TW593587B - Acrylic microgel resin composition and coating composition containing the same - Google Patents

Abstract

An acrylic microgel resin composition is a non-aqueous dispersion system (NAD) having substantial cross-linking, made by the dispersion copolymerization of acrylic monomers having epoxy, carboxyl, or hydroxyl groups, or the combination, mono-functional acrylic monomers, ethylenically unsaturated monomers, a wholly acrylic dispersing agent having hydroxyl groups and short pendant chains, and amino resin which can react with the above hydroxyl groups to increase cross-linking, in an aliphatic hydrocarbons-rich solvent mixture; wherein acrylic dispersing agent comprises acrylic C8-36 alkyl ester to offer short pendant chains and the amino resin comprises totally or partially alkoxylated melamine-formaldehyde resins. The coating composition containing the acrylic microgel resin composition of the present invention has excellent physical properties and is suitable for the use in automotive multi-layer coatings.

Description

593587 __Case No. 91137447_ Year Month__ V. Description of the invention (1) Technical field to which the invention belongs The invention relates to an acrylic microgel resin composition and a coating composition containing the same, which have good physical properties and can be Used in the ingredients of automotive coatings and silver paints. Prior art The coating industry has actively reduced the use of volatile organic compounds (VOC) in response to environmental protection demands. However, when it is necessary to use coatings with medium or low solid content, volatile organic compounds are still needed as solvents, so the development of Non-Aqueous Dispersions (NAD) resins is aimed at Designed to reduce the V0C and increase the solid content of the resin batching system. In order to allow NAD resin to disperse in various solvents without increasing the viscosity of the coating system, it is generally an effective and feasible method to internally cross-link the dispersed phase of NAD resin to form microgels (M i c 〇 g e 1 s). However, during the synthesis of traditional microgel resins, it is easy to agglomerate and agglomerate and sink to the bottom. When stored, the majority of microgel resins will aggregate to form phase separation and precipitate. Furthermore, the dispersibility of pigment coloration is poor when traditional microgel resins are used. One of the reasons is that the particle size of the microgel is too large, which causes the microscopic pigment phase to condense, and the entire resin system tends to be opaque. Can not meet the bright color requirements of modern automotive coatings. U.S. Patent No. 3,8 0,7,96 discloses a method for preparing an acrylic microgel-containing coating. Among them: the microgel is mainly composed of a hydroxyl-containing acrylic monomer, a carboxyl-containing acrylic monomer, and an epoxy-containing graft polymer dispersant, and is dispersed and copolymerized in an aliphatic hydrocarbon solvent to obtain a non-aqueous dispersion system. And substantially cross-linked. The dispersant was grafted with long chain poly (12-hydroxystearic acid). This microgel is also copolymerized using non-acrylic monomers such as stupid ethylene. The microgel can be generally amino-based

Page 7 593587 Case No. 91137447 Amendment V. Description of the invention (2) Cross-linking and hardening. U.S. Patent No. 4,34 0,5 1 1 discloses a method for producing acrylic microgels. The microgel is mainly composed of a functional acrylic monomer, at least part of: an alkyl-etherified amine resin, and a graft polymer dispersant, which is dispersed and copolymerized in an aliphatic hydrocarbon solvent to obtain a non-aqueous dispersion system. ; And acrylic monomer functional groups and amine resins produce substantial cross-linking. The dispersant is grafted with long-chain poly (12-hydroxystearic acid). The patent also discloses the composition of an acrylic paint containing the acrylic microgel. These include: acrylic copolymers containing hydroxyl and carboxyl acrylic, organic solvents that dissolve acrylic copolymers, and acrylic microgels prepared. 18 U.S. Patent No. 4,4 25,4 50 discloses an acrylic paint containing a stabilized acrylic microgel containing melamine resin. These include: hydroxyl-containing acrylic copolymers, amine-based resins or isocyanate resins for cross-linking and hardening, and melamine resins for stabilization of acrylic microgels for flow control additives. The method for preparing the stabilized acrylic microgel includes: (A) the acrylic microsusceptible gel is firstly composed of a long-chain poly (12-hydroxystearic acid) ester group, a C-branyl ester group, Epoxy-containing acrylic copolymers synthesized from epoxy-based acrylic monomers react with carboxyl-containing acrylic monomers to obtain unsaturated acrylic dispersants; then, using the dispersants, and A non-aqueous dispersion system is synthesized by a non-aqueous dispersion copolymerization method containing a C alkyl ester group, an epoxy group, an carboxyl group, and a hydroxyl acrylic monomer, and at the same time, a substantially crosslinked acrylic microgel is formed. (B) Obtained by mixing the microgel with a butyl etherified melamine resin. Due to the poor coloring properties of NAD hawthorn f, it is not usually used alone. Instead, use NAD resin with high solids acrylic resin and melamine-formaldehyde (dehyde) resin hardener. While having reduced

Page 8 593587 Case No. 91137447 A: _ Amendment V. Explanation of the invention (3) High solid content acrylic resin viscosity, maintaining high solid content of coating, giving bright color to silver paint and other effects. It is characterized by the design of the degree of crosslinking between the polymeric dispersant system and the microgel. The polymer dispersant of acrylic NAD resin of the prior art is a comb type (C omb-) press using a polyester long side chain containing poly (carboxy stearic acid) (P 0 1 y (hydr ο X ystearicacid)) Acrylic copolymer, or acrylic copolymer using fully acrylic short side chains. However, the increase in the amount of cross-linking agent in the microgel not only increases the degree of cross-linking inside the microgel particles, but also increases the chance of cross-linking between the microgel particles. The latter will cause the microgel NAD resin viscosity to rise and agglomerate. Therefore, it is necessary to select an appropriate polymeric dispersant system to manufacture a good non-aqueous dispersion resin and form a coating composition with good physical properties to avoid the problems described above and the like. If the microgel synthesis system also contains an appropriate amount of melamine resin and epoxy-based acrylic monomers (such as Glycidyl methacrylate (GMA)), the melamine resin is completely Acrylic copolymers with short acrylic side chains react to form dispersants containing melamine resin functional groups, which improves the dispersion and storage stability of NAD resins. On the other hand, it works with GMA to promote hydroxyl and carboxyl-containing acrylic NADs. Degree of crosslinking within the resin molecule. In this way, the problems described above can be improved, and the microgel NAD resin can be applied to the formulation of automotive color paints or silver paints. SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide an acrylic microgel resin composition comprising (a) an acrylic monomer having an epoxy group, a carboxyl group, or a hydroxyl group, or a combination thereof, (b) Monofunctional acrylic monomer, (c) ene

593587 Case No. 91137447 Λ_ is the amendment. Description of the invention (4) type monomer, (d) acrylic dispersant with complete acrylic short side chain containing hydroxyl group, the acrylic dispersant has a C 8_3 alkyl ester pressure Acrylic short side chains, and (e) amine-based resins that can react with these groups to form conjugates. 5 The amine-based resins include melamine-formaldehyde resins, which are fully or partially etherified, and are based on aliphatic hydrocarbons. Non-aqueous dispersion system (NAD) is obtained by dispersing and copolymerizing in the main solvent. Another object of the present invention is to provide an acrylic transparent coating composition containing the above-mentioned acrylic microgel resin composition. Another object of the present invention is to provide an acrylic coloring coating composition containing the above-mentioned acrylic microgel; needle fat composition. Still another object of the present invention is to provide an acrylic microgel composition silver powder paint coating composition containing the above-mentioned acrylic microgel resin composition. Compared with the prior art, because the acrylic microgel resin composition of the present invention has better microscopic composition and better refractive index, the refractive index difference is small, so the coating containing the acrylic microgel resin composition of the present invention The coating film formed by the composition has higher transparency, and the difference can be shown by the coating film imaging test. In addition, the amount of VOC used can be reduced, but the viscosity does not change, and it still has good physical properties, such as rheology and processing suitability. It is more suitable for the ingredients of automotive coatings and silver powder paints. Embodiments The present invention provides an acrylic microgel resin composition comprising (a) an acrylic monomer having an epoxy group, a carboxyl group, or a hydroxyl group, or a combination thereof (b) an acrylic having a monofunctional group Force monomer, (c) dilute monomer,

Page 593587 ___Case No. 91137447_Year_Month__ V. Description of the invention (5) (d) Acrylic dispersant with hydroxyl-containing full acrylic short side chain, the acrylic dispersant has C 8_3 Probe the short acrylic ester side chain, and (e) can react with these hydroxyl groups to form a crosslinked amine-based resin. The amine-based resin includes a melamine-formaldehyde resin with alkyl groups fully or partially etherified. The non-aqueous dispersion system (NAD) is obtained by dispersing and copolymerizing an aliphatic hydrocarbon-based solvent, and is substantially cross-linked. This acrylic microgel is a saturated acrylic copolymer with a molecular weight in the range of about 2,0 0 to 1 0 0,0 0 0, preferably 4,0 0 0 to 4 0,0 0 0 Within the range, the C 8_3 anti-S purpose acrylic short side chain is preferably C 12_18. "Acrylic monomer and acrylic (A cry 1 ics)" in this document refers to acrylic, methacrylic, acrylic, methacrylic, etc. having monofunctional or polyfunctional groups Monomers, and copolymers of these monomers to obtain polymers. The aforementioned acrylic monomer having an epoxy group is glycidyl acrylate or glycidyl acrylate. The acrylic monomer having a carboxyl group is acrylic acid or methacrylic acid. The acrylic monomer having a hydroxy group is hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, or hydroxy acrylate. Propyl ester. The monofunctional acrylic monomer is a C1-alkyl ester or a cycloalkyl ester of acrylic acid or methacrylic acid. The olefinic monomer is styrene, acrylonitrile, maleic anhydride, styrene, or vinyl acetate. The above-mentioned amine-based resin is a melamine-formaldehyde resin in which an alkyl group is fully or partially etherified, and a melamine in which a C alkyl group is fully or partially etherified is preferred.

Page 11 593587 Amendment No. 91137447 V. Description of Invention (6) Formaldehyde resin. Containing amine-based resins, especially polyalkylamine-formaldehyde resins in which the alkyl group is fully or partially etherified, has the effect of modification, making the acrylic microcoagulation resin composition more dispersible. When the coating composition is made together with a blocked isocyanate resin, the dispersion and storage stability of the pressure-sensitive side chain of the invention can be improved. The monofunctionality is based on the acrylic monomer of the solution polymer as the ester, or acrylic. Monoester, preferably. The pressure of the ethylenic acid monoester invention is soluble in the pressure of other parts of the invention. The acrylic pressure is preferably about the pressure of the invention. The pressure of the invention is short. The acrylic monomer is short. The monomer has a pressure of carboxyl. Cycloalkyl pityl ester of hydroxypropyl side chain of gram acid or acetic acid side chain agent molecular weight of solvent,%, fully acrylic dispersant containing hydroxyl group in dry, acrylic microgel resin composition It is an acrylic resin solution obtained by copolymerizing acrylic monomers having short side chains of acrylic esters having a carboxyl group or a hydroxyl group, and an ethylenic type. The force monomer is acrylic acid or methacrylic acid. It has hydroxy acrylic acid via ethyl ester, methacrylic acid via ethyl ester, and acrylic acid via acrylic acid. The monofunctional C η and S radicals are C alkyl alkyl esters of acrylic acid or methacrylic acid, or C κ alkyl esters of acrylic acid or methacrylic acid, or the ring is styrene, acrylonitrile, maleic anhydride, The C 8_3 ester-based short aliphatic hydrocarbon-based solvent on the styrene-based acrylic microgel resin composition, and the microgel includes a dispersion that is insoluble in the aliphatic hydrocarbon-based solvent. The acrylic microgel resin composition is mainly composed of aliphatic hydrocarbons. The total weight of the microgel resin composition is about 25 to 95% by weight, 35 to 80% by weight, and more preferably about 40 to 70% by weight. The acrylic microgel resin composition is an emulsion-colored fine powder after manufacturing. In the acrylic microgel resin composition, the hydroxyl group is completely pressed.

Page 12 593587 Amendment No. 91137447, Description of Invention (7) The content of the acrylic dispersant of the acrylic short side chain accounts for about 3 to 75% by weight of the solid content of the acrylic microgel resin composition, preferably It is 5 to 40% by weight. Wherein there is a repeating unit having a C 8_3 ester-based acrylic short side chain, which accounts for about 20 to 80% by weight of the solid content of the acrylic dispersant of the hydroxyl-containing complete acrylic short side chain, preferably 30 to 75% by weight. The repeating unit with a short acrylic side chain is based on about 3 to 50% by weight, preferably 5 to 40% by weight of the solid content of the acrylic dispersant of the complete acrylic short side chain containing hydroxyl groups. . The acid value of the solid dispersant of the acrylic dispersant containing the complete hydroxyl short side chain of the hydroxyl group is about 0.4 to 150 mgKOH / g, and preferably 1.0 to 100 mgKOH / g. The repeating unit having a CV alkyl ester-based short acrylic side chain and the repeating unit of a fluorene type monomer collectively account for about 3 to 70% by weight of the solid content of the acrylic dispersant containing the complete hydroxyl short acrylic side chain. , Preferably 5 to 40% by weight. Wherein, the content of the amine-based resin participating in the non-aqueous dispersion (N AD) microgel polymerization reaction is about 0.1 to 30% by weight of the solid content of the acrylic microgel resin composition, preferably 0.5 to 20% by weight. In the acrylic microgel resin composition of the present invention, the amount of the acrylic monomer having an epoxy group is about 0.2 to 15 weight of the solid content of the acrylic microgel resin composition. %, Preferably 0.5 to 10% by weight. The amount of the acrylic monomer having a base is about 2 to 60% by weight, preferably 5 to 50% by weight, of the solid content of the acrylic microgel resin composition. The acid value of the solid content of the acrylic microgel resin composition is about 0.4 to 150 mgKOH / g, preferably 1.0 to 100 mg K 0 H / g. The monofunctional acrylic monomer is used in an amount of about 2 to 55 wt%, preferably 5 to 40 wt%, based on the solid content of the acrylic microgel resin composition. The amount of the olefinic monomer is about 0.2 to 40% by weight of the solid content of the acrylic microgel resin composition, preferably

Page 13 593587 Case No. 91137447 Amendment 1. Description of the invention (8) is 1.0 to 30% by weight. In the acrylic microgel resin composition of the present invention, when an acrylic monomer repeating unit having a hydroxyl group is included, the microgel is internally connected by a warp group of an acrylic monomer repeating unit and an amine-based resin -NHCH 20 R or -NHCH 20 所 formed by cross-linking reaction; when an acrylic monomer repeating unit having an epoxy group and a carboxyl group is included, the internal cross-link of the microgel is formed by the acrylic monomer repeating unit. Formed by crosslinking reaction of epoxy group and carboxyl group. The acrylic microgel resin composition of the present invention, whether in a liquid state or a powder state, can be uniformly mixed with an amine-based resin including a melamine-formaldehyde resin fully or partially etherified with an alkyl group. The mixture can be cross-linked and hardened by baking; its solid content mixing ratio is about 0.02 to 100, preferably 0.05 to 20. The invention also provides an acrylic transparent coating composition containing an acrylic microgel resin composition, including: (a) a hydroxyl- and carboxyl-containing acrylic copolymer, (b) a soluble (a) pressure Organic solvents for acrylic copolymers, (c) the acrylic microgel resin composition of the present invention as described above, and (d) amine-based resins that can react with hydroxyl groups to form crosslinked, blocked isocyanates Resin, or a combination thereof. In the above-mentioned acrylic transparent coating composition containing the acrylic microgel resin composition of the present invention, the hydroxyl- and carboxyl-containing acrylic copolymer, the acrylic microgel resin composition, and the above components (D) The mixture can be cured by baking and cross-linking; the solid form of its acrylic and amine-based resin (if it includes a blocked isocyanate resin, it is the combination of amine-based resin and isocyanate resin) The mixing ratio of parts is about 0.02 to 100, and preferably 0.05 to 20. The acrylic copolymer containing hydroxyl and carboxyl groups and the acrylic microgel resin composition

Page 14 593587 __Case No. 91137447_Year_Month__ 5. Explanation of the invention (9) What proportions are mixed. The present invention further provides an acrylic coloring coating composition containing an acrylic microgel resin composition, which includes (a) acrylic copolymers containing a base and a base, (b) soluble (a) The organic solvent of the acrylic copolymer, (c) the acrylic microgel resin composition of the present invention as described above, (d) an amine-based resin that can react with a hydroxyl group to form a blocked isocyanate Sealant, or a combination thereof, (e) color paste, and (f) coating additives. In the acrylic colored coating composition containing the acrylic microgel resin composition, the hydroxyl- and carboxyl-containing acrylic copolymer, the acrylic microgel resin composition, and the component (d) The mixture can be cured by baking and cross-linking; the mixing ratio of its acrylic and the solid content of the amine-based resin (if it includes a blocked isocyanate resin, it is the total of the amine-based resin and the isocyanate resin) It is about 0.02 to 100, and preferably 0.05 to 20. The hydroxyl- and carboxyl-containing acrylic copolymer and the acrylic microgel resin composition may be mixed in any ratio. The invention further provides an acrylic silver powder paint coating composition containing an acrylic microgel resin composition, including: (a) a hydroxyl- and carboxyl-containing acrylic copolymer, (b) soluble (a) The organic solvent of the acrylic copolymer, (c) the acrylic microgel resin composition of the present invention as described above, (d) an amine-based resin that can react with a hydroxyl group to form a cross-linked isocyanate Acid resin, or a combination thereof,

Page 15 593587 Case No. 91137447 V. Description of the invention (10) e) Metal powder paste, and 0 Coating additives. In the acrylic silver powder paint I composition containing the acrylic microgel resin composition, the hydroxyl- and carboxyl-containing acrylic copolymer, the acrylic microgel is fastened to the fat composition, and the component (d ) Mixture, which can be cured by baking cross-linking • its acrylic and solid form of the amine-based resin (if it includes a blocked isocyanate resin 'is the sum of the amine-based resin and the isocyanate resin) The mixing ratio of parts is about 0.02 to 100, preferably 0.05 to 100. The hydroxyl- and carboxyl-containing acrylic copolymer and the acrylic microgel resin composition may be mixed in any ratio. The method for manufacturing the acrylic microgel resin composition of the present invention is to first prepare a unique dispersant as disclosed in the present invention by using the technique of the traditional solution polymerization method, and then to prepare it by the technique of the conventional dispersion copolymerization method. Microgel. The traditional solution polymerization method can refer to the EH 4 (116 n Monomer ic crylic Esters "(1954) (Reinhold) page 40 ~ 48 for examples and descriptions. For the dispersion copolymerization method, refer to KE J. Barrere 11" Dispersion Polymerization Examples and explanations in Organic Median (1975) (John Wiley & Sons), pages 234 to 37. The acrylic microgel resin composition of the present invention is applied to acrylic transparency by a method known in the art. Coating composition, acrylic color coating composition, acrylic silver powder paint coating composition. For the preparation of the coating composition, refer to US Patent No. 4 3 9 1 8 5 8 "Coating Process" (1983) Disclosed. These acrylic microgel resin composition-containing coating compositions of the present invention

Page 16 593587 __Case No. 91137447_year month_ifi_ V. Description of the invention (11) The substance contains less V 0 C, but the viscosity does not increase, it has excellent physical properties, especially the required rheological properties This acrylic coating composition can be applied to the surface of articles such as metal, automobile, woodware, ceramics, etc. by methods known in the art, such as spray coating, brush coating, roller coating, and shower coating. In the application of silver powder paint coating composition, the metal powder paste in the composition can be evenly distributed to achieve the desired effect. For example, the measurement of the Ford resolution of the coating film is to explain the dispersion state of the metal powder paste. In order to make the above and other objects, features, and advantages of the present invention more comprehensible, the preferred embodiments are exemplified below and described in detail as follows, where the "parts" mentioned are parts by weight unless otherwise specified . Example 1 Synthesis of hydroxyl-containing complete acrylic copolymer dispersant (code D-1) 28.8. 6 parts of dibenzobenzene, 32.0 parts of butanol, 12.0 parts of fluorenyl acrylic acid Phenyl ester, 26.0 parts of lauryl methacrylate, 9 1.2 parts of 2-hydroxyethyl methacrylate, 4.8 parts of methacrylic acid, and 12.0 parts of benzene peroxide The olefinic monomer mixture was fed into a 500 m 1 four-necked flask. Under nitrogen flow and constant speed stirring, the reactor was allowed to react at 115 ° C for 290 minutes. Light yellow clear solution, code D-1. The solid content of the solution was 57.1% by weight, the weight average molecular weight = 1 2, 0 0, and the molecular weight distribution = 11.8. Example 2 Synthesis of hydroxyl-containing complete acrylic copolymer dispersant (code D-2) 108.1 parts of butyl acetate, 12.3 parts of butanol, 33.6 parts of fluorenyl acrylic acid Methyl ester, 108. 1 part of octadecyl methacrylate (which contains 35% hexadecyl methyl methacrylate), 3 6 · 2 parts of 2-hydroxyethyl methacrylate Radicals, 2.7 parts of methacrylic acid and 4.2 parts of olefinic monomer mixture of phenylhydrazine.

Page 17 593587 Case No. 91137447 ^ ___ η Amendment V. Description of the Invention (12) In a 500 m 1 four-necked flask, under nitrogen flow and constant speed stirring, the reactor was reacted at 1 0 (TC reaction 4 1 0 After a minute of cooling, the material is cooled to obtain a light yellow clear transparent solution, code D-2. The solid content of the solution is 59.4% by weight, the weight average molecular weight = 1 7,600, and the molecular weight distribution = 2.0. Implementation Example 3 Synthesis of hydroxyl-containing complete acrylic copolymer dispersant (code D-3) 108.1 parts of butyl acetate, 12.0 parts of butanol, 3 3.3 parts of methacrylate , 108.1 parts of octadecyl methacrylate, 36.7 parts of 2-hydroxyethyl methacrylate, 2.7 parts of methacrylic acid, and 4.2 parts of benzene peroxide The monomer mixture was fed into a 500 m 1 four-necked flask. Under nitrogen flow and constant speed stirring, the reactor was reacted at 100 ° C for 3 6 1 minutes. The material was cooled to obtain a pale yellow clear. Transparent solution, code D-3. The solid content of the solution is 59.9% by weight, the weight average molecular weight = 1 3,60, and the molecular weight distribution = 2.3. Example 4 Acrylic microgel resin composition (Code DG-1) Preparation: 15.2 5 parts of EXX ο η company's Iparpar C, 35.0 parts of xylene, 70.0 parts of D-1, 20.1 parts of benzene Ethylene, 50.0 parts of methacrylic acid ester, 24.2 parts of acrylic acid 2-ethyl ethyl ester, 4.0 parts of ethyl propylpropionate glycidyl ester, 2.0 parts of methacrylic acid, and 1. 7 parts of olefinic monomer mixture of phenylhydrazone is fed into a 500 m 1 four-necked flask, and the reactor is reacted at 100 ° C for 3 8 5 minutes under nitrogen flow and stirring. Cooling and feeding, a low viscosity white suspension solution is obtained, which is an acrylic non-aqueous dispersion microgel, code DG-1. The solid content of the solution is 42.2% by weight. After the solution is dried, it is a white fine powder 65.0 parts of DG-1 was mixed with 30.0 parts of Cymel㊣ 1158 of Cyanoamine Corporation and 3.5 parts of Isopar® E of Exxon Corporation to obtain a solid content of 52.1% by weight of the mixture containing pressure Acrylic non-aqueous dispersion type microgel coating composition,

Page 18 593587 Case No. 91137447 Amendment V. Description of the Invention (13) Code DGM-1. Its Brookfiel viscosity (20 ° C) is 9 8 cps, and it can be used for spraying industrial baking paint ingredients. However, DG-1 gradually formed flocculated sediments after standing for 2 weeks, showing that its storage dispersibility was insufficient. Example 5 Preparation of Acrylic Microgel Resin Composition (Code d G-2) 120 · 1 part of ISOpar (g) C of Exxon Corporation, 60.2 parts of Isopar® E of Exxon Corporation, 67.4 parts D-2, 10.0 parts Cyme 1 (g) 1 5 8, 27.0 parts styrene, 3 2.1 parts fluorenyl acrylic acid g cyanamide 3 g 2-hydroxyethyl methacrylate, 4.1 parts glycidyl methacrylate

, 2 _ 0 parts of methacrylic acid, and 1.7 parts of olefinic monomer mixture made of benzene peroxide, fed into a 500 m 1 four-necked flask, under nitrogen flow and stirring, the reactor The reaction was carried out at 95 C for 3 to 5 minutes, and the material was cooled to obtain a low-viscosity white suspension> Valley liquid 'is waste acrylic non-aqueous dispersing microgel' code DG-2. The solids content of the solution was 42.7 wt%, and the Brookfield viscosity (25 ° C, 60 rpm) was 20 · 3 c p s. After D G-2 was left to stand for 110 days, the container had only a small amount of dispersible flocculent deposits, showing that it had excellent storage dispersibility. After the solvent was dried, it was white fine powder.

Take 72.0 parts of DG-2 and mix with 25.5 parts of Cyme 1 (g) 1 158 to obtain a solid content of 52.2% by weight, which is a coating composition containing acrylic non-aqueous dispersion microgel Material, code DGM-2, has a Brookfiel viscosity (25 ° C, 60 rpm) of 210 cps and a fineness <0.5 // m, which can be used for spraying industrial baking paint ingredients. Example 6 Preparation of Acrylic Microgel Resin Composition (Code DG-3) 10.1 parts of Isopar (R) of Exxon Company, 60.1 parts of Ispar (E) of Exxon Company, 6 7 · 3 Parts of D-3, 10.0 parts of the cyanamide company

Page 19593587 ---- Case No. 91137447 _ Amended Date ____ V. Description of the invention (14) cyme _ 1 1 5 8, 2 7 · 7 parts styrene, 3 2.0 parts methyl methacrylate , 35.0 parts of 2-hydroxyethyl methacrylate, 4.0 parts of glycidyl methacrylate-, 2.0 parts of methacrylic acid, and 1.7 parts of benzene peroxide The bulk mixture was fed into a 500 m 1 four-necked flask, and the reactor was reacted at 95 ° C for 3 3 5 minutes under nitrogen gas flow and stirring. The feed was cooled to obtain a low-viscosity white suspension solution. Acrylic non-aqueous dispersion microgel, code DG-3. The solids content of the solution was 41.5% by weight, and the taper of B r ο κ k f i e 1 (25 ° C, 60 r p m) was 21.5 cps. After DG-3 was left to stand for 100 days, the container had only a small amount of dispersible flocculent deposits', which showed excellent storage dispersibility. After the solvent was dried, it was white fine powder. Take 7 0.0 parts of DG-3 and mix with 28.0 parts of Cyme 1® 1 158 to obtain a mixture of 5 2 · 2 wt% solids, which is a coating composition containing acrylic non-aqueous dispersion microgel , Code DGM-3, has a Brookfield viscosity (25 ° C, 60 · rpm) of 10 2 0 cps, fineness &lt; 0.5 / m, and can be used for spraying industrial baking-paint ingredients applications. Example 7 Manufacture of high solid content automotive silver powder paint 14.65 parts of hydroxyl-containing high solid acrylic resin (solid content 74.0% by weight), 6.14 parts of thickened hydroxyl-containing acrylic Resin (solid content of 60.0% by weight), 34.31 parts of DG-2 (from Example 5), 3.93 parts of baking paint wetting agent_MA, 1 4 · 3 6 彳 77 dimer oxygen Amine resin M B-2 9 6 6 7, 6 · 6 9 parts of cross-linking hardening catalyst I 3 4 6-3 0, 1 5 · 1 2 parts of silver paste and 4.7 parts of baking paint solvent R- 1 〇4 -0 3, etc., can be adjusted to make a silver powder paint with good dispersibility, which is a coating composition containing acrylic microgel. Its spray viscosity (No. 4 Ford Cup, 25 ° C) was 15.8 seconds, and the solid content was 27.3% by weight. Paint film 2 0 ◦ gloss is 9 2, 6 0 ◦ gloss

Page 20593587 ----- Case No. 91137447_ Car Moon Day ___ V. Description of the invention (15) is 1 0 1; Ford image is 1, color difference △ E (M i η ο 11 a 1 0 light source D6 5) is 1.8 to 2.2. Example 8 Manufacture of high-solid-state automotive silver powder paint Take 15.50 parts of acrylic resin with high-solids content (solid content 7 4 · 0 reset%), 6.50 parts of thickening type containing Hydroxy acrylic resin (solid content 60. 0% by weight), 30. 50 parts of DG-3 (from Example 6), 4. 15 parts of baking humectant MA, 15. 20 parts of melamine Resin mb- 2 9 6 6 7, 7.0 0 parts of cross-linking curing catalyst 1 3 4 6-3 0, 16. 00 parts of silver paste and 5. 07 parts of baking paint solvent R- 1 0 4- 0 3 etc.

Xinhe ’can be adjusted to make a silver powder paint with good dispersibility. Coating composition. Its spray viscosity (No. 4 Ford Cup, 20.5 ° C) is 14 · 2 seconds' solid content of 29 · 5% by weight. The paint film surface is good, 20. The gloss was 9 3 '6 0. The gloss is 10 2; the Ford image is 6, and the color difference Δ E (Mlno1 ta 10 ° / light source D65) is 0.4 to 1.2. ^ From the above examples, it can be known that melamine resin (such as Cymel® 1 158) etherified with part or all of butane, combined with other reactive functions ^ = unsaturated monomer (such as methacrylic acid, methyl Acrylic glycidol 'from 2nd, etc.)' Synthesizable microgel non-aqueous dispersion system with good dispersibility and storage stability 'and better compatibility with melamine-formaldehyde resin hardener; 1⑧115 8 instead of complete formazan Etherified melamine-formate E].歹 口 ymel㊣3 0 3), it is not necessary to use a higher boiling point (higher than 40 C) ♦ 刎, and it is not necessary to temperature in the microgel non-aqueous dispersion system to complete the cross-linking reaction in a single period so it can be significant = = $ 2 and using Cymel® 1158 with pendant acrylic resin: 2 2 Post-crosslinking can prevent premature agglutination of NAD, improve NAD team girls, and help with melamine-formaldehyde Resin hardener compatibility

Page 22 593587 Case No. 91137447 Revised

Page 23

Claims (1)

593587 Case No. 91137447 A_η Modification Γ, patent application scope. An acrylic microgel resin composition, the solid content of which is from a) 3 to 65% by weight acrylic sheet having an epoxy group, a carboxyl group, or a hydroxyl group Or a combination thereof, the monomer is selected from glycidyl propionate, glycidyl methacrylate, acrylic acid, methacrylic acid, acrylic acid, ethyl methacrylate, hydroxyethyl methacrylate, hydroxy acrylate (B) 2 to 55% by weight of acrylic monomers having monofunctional groups, the monomers being C propane selected from acrylic acid or methacrylic acid Groups consisting of alkyl esters or cycloalkyl esters, c) 0.2 to 40% by weight of olefinic monomers, the monomers being styrene, acrylonitrile, maleic anhydride, styrene, vinyl acetate, etc. Composition group, d) 3 to 75% by weight of acrylic dispersant containing hydroxyl group and short side chain, the acrylic dispersant is composed of acrylic monomer having Wei group or mesogen, monofunctional C b36 Acrylic monomers with short side chains of alkyl ester groups and olefinic monomers are obtained by solution polymerization, It has a C 8_3 ethyl acetate-based short acrylic side chain, and (e) 0.1 to 30% by weight can react with these hydroxyl groups to form a crosslinked amine-based resin, the amine-based resin including all or part of an alkyl group The etherified melamine-acetaldehyde resin is dispersed and copolymerized in a solvent containing 25 to 95% by weight of an acrylic microgel resin composition mainly composed of an aliphatic hydrocarbon to obtain a non-aqueous dispersion system (NAD), and With the characteristics of substantial cross-linking. 2. The composition according to item 1 of the scope of the patent application, wherein (d) the acrylic dispersant having a hydroxyl group and a short side chain is composed of an acrylic monomer having a Wei group or a Jing group, a monofunctional C Acrylic monomers with short side chains of η-alkyl ester groups, and olefinic monomers P.24 593587 __Case No. 91137447_Year_Month__ VI. The scope of the patent application, copolymerization by solution polymerization method, and the acrylic resin solution obtained. 3. The composition according to item 2 of the scope of patent application, wherein the acrylic monomer having a Wei group is acrylic acid or methacrylic acid. 4. The composition according to item 2 of the scope of the patent application, wherein the acrylic monomer having a hydroxyl group is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, or methacrylic acid Hypromelline purpose. 5. The composition as described in item 2 of the scope of the patent application, wherein the acrylic monomer of the short-chain monofunctional C-endyl group is C 1 3 4-endyl group of acrylic acid or methacrylic acid. Finish the base vinegar. 6. The composition according to item 2 of the scope of the patent application, wherein the olefinic monomer is styrene, acrylonitrile, maleic anhydride, styrene divinyl, or vinyl acetate. 7. The acrylic microgel resin composition as described in item 1 of the scope of the patent application, wherein the minimum radical of the melamine-acetaldehyde resin in which the alkyl group is fully or partially etherified is C1- "end group. 8. The acrylic microgel resin composition according to item 1 of the scope of patent application, wherein the acrylic microgel resin composition is a white fine powder after drying. 9. The composition as described in item 2 of the scope of the patent application, wherein the repeating unit with a short side chain of C 8-3 ester ester acrylic group accounts for 20 to 80% by weight of the solid content of the acrylic dispersant. 10. The composition as described in item 2 of the scope of the patent application, which has a hydroxyl group :): a repeating unit of short acrylic side chain, which accounts for 3 to 50% by weight of the solid content of the acrylic dispersant. 1 1. The composition according to item 2 of the scope of patent application, wherein the acrylic point Page 25 593587 __Case No. 91137447_Year_Month__ VI. Scope of patent application The acid value of the solid content of the powder is 0.4 to 150 m g K 0 H / g. 1 2. The composition according to item 2 of the scope of the patent application, wherein the repeating unit having a short-chain side chain of C alkyl ester group and the repeating unit of the olefinic monomer together occupy the solid form of the acrylic dispersant 3 to 70% by weight. 1 3. The acrylic microgel resin composition according to item 1 of the scope of patent application, wherein the amount of the acrylic monomer having an epoxy group is the solid state of the acrylic microgel resin composition Parts from 0.2 to 15% by weight. 14. The acrylic microgel resin composition according to item 1 of the scope of the patent application, wherein the amount of the acrylic monomer having a hydroxyl group is the solid content of the acrylic microgel resin composition. 2 to 60% by weight. 1 5. The acrylic microgel resin composition according to item 1 of the scope of patent application, wherein the acid value of the solid content of the acrylic microgel resin composition is 0.4 to 15 0 mg K 0 H / g 〇 16. The acrylic microgel resin composition according to item 1 of the scope of patent application, wherein the internal cross-linking of the microgel includes the hydroxyl group of the acrylic monomer repeating unit and the amine -NHCH2OR or -NHCH2OH reaction mode of the base resin. 17. The acrylic microgel resin composition according to item 1 of the scope of the patent application, wherein the internal crosslinking of the microgel includes the reaction of the epoxy group of the acrylic monomer repeating unit with the carboxyl group. the way. 18. The acrylic microgel resin composition according to item 1 of the scope of patent application, wherein the acrylic microgel resin composition in a liquid or powder state can be fully or partially etherified with an alkyl group. The melamine-formaldehyde resin is homogeneously mixed with the amine-based resin. Page 26 593587 __Case No. 91137447_Year_Month__ VI. The scope of patent application 19. The acrylic microgel resin composition as described in the scope of patent application item 1, wherein the liquid or powder state Mixture of acrylic microgel resin composition and amine-based resin including melamine-formaldehyde resin with fully or partially etherified alkyl group can be baked and cross-linked and hardened at 90 ° to 230 ° C; its solid content mixing ratio From 0.05 to 100. 2 0. An acrylic transparent coating composition containing an acrylic microgel resin composition, including: (a) 0.4 to 7 2% by weight of a solid content of an acrylic copolymer containing a hydroxyl group and a carboxyl group, (b) 1 to 7 2 weight ° / ◦ solid content of the acrylic microgel resin composition as described in the first item of the patent application scope, and (c) 0.04 to 73.6% by weight can be combined with The hydroxyl group reacts to form a cross-linked amine-based resin, a blocked isocyanate resin, or a combination thereof, and (d) 25 to 95.5% by weight can be dissolved or dispersed (a) to (c). Organic solvent; wherein the ratio of [component (a) + component (b)] / [component (c)] is 0 · 0 2 to 10 0. 2 1. The acrylic transparent coating composition containing an acrylic microgel resin composition as described in item 20 of the scope of patent application, which can be hardened by baking and crosslinking at 90 to 230 ° C. 2 2. —Acrylic coloring coating composition containing acrylic microgel resin composition; including # · (a) 0.4 ~ 70% by weight of solid content of hydroxyl-containing and carboxyl-containing acrylic copolymer (B) 1 to 70% by weight of the solid content of the acrylic microgel resin composition as described in item 1 of the scope of patent application, (c) 0. 4 to 7 2% by weight can be formed by reacting with a hydroxyl group Crosslinked Amine Tree Page 27 593587 __Case No. 91137447_Year_Month__ VI. The scope of patent application, sealed isocyanate resin, or a combination of solid components, (d) 0 · 0 1 ~ 50 0% by weight color Solid content of paste, (e) 0 · 0 1 ~ 30 wt% solid content of coating additive, and (f) 2 0 ~ 95 wt% organic solvent which can dissolve or disperse (a) ~ (e) solid content; The ratio of [component (a) + component (b)] / [component (c)] is 0 · 0 2 to 10 0. 2 3. The acrylic coloring coating composition containing the acrylic microgel resin composition according to item 22 of the scope of the patent application can be cured by baking cross-linking at 90 ~ 230 ° C. 2 4. —Acrylic silver powder paint coating composition containing acrylic microgel resin composition, including: (a) 0.4 to 70% by weight of solid content of hydroxyl- and carboxyl-containing acrylic copolymer (B) 1 to 70% by weight of the solid content of the acrylic microgel resin composition as described in item 1 of the scope of patent application, (c) 0. 4 to 7 2% by weight can be formed by reacting with a hydroxyl group Solid content of crosslinked amine-based resin, blocked isocyanate resin, or a combination thereof, (d) 0. 1 to 60 0% by weight of metal powder solid content, (e) 0. 0 1 to 3 0 Solid content of coating additive by weight, and (f) 15 to 95% by weight of organic solvent that can dissolve or disperse (a) to (e) solid content; wherein, [ingredient (a) + ingredient (b)] / [ The ratio of component (c)] is 0 · 0 2 to 10 0. 25.Acrylic silver powder paint coating composition containing acrylic microgel resin composition according to item 24 of the scope of patent application, which can be crosslinked by baking at 90 ~ 230 at 0 ° C. (The above columns are filled in by the Bureau.) Replace this. 9 ^ 3, Japanese application number: 91137447 Invention Patent Specification Chinese acrylic microgel resin composition and coating composition containing it Invention name English composltlon and coating comp〇sition Name (Chinese) Chen Zhizhen 2. Xu Yayi 3. Zhang Yihe inventors (total of 5 people), residence (Chinese 1. Chen, Chih-Chien 2. Hsu, Ya-I 3. Chang, Yih-Her 1. ROC ROC 2. ROC 3. ROC No. 321, Section 2, Guangfu Road, Zhushi City, Republic of China 1 f No. 321, Section 2, Guangfu Road, Jinzhu City i New Vr Ancient Land Index Yixun Q01 s account J · 嵆 corporate Industrial Technology Research Institute 2 · Central Coatings Industry Co., Ltd. applicant (total of 2 people) claims or names | (¾) Γ INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE Central paints industrial, Inc. 1 · ROC 2. ROC 1-Weng, Cheng-1 2.Chen Lien Hui