyoxal are disclosed in JP-A-5 3044-567, but they too do not have satisfactory properties. US-A-4,343,655 teaches the use of the alkylated products of the reaction of glyoxal and cyclic ureas as crosslinking resins for binders for paper coating compositions. The use of the reaction products of glyoxal and polyol are disclosed in US-A-4,656,296 and US-A-4537634. A reaction product according to the invention is obtainable by reacting glyoxal with a polyhydroxyl substituted ester of a fatty acid and then with a polyol containing two or more hydroxyl groups according to claim 1. The present invention further relates to the use of the reaction product as defined in claim 8 and to an insolubiliser composition as defined in claim 3 and to a paper coating composition as defined in claim 5. Such reaction products are excellent crosslinking resins for binders for paper coating compositions. They do not build viscosity as does glyoxal; they do not contain or evolve free formaldehyde; in smaller amounts, they have insolubilising effects similar to those of the previously known agents; they provide lubrication in addition to insolubilising the binder; and they provide a high gloss finish to the paper. In general, 20 to 60% by weight of glyoxal is reacted with 30 to 70% by weight of polyhydroxyl substituted ester and then with 5 to 25% by weight of polyol. The ester is selected from the group consisting of sorbitan monolaurate, sorbitan mono-oleate, sorbitan monostearate, sorbitan monopalmitate, glycerol monostearate, glycerol monopalminate, glycerol myristate, trimethylol ethane monostearate, trimethylol ethane monopalminate, trimethylol ethane monomyristate, trimethylol propane monostearate, trimethylol propane monopalminate, trimethylol propane monomyristate, pentaerythritolmonostearate, pentaerythritolmonopalminate and pentaerythritol monomyristate and their mixtures. The polyol, with which the reaction product of glyoxal and polyhydroxyl substituted ester is then reacted, contains two or more hydroxyl groups and is selected from ethylene glycol, glycerine, sorbitol, propylene glycol or trimethylol propane and mixtures thereof. This reaction is to provide stability to the system in emulsion form and as a paper coating. The reaction of the glyoxal, with the polyhydroxyl substituted ester and then the polyol generally takes place at a temperature between room temperature and reflux, and preferably at about 70° to 90°C. The reaction time is generally about 1 hour to 8 hours, and preferably it is about 4 hours. Vacuum may be applied to remove water until the desired solids content is attained. In general about 5.1 x 10³ to 8.1 x 10³ Pa (15 to 24'' Hg) of vacuum is applied at a temperature necessary to distill water. The pH of the reaction mixture must be less than 8, and preferably it is between about 3 and 6. If it is necessary to raise the pH, a reagent such as sodium bicarbonate can be used. A composition containing the reaction product for use as an insolubiliser preferably contains a surfactant. Such a composition preferably contains 10 to 50% by weight of the reaction product, 1 to 15% by weight of a surfactant and 35 to 90% by weight of water. Preferably the surfactant is a non-ionic surfactant such as a nonylphenol-ethylene oxide adduct (1 to 40 moles), a octylphenol-ethylene oxide adduct (1 to 40 moles), a lauryl alcohol-ethylene oxide adduct (4 to 23 moles), a stearyl alcohol-ethylene oxide adduct (20 to 25 moles), a tridecyl alcohol-ethylene oxide adduct (5 to 18 moles), a sorbitan mono-oleate-ethylene oxide adduct (5 to 20 moles) or a sorbitan monostearate-ethylene oxide adduct (3 to 10 moles). The binders used in the paper coating composition of this invention include, but are not limited to: unmodified starch; oxidised statch; starches having functional groups such as hydroxyl, carbonyl, amido, and amino groups; proteins, such as casein; latexes, such as styrene-butadiene copolymer; and the like, and their mixtures. The pigments may be clay with or without titanium dioxide and/or calcium carbonate, and the like, and mixtures thereof. In addition to the binder, the pigment material, and the insolubiliser described above, paper compositions may also include conventional materials such as lubricants, defoamers, preservatives, colored pigments, and the like, in conventional amounts. In the paper coating compositions described herein the amount of binder is based upon the amount of pigment; the ratio varies with the amount of bonding desired and with the adhesive characteristics of the particular binder employed. In general, the amount of binder is about 4 to 25 percent, and preferably about 10 to 20 percent, based on the weight of the pigment. The amount of insolubiliser varies with the amount and properties of the binder and the amount of insolubilisation desired; in general it is about 1 to 12 percent, and preferably about 4 to 8 percent, based on the weight of the binder. The total solids content of the paper coating compositions generally is within the range of about 50 to 70 percent, depending upon the method of application and the product requirements. The paper coating compositions of this invention can be applied to paper or paper-like substrates by any known and convenient means. It is believed that the novel compounds of this invention function by breaking down, during cure conditions and not before, into the polyol, polyhydroxyl substituted ester and glyoxal, the glyoxal then reacting with the binder. Thus, for example, when decomposed in the presence of starch, the breakdown product glyoxal reacts with the starch. Because of their monomeric nature, these new compounds can be dispersed more easily and more uniformly, giving better printing properties on the paper. Although this invention is described in relation to insolubilisers for binders for paper coating compositions, it is not intended to be limited thereto. The products of this invention can be used in other applications where glyoxal is commonly used, such as for example in treating textiles, strength resins, acrylic polymers, and the like. In order that the present invention may be more fully understood, the following examples are given by way of illustration. Unless otherwise specified, all parts and percentages are by weight. Example #1 To a clean kettle, the polyhydroxyl substituted ester and glyoxal are charged. The mixture is heated with agitation to 40-70°C and held for two hours. The polyol and mineral acid is then charged and held for one to two hours. Vacuum is applied to remove the water and water is distilled until at least of 90% calculated water is collected. Sample A Sample B Sample C Sorbitan Monostearate 51.12 61.50 - Glycerol Monostearate - - 67.69 Glyoxal 38.14 29.95 25.16 Propylene Glycol 10.58 8.39 6.99 Sulfuric Acid .10 .10 .10 Sodium Hydroxide .06 .06 .06 Sodium Bicarbonate - - .01 Each of the above reaction products was mixed with a surfactant and water to a level of 30% solids, with Samples A and B mixed with 2.6% of a surfactant (a mixture of stearyl alcohol-23 moles ethylene oxide adduct and lauryl alcohol-23 moles ehtylene oxide adduct) and Sample C mixed with 2.8% of a surfactant (nonylphenol-40 moles ethylene oxide adduct). The water, reaction product and surfactant were charged to a kettle, heated to 60-80°C with agitation until all was melted, evenly dispersed and emulsified. Examples #2-6 The samples A, B and C prepared in Example #1 were then evaluated and compared to a cyclic urea-glyoxal condensate insolubilser (Sunrez R 700 by Sequa Chemicals, Inc.) in a coating mix as follows: Example 2 3 4 5 6 #1 Clay 100 100 100 100 100 Dispex N-40 (Allied Colloids Limited) -acrylic dispersant .15 .15 .15 .15 .15 Dow 620A (Dow Chemical Co.) -styrene-butadiene copolymer 8 8 8 8 8 PG 280 (Penick and Ford Corp.) -hydroxyethylated starch 8 8 8 8 8 Calcium Stearate - 1.0 - - - Insolubiliser(Sunrez R - .25 - - - 7000M) Sample A - - 1.25 - - Sample B - - - 1.25 - Sample C - - - - 1.25 Solids 59.7 59.7 59.7 59.6 59.0 pH 8.1 8.1 8.1 8.1 8.0 The above coatings were applied to a groundwood free paper with a laboratory web blade coater and the following tests were run with the following results: The examples show that Samples A, B and C work as both a lubricant and an insolubiliser. The gloss numbers for Samples A, a and C were at least equal to or improved compared to a conventional lubricant (calcium stearate). The Pick Numbers for Examples 2-5 were all run at the same time and there was no significant difference in the surface strength measured therein compared to a commercially available cyclic urea-glyoxal condensate insolubiliser. Example 6 was run at a separate time, but showed no difference in surface strength from repeat of a control of Examples 2 and 3. The SIWA brightness indicated no significant variation between Examples 2-5, with Example 6 showing a decrease in the ability to absorb water. In the Adams Wet Rub, a lower number indicated resistance to water, with the Samples A, B and C showing improved resistance.

Claims: Claims for the following Contracting States : AT, BE, CH, DE, FR, GB, GR, IT, LI, LU, NL, SE A reaction product obtainable by reacting glyoxal with a polyhydroxyl substituted ester of a fatty acid selected from the group consisting of sorbitan monolaurate, sorbitan mono-oleate, sorbitanmonostearate, sorbitanmonopalmitate, glycerol monostearate, glycerol monopalminate, glycerol monomyristate, trimethylol ethane monostearate, trimethylol ethane monopalminate, trimethylolethane monomyristate, trimethylol propane monostearate, trimethylol propane monopalminate, trimethylol propane monomyristate, pentaerythritol monostearate, pentaerythritol monopalminate, pentaerythritol monomyristate and their mixtures and then with a polyol containig two or more hydroxyl groups selected from the group consisting of ethylene glycol, glycerin, propylene glycol, trimethylol propane, sorbitol and their mixtures. A reaction product according to claim 1 wherein the polyhydroxyl substituted ester is present in an amount of about 30 to 70% by weight, the glyoxal is present in an amount of about 20 to 60% by weight and the polyol is present in an amount of about 5 to 25% by weight. An insolubiliser composition comprising a reaction product according to claim 1 or claim 2 and further comprising a surfactant. The insolubiliser composition according to claim 3 comprising 10 to 50% by weight of the reaction product, 1 to 15% by weight of the surfactant and 35 to 90% by weight of water. A paper coating composition comprising a reaction product according to claim 1 or claim 2, a pigment and a binder. A paper coating composition according to claim 5 wherein the binder is a starch. A paper coating composition according to claim 5 or claim 6 wherein the reaction product is present at 1 to 12% by weight of the binder. Use of the reaction product according to claim 1 or claim 2 as a lubricating insolubiliser for binder for paper coating compositions. Claims for the following Contracting State : ES A process for obtaining a reaction product comprising reacting glyoxal with a polyhydroxyl substituted ester of a fatty acid selected from the group consisting of sorbitan monolaurate, sorbitan mono-oleate, sorbitanmonostearate, sorbitanmonopalmitate, glycerol monostearate, glycerol monopalminate, glycerol monomyristate, trimethylol ethane monostearate, trimethylol ethane monopalminate, trimethylolethane monomyristate, trimethylol propane monostearate, trimethylol propane monopalminate, trimethylol propane monomyristate, pentaerythritol monostearate, pentaerythritol monopalminate, pentaerythritol monomyristate and their mixtures and then with a polyol containig two or more hydroxyl groups selected from the group consisting of ethylene glycol, glycerin, propylene glycol, trimethylol propane, sorbitol and their mixtures. A process according to claim 1 wherein the polyhydroxyl substituted ester is present in an amount of about 30 to 70% by weight, the glyoxal is present in an amount of about 20 to 60% by weight and the polyol is present in an amount of about 5 to 25% by weight. A process for producing an insolubiliser composition comprising mixing a reaction product produced according to claim 1 or claim 2 with a surfactant. A process according to claim 3 in which 10 to 50% by weight of the reaction product is mixed with 1 to 15% by weight of the surfactant and 35 to 90% by weight of water. A process for producing a paper coating composition comprising mixing a reaction product produced according to claim 1 or claim 2, a pigment and a binder. A process according to claim 5 wherein the binder is a starch. A process according to claim 5 or claim 6 wherein the reaction product is present at 1 to 12% by weight of the binder. Use of the reaction product according to claim 1 or claim 2 as a lubricating insolubiliser for binder for paper coating compositions.

Inventors: DRAGNER LOUIS ROBERT, DRAGNER, LOUIS ROBERT
Applicants: SEQUA CHEMICALS INC, SEQUA CHEMICALS INC.
Application year: 1989
Main classification: D21H19
IPC codes: D21H19, C09D7