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Patent US4016306 - Process for forming a coated film in water - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsAn acrylic resin composition containing a thermoplastic acrylic polymer in combination with a specific ethylenically unsaturated diacrylate such as diacrylate of hydroxypivalyl hydroxypivalate is found to be cured by irradiation of active rays in an aqueous medium in the presence of a photo-sensitizer...http://www.google.com/patents/US4016306?utm_source=gb-gplus-sharePatent US4016306 - Process for forming a coated film in waterAdvanced Patent SearchPublication numberUS4016306 APublication typeGrantApplication numberUS 05/592,893Publication dateApr 5, 1977Filing dateJul 3, 1975Priority dateJul 15, 1974Also published asDE2531105A1Publication number05592893, 592893, US 4016306 A, US 4016306A, US-A-4016306, US4016306 A, US4016306AInventorsNorio Miyagawa, Mitsuo Sato, Juichi Kobayashi, Takashi KobayashiOriginal AssigneeMitsubishi Rayon Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (3), Referenced by (15), Classifications (8) External Links: USPTO, USPTO Assignment, EspacenetProcess for forming a coated film in water
US 4016306 AAbstract
An acrylic resin composition containing a thermoplastic acrylic polymer in combination with a specific ethylenically unsaturated diacrylate such as diacrylate of hydroxypivalyl hydroxypivalate is found to be cured by irradiation of active rays in an aqueous medium in the presence of a photo-sensitizer to form a cured film with excellent properties. This composition is especially suitable for coating a plastic tile.
1. A process for forming a coated film which comprises:coating a substrate with an acrylic resin composition, which is curable upon irradiation by active rays, comprising a photopolymerization initiator and a resin component consisting of a combination of A. an acrylic polymer obtained by polymerization of an acrylic monomer of formula I: ##STR8## wherein R1 represents hydrogen atom or methyl group, R2 represents hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group having 1 to 8 carbon atoms, or an aryl group; B. an ethylenically unsaturated diacrylate of formula (II) or (III): ##STR9## wherein R1 is as defined above; R3 represents a divalent aliphatic or cycloaliphatic hydrocarbon residue having 2 to 10 carbon atoms or a polyalkylene glycol residue having 1 to 10 ether bonds in the molecule; R4 represents a carboxyl eliminated divalent fatty acid residue having 1 to 20 carbon atoms or an aromatic or an aliphatic hydrocarbon residue; each of R5, R6, R7, and R8 represents hydrogen atom, a substituted alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or an aryl group; each of R9, R10, R11 and R12 represents hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or an aryl group; n represents an integer of 1 to 10; and each of k, l, m, j, p and q represents an integer of 0 to 5; providing the coated layer with a water layer and subjecting said combined layers to irradiation from a source of active rays to cure the coated film. 2. A process as claimed in claim 1, wherein the resin composition contains the acrylic polymer (A) in an amount ranging from 1 to 50 % by weight based on the composition.
A. an acrylic polymer obtained by polymerization of an acrylic monomer of the general formula (I): ##STR1## wherein R1 represents hydrogen atom or methyl group, R2 represents hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group having 1 to 8 carbon atoms, or an aryl group;
B. an ethylenically unsaturated diacrylate of the general formula (II) or (III): ##STR2## wherein R1 is as defined above; R3 represents a divalent aliphatic or cycloaliphatic hydrocarbon residue having 2 to 10 carbon atoms or a polyalkylene glycol residue having 1 to 10 ether bonds in the molecule; R4 represents a carboxyl eliminated divalent fatty acid residue having 1 to 20 carbon atoms or an aromatic or an aliphatic hydrocarbon residue; each of R5, R6, R7 and R8 represents hydrogen atom, a substituted alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or an aryl group; each of R9, R10, R11 and R12 represents hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or an aryl group; n represents an integer of 1 to 10; and each of k, l, m, j, p and q represents an integer of 0 to 5, and
The ethylenically unsaturated diacrylate (B) represented by the general formula (III) can be prepared by condensing a mono-ester diol with (meth)acrylic acid or (meth)acrylic acid anhydride in the presence of an acid catalyst such as sulfuric acid, p-toluene sulfonic acid, phosphoric acid, etc. or by subjecting said mono-ester diol to dehalogenation reaction with a halogenated product of (meth)acrylic acid in the presence of a dehalogenating catalyst such as pyridine. The mono-ester diol to be used in producing the ethylenically unsaturated diacrylate (B) represented by the general formula (III) has preferably a neopentyl type structure, namely, the compound wherein R5, R6, R7 and R8 are methyl, ethyl or propyl group, R9, R10, R11 and R12 are hydrogen atoms, q and k are zero, l and q are 1, and m and j are 1 or 2. For example, the compound, wherein R5 and R6 are methyl groups, R7 to R12 are hydrogen atoms, k and q are zero, l, m and p are 1, and j is 2, is hydroxylpivalyl hydroxybutyrate; the compound, wherein R7 and R8 are methyl groups, R9 to R12 are hydrogen atoms, k and p are 1, and l, m, j and q are zero, is hydroxyethyl hydroxypivalate; and the compound, wherein R5 to R8 are methyl groups, R9 to R11 are hydrogen atoms, m, l, and p are 1, and k, j and q are zero, is hydroxypivalyl hydroxypivalate. These mono-esters diols can be used either alone or in mixtures.
Preparation of Acrylic Polymer (A)
Into a reactor equipped with a stirrer, a nitrogen injection pipe, a thermometer and a reflux condenser are charged 1500 parts of xylene, followed by heating at 130� C. Then a mixture of 1350 parts of methyl methacrylate, 1350 parts of ethyl acrylate, 300 parts of methacrylic acid, 60 parts of di-tert-butyl peroxide and 30 parts of tert-dodecyl mercaptan is added dropwise over 2 hours and the mixture is maintained at 140� C for an additional 5 hours. The resulting acrylic resin solution is supplied to a thin membrane evaporator to evaporate xylene, whereby an acrylic polymer (A) is obtained.
Preparation of Acrylic Polymer (B)
Into the same reactor as used in preparative Example 1 are charged 2100 parts of water, 0.5 part of sodium polyacrylic acid, 3 parts of sodium primary phosphate and 11 parts of sodium secondary phosphate and the mixture is heated at 70� C. Then, a mixture of 310 parts of ethyl acrylate, 680 parts of methyl methacrylate, 14 parts of benzoyl peroxide and 11 parts of tert-dodecyl mercaptan is added dropwise to the reactor and the reaction mixture is thereafter heated to 80� C and maintained at said temperature for 4 hours. After evaporation of water, an acrylic polymer (B) is obtained.
Preparation of Ethylenically Unsaturated Diacrylate (C):
Into a reactor equipped with a stirrer, a nitrogen injection pipe, a thermometer and a reflux condenser are charged 2960 parts of phthalic acid anhydride and 730 parts of ethylene glycol and the reaction is performed at 210� C for 6 hours while removing condensed water to obtain hydroxylterminated polyester resin having hydroxyl value of 454. 2000 Parts of acrylic acid are added to 3170 parts of this polyester resin and the reaction is carried out at 95� C for 6 hours, followed by evaporation of toluene, to give a purified ethylenically unsaturated diacrylate (C) having the following resin properties:
Preparation of Ethylenically Unsaturated Diacrylate (D):
2960 Parts of phthalic acid anhydride and 4576 parts of neopentyl glycol are charged in the same reactor as in preparative Example 3 and the reaction is performed at 210� C for 6 hours while removing condensed water to obtain a hydroxylterminated polyester resin having a hydroxyl value of 360. To 3480 parts of this polyester resin are added 2300 parts of acrylic acid, 30 parts of hydroquinone, and 3800 parts of toluene. The reaction is performed at 95� C for 6 hours, followed by evaporation of toluene, to give a purified ethylenically unsaturated diacrylate (D) with the following resin properties:
Preparation Of Ethylenically Unsaturated Diacrylate (E):
Into the same reactor is preparative Example 3 are charged 3265 parts of hydroxypivalyl hydroxypivalate, 2420 parts of acrylic acid, 55 parts of hydroquinone and 4410 parts of cyclohexane. The reaction is carried out at 95� C for 5 hours, followed by evaporation of toluene, to give purified ethylenically unsaturated diacrylate (E) with the following resin properties:
EXAMPLE 1 - 4
The acrylic polymers (A) and (B) obtained in preparative Examples 1 and 2 were compounded with the ethylenically unsaturated diacrylates (C), (D) and (E) obtained in preparative Examples 3 to 5 according to the combinations set forth in Table 1, each mixture being admixed with 2.0 wt. % of benzoin methyl ether as photosensitizer to prepare acrylic resins F, G, H and I. These coating compositions were coated on the substrates as shown in Table 1 by means of the coaters as shown in Table 1. These coated products were dipped in water to the depth as shown in Table 1 and the coated films were cured by irradiation of active rays under the conditions as set forth in Table 1. The results of measurement of the properties of the cured coated films of the resulting products are also shown in Table 1.
Table 1__________________________________________________________________________Acrylic resincomposition:       Example 1              Example 2  Example 3                                Example 4__________________________________________________________________________Acrylic polymer (A)       158 parts              98 partsAcrylic polymer (B)              118 parts  118 parts                                98 partsEthylenicallyunsaturateddiacrylate (C)       822 partsEthylenicallyunsaturateddiacrylate (D)     764 parts  30 partsEthylenicallyunsaturateddiacrylate (E)                832 parts                                882 partsSensitizer(benzoin methylether       20 parts              20 parts   20 parts                                20 partsConditions: Example 1              Example 2  Example 3                                Example 4__________________________________________________________________________Substrate   Aluminum              Acrylo-    Asbestos                                Polyvinyl       plate  nitrile-   plate  chloride              butadiene-        tile              styrene              co-polymer              sheetCoater      Knif-  Flow-      Sprayer                                Roll-       coater coater            coaterCuring conditions  Two high-pressureby irradiation in         --   mercury lamps with                                  --water              output of 5 KW,              200W/inch, with              travelling speed of              12 m/min. and water              depth of 5 cmAmount ofcoating (g/ft2)         1      3          5      2Results:State of curing       Good   Good       Good   GoodAppearance(surface smoothness)       Good   Good       Good   GoodAdhesiveness (peel-off of cross-cuts       No peel-              No peel-   No peel-                                No peel-with cellophane       off    off        off    offtape)Pencil hardness        2 H     H         2 H     HAcid resistance(5% H2 SO4, spot       no change              no change  no change                                no changetest, 24 hours)       (5*)   (5)        (5)    (5)Alkali resistance(1% Na2 CO3, spot       no change              no change  no change                                no changetest, 24 hours)       (5)    (5)        (5)    (5)Gasoline resistance(Regular, spot       no change              no change  no change                                no changetest, 24 hours)       (5)    (5)        (5)    (5)Abrasion resistance(Taber abrasiontester: 500 g         --     --         --    12 mgloading, H-18,5000 rotations)__________________________________________________________________________ *) expressed by a 5-grade visual measurement (1 means the worst, 5 means the best)
COMPARATIVE EXAMPLE 1 - 3
A resinous composition is prepared by mixing 580 parts of the acrylic polymer (A) obtained in preparative Example 1 and 400 parts of the ethylenically unsaturated diacrylate (D) obtained in preparative Example 4 with 20 parts of benzoin methyl ether (Comparative example 1). Another resinous composition is prepared by mixing 980 parts of the ethylenicaly unsaturated diacrylate (E) obtained in preparative Example 5 with 20 parts of benzoin methyl ether (Comparative example 2). Still another resinous composition is prepared by mixing 980 parts of an unsaturated polyester resin composition (comprising 590 parts of a polycondensate prepared from 1 mole of phthalic anhydride, 1 mole of maleic anhydride and 2.2 mole of propylene glycol and 410 parts of styrene) with 20 parts of benzoin methyl ether (Comparative Example 3). These compositions are coated on polyvinyl chloride tiles by means of roll coater under the conditions as shown in Table 2. The coated tiles are irradiated in water under the same conditions as in Examples to obtain tiles having cured coatings. The results are shown in Table 2.
Table 2__________________________________________________________________________        Comparative                 Comparative                          ComparativeComposition: example 1                 example 2                          example 3__________________________________________________________________________Acrylic polymer (A)        580 partsEthylenicallyunsaturateddiacrylate (D)        400 partsEthylenicallyunsaturateddiacrylate (E)        980 partsUnsaturatedpolyester resin                980 partsSensitizer (benzoinmethyl ether)        20 parts 20 parts 20 partsConditions:Substrate    PVC tile PVC tile PVC tileCoater       Roll coater                 Roll coater                          Roll coaterCuring conditions        Same as in                 Same as in                          Same as inin water     Examples Examples ExamplesAmount of coating(gr/ft3)          2        2        2Results:State of curing        Not good Not good Not goodAppearance(surface smoothness)        Not good Not good Not goodAdhesiveness(same as in Table 1)        peeled off                 peeled off                          peeled offPencil hardness         5 B      H B      5 BAcid resistance(same as in Table 1)        Not good(1)                   (3)    Not good(1)Alkali resistance(same as in Table 1)        Not good(1)                   (3)    Not good(1)Gasoline resistance(same as in Table 1)        Not good(1)                   (3)    Not good(1)Abrasion resistance(same as in Table 1)        unmeasurable                 180 mg   unmeasurable__________________________________________________________________________
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