CN1521225A - Acryl microgel resin composition and coating composition containing the same - Google Patents
Acryl microgel resin composition and coating composition containing the same Download PDFInfo
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- CN1521225A CN1521225A CNA031035736A CN03103573A CN1521225A CN 1521225 A CN1521225 A CN 1521225A CN A031035736 A CNA031035736 A CN A031035736A CN 03103573 A CN03103573 A CN 03103573A CN 1521225 A CN1521225 A CN 1521225A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 104
- 239000008199 coating composition Substances 0.000 title claims abstract description 31
- -1 Acryl Chemical group 0.000 title claims description 128
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 239000006185 dispersion Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 30
- 239000003973 paint Substances 0.000 claims abstract description 29
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 14
- 239000004615 ingredient Substances 0.000 claims abstract description 11
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract 7
- 150000002148 esters Chemical class 0.000 claims abstract 3
- 239000007787 solid Substances 0.000 claims description 53
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 208000034189 Sclerosis Diseases 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 4
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims 2
- VMKFRRNZAJNPPD-UHFFFAOYSA-N [Ag]C(=O)C=C Chemical compound [Ag]C(=O)C=C VMKFRRNZAJNPPD-UHFFFAOYSA-N 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 144
- 239000002270 dispersing agent Substances 0.000 abstract description 28
- 229920003180 amino resin Polymers 0.000 abstract description 17
- 238000004132 cross linking Methods 0.000 abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 16
- 230000000704 physical effect Effects 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 239000004332 silver Substances 0.000 abstract description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 22
- 229920003270 Cymel® Polymers 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 7
- 239000004640 Melamine resin Substances 0.000 description 7
- 125000005907 alkyl ester group Chemical group 0.000 description 7
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000004848 polyfunctional curative Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 229920006397 acrylic thermoplastic Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- JHGDVEYCZZGUIW-UHFFFAOYSA-N ethene styrene Chemical group C=C.C=C.C=CC1=CC=CC=C1 JHGDVEYCZZGUIW-UHFFFAOYSA-N 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种压克力微凝胶树脂组合物及含有它的涂料组合物，其具有良好物性，可应用于作为汽车涂料及银粉漆的配料。The invention relates to an acrylic microgel resin composition and a coating composition containing it. The composition has good physical properties and can be used as an ingredient for automobile coatings and silver powder paints.
背景技术Background technique
涂料工业从环保的观点出发，已积极降低挥发性有机化合物(VOC)的使用量。但当必须使用具有中或低固体份的涂料时，仍需要以挥发性有机化合物作为溶剂，所以发展了非水分散系(Non-Aqueous Dispersions，NAD)树脂，其是针对降低VOC、提高固体份的树脂配料系统所需而设计。为了让NAD树脂能分散于各种溶剂中，又不提高涂料系统的粘度，一般使NAD树脂分散相进行内部交联，形成微凝胶(Microgels)，这是一种有效可行的办法。然而，传统微凝胶树脂合成时，极易凝结集聚而结块沉底焦化；下料储存时，多数微凝胶树脂会凝集形成分离相而沉淀。再者，传统微凝胶树脂在使用时，颜料着色的分散性不良，原因之一是微凝胶的粒径太大，导致微观上的颜料相凝结，整个树脂系统倾向于不透明的色彩，因此无法适应现代汽车涂料色彩鲜明的要求。From an environmental standpoint, the coatings industry has actively reduced the use of volatile organic compounds (VOCs). However, when it is necessary to use a coating with a medium or low solid content, it is still necessary to use volatile organic compounds as a solvent, so a non-aqueous dispersion (Non-Aqueous Dispersions, NAD) resin has been developed, which is aimed at reducing VOC and increasing solid content. The resin batching system needs to be designed. In order to allow NAD resin to be dispersed in various solvents without increasing the viscosity of the coating system, the dispersed phase of NAD resin is generally internally cross-linked to form microgels (Microgels), which is an effective and feasible method. However, when the traditional microgel resin is synthesized, it is very easy to coagulate and aggregate, causing agglomerates to sink to the bottom and coke; when the material is stored, most microgel resins will coagulate to form a separated phase and precipitate. Furthermore, when the traditional microgel resin is used, the dispersibility of pigment coloring is poor. One of the reasons is that the particle size of the microgel is too large, which causes the microcosmic pigment phase to coagulate, and the entire resin system tends to be opaque. Therefore, It cannot adapt to the colorful requirements of modern automotive coatings.
美国专利第3,880,796号公开了一种含压克力微凝胶涂料的制法，其中：该微凝胶主要由含羟基压克力单体、羧基压克力单体，及含环氧基的接枝聚合物分散剂，在脂肪族烃溶剂中分散共聚而得到非水分散系统，并实质交联。该分散剂的接枝为长链聚(12-羟基硬脂酸)。该微凝胶也使用苯乙烯类非压克力单体共聚，可以一般胺基树脂交联硬化。U.S. Patent No. 3,880,796 discloses a method for preparing acrylic microgel coatings, wherein: the microgel is mainly composed of hydroxyl-containing acrylic monomers, carboxyl acrylic monomers, and epoxy-containing acrylic monomers. Graft polymer dispersant, dispersed and copolymerized in aliphatic hydrocarbon solvent to obtain a non-aqueous dispersion system, and substantially cross-linked. The dispersant is grafted with long chain poly(12-hydroxystearic acid). The microgel is also copolymerized with styrene-based non-acrylic monomers, which can be cross-linked and hardened with general amino-based resins.
美国专利第4,340,511号公开了一种压克力微凝胶的制法，其中该微凝胶主要由含官能基压克力单体、至少部分已烷基醚化的胺基树脂、及接枝聚合物分散剂，在脂肪族烃溶剂中分散共聚而得非水分散系；并以压克力单体官能基与胺基树脂产生实质交联。该分散剂的接枝为长链聚(12-羟基硬脂酸)。该专利也公开了一种含该压克力微凝胶的压克力涂料组成，其中包括：含羟基压克力与羧基压克力的共聚物、可溶解压克力共聚物的有机溶剂、及所制备的压克力微凝胶。U.S. Patent No. 4,340,511 discloses a method for preparing acrylic microgels, wherein the microgels are mainly composed of functional group-containing acrylic monomers, at least partially alkyl-etherified amino resins, and grafted Polymer dispersant, disperse and copolymerize in aliphatic hydrocarbon solvent to obtain non-aqueous dispersion system; and use acrylic monomer functional group to produce substantial crosslinking with amino resin. The dispersant is grafted with long chain poly(12-hydroxystearic acid). This patent also discloses an acrylic paint composition containing the acrylic microgel, which includes: a copolymer containing hydroxyl acrylic and carboxyl acrylic, an organic solvent that can dissolve the acrylic copolymer, and the prepared acrylic microgels.
美国专利第4,425,450号公开了一种含三聚氰胺树脂稳定化的压克力微凝胶的压克力涂料。其中包括：含羟基压克力共聚物、供交联硬化用的胺基树脂或异氰酸酯树脂、供流动控制添加剂用的三聚氰胺树脂稳定化的压克力微凝胶。该稳定化的压克力微凝胶的制法包括：(A)压克力微凝胶的部分是首先将含长链聚(12-羟基硬脂酸)酯基、C1-18烷酯基、环氧基压克力单体所合成的含环氧基压克力共聚物，与含羧基压克力单体反应，而得到具有不饱和基的压克力分散剂；然后利用该分散剂，与含C1-3烷酯基、环氧基、羧基、羟基压克力单体，以非水分散共聚方式合成非水分散系，并同时形成实质交联的压克力微凝胶。(B)将该微凝胶与丁基醚化的三聚氰胺树脂混合而得。US Patent No. 4,425,450 discloses an acrylic paint containing acrylic microgel stabilized with melamine resin. These include: acrylic copolymers containing hydroxyl groups, amine-based or isocyanate resins for cross-linking and hardening, and acrylic microgels stabilized with melamine resins for flow control additives. The preparation method of the stabilized acrylic microgel comprises: (A) the part of the acrylic microgel is first to contain long-chain poly(12-hydroxystearic acid) ester group, C 1-18 alkyl ester Epoxy group-containing acrylic copolymer synthesized from epoxy group-containing acrylic monomer, and react with carboxyl-containing acrylic monomer to obtain an acrylic dispersant with unsaturated groups; then use the dispersion agent, with acrylic monomers containing C 1-3 alkyl ester groups, epoxy groups, carboxyl groups, and hydroxyl groups, to synthesize a non-aqueous dispersion system by non-aqueous dispersion copolymerization, and at the same time form a substantially cross-linked acrylic microgel . (B) The microgel is mixed with butyl-etherified melamine resin.
由于NAD树脂的着色性差，通常并不单独使用，而是将NAD树脂搭配高固体份的压克力树脂、及三聚氰胺-甲醛(Melamine-formaldehyde)树脂硬化剂使用，具有降低高固体份压克力树脂的粘度、维持涂料的高固体份、赋予银粉漆的色彩鲜明等效果。其特点在于聚合分散剂系统与微凝胶交联度的设计。现有技术中压克力NAD树脂的聚合分散剂，是使用含聚(羟基硬脂酸)(Poly(hydroxystearic acid))的聚酯长侧链的梳型(Comb-)压克力共聚物，或使用完全压克力短侧链的压克力共聚物。但是，微凝胶中交联剂用量增加，不仅提高了微凝胶微粒内部的交联度，也提高了微凝胶微粒间交联的机会。后者将导致微凝胶NAD树脂粘度的窜升与凝集结块。Due to the poor colorability of NAD resin, it is usually not used alone. Instead, NAD resin is used together with high-solid acrylic resin and melamine-formaldehyde resin hardener to reduce high-solid acrylic. The viscosity of the resin, the maintenance of high solid content of the paint, and the vivid color of the silver powder paint. It is characterized by the design of the polymeric dispersant system and the degree of cross-linking of the microgel. The polymerization dispersant of acrylic NAD resin in the prior art is to use the comb-type (Comb-) acrylic copolymer containing the polyester long side chain of poly(hydroxystearic acid) (Poly(hydroxystearic acid)), Or use an acrylic copolymer with full 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 lead to a jump in the viscosity of the microgel NAD resin and coagulation and agglomeration.
因此，须选择适当的聚合分散剂系统，制造良好的非水分散系树脂，形成具有良好物性的涂料组合物，才能避免上述等等问题。Therefore, it is necessary to select an appropriate polymeric dispersant system, produce a good non-aqueous dispersion resin, and form a coating composition with good physical properties, in order to avoid the above problems and so on.
若微凝胶的合成系统中，同时含有适量的三聚氰胺树脂，以及环氧基压克力单体(例如甲基丙烯酸缩水甘油酯(Glycidyl methaerylate，GMA))，则三聚氰胺树脂一方面与含羟基压克力短侧链的压克力共聚物反应，生成含三聚氰胺树脂官能基的分散剂，增进了NAD树脂的分散与储存稳定性；另一方面与GMA共同增进含羟基及含羧基压克力NAD树脂分子内的交联度。因此可改善上述的问题，使微凝胶NAD树脂可应用于汽车着色涂料或银粉漆的配料。If the microgel synthesis system contains an appropriate amount of melamine resin and epoxy-based acrylic monomer (such as glycidyl methacrylate (Glycidyl methaerylate, GMA)), then the melamine resin and hydroxyl-containing acrylic The reaction of acrylic copolymers with short side chains of acrylics produces dispersants containing melamine resin functional groups, which improves the dispersion and storage stability of NAD resins; The degree of crosslinking within the resin molecule. Therefore, the above-mentioned problems can be improved, so that the microgel NAD resin can be applied to the ingredients of automobile colored paint or silver powder paint.
发明内容Contents of the invention
本发明的目的是提供一种压克力微凝胶树脂组合物，其由(a)具有环氧基、羧基、或羟基的压克力单体或其混合物，(b)具有单官能基的压克力单体，(c)烯型单体，(d)含羟基压克力短侧链的压克力分散剂，该压克力分散剂具有C8-36烷酯基压克力短侧链，及(e)可与所述羟基反应而形成交联的胺基树脂，该胺基树脂包括烷基完全或部分醚化的三聚氰胺-甲醛树脂，在以脂肪族烃为主的溶剂中分散共聚而得非水分散系统(NAD)，并实质交联而得。The object of the present invention is to provide an acrylic microgel resin composition, which consists of (a) acrylic monomers or mixtures thereof with epoxy groups, carboxyl groups, or hydroxyl groups, (b) acrylic monomers with monofunctional groups Acrylic monomer, (c) ethylenic monomer, (d) acrylic dispersant containing hydroxyl acrylic short side chain, the acrylic dispersant has C 8-36 alkyl ester group acrylic short side chains, and (e) an amino resin capable of reacting with said hydroxyl groups to form a crosslink, the amino resin comprising a fully or partially etherified melamine-formaldehyde resin in an aliphatic hydrocarbon-based solvent Non-aqueous dispersion system (NAD) obtained by dispersion copolymerization, and obtained by cross-linking substantially.
本发明的又一目的是提供一种含有上述压克力微凝胶树脂组合物的压克力透明涂料组合物。Another object of the present invention is to provide an acrylic clear coating composition containing the acrylic microgel resin composition.
本发明的又一目的是提供一种含有上述压克力微凝胶树脂组合物的压克力着色涂料组合物。Another object of the present invention is to provide an acrylic colored paint composition containing the above-mentioned acrylic microgel resin composition.
本发明的再一目的是提供一种含有上述压克力微凝胶树脂组合物的压克力微凝胶组合物银粉漆涂料组合物。Another object of the present invention is to provide an acrylic microgel composition silver powder paint coating composition containing the acrylic microgel resin composition.
与现有技术相比较，由于本发明的压克力微凝胶树脂组合物微观组成均匀性较优，折射率差异性小，故含有本发明压克力微凝胶树脂组合物的涂料组合物所形成的涂膜透明性更高，由涂膜映像度测试可说明其差异；且其VOC使用量可降低，且粘度并不变大，仍具有良好物性，例如流变性、加工性优良等，更适用于用作汽车涂料及银粉漆的配料。Compared with the prior art, because the microscopic composition uniformity of the acrylic microgel resin composition of the present invention is better, and the difference in refractive index is small, the coating composition containing the acrylic microgel resin composition of the present invention The formed coating film has higher transparency, and the difference can be explained by the coating film image degree test; and its VOC consumption can be reduced, and the viscosity does not increase, and it still has good physical properties, such as rheological properties, excellent processability, etc. It is more suitable for use as an ingredient in automotive coatings and silver powder paints.
本发明提供了一种压克力微凝胶树脂组合物，其由The invention provides an acrylic microgel resin composition, which consists of
(a)具有环氧基、羧基、或羟基的压克力单体、或其混合物，(a) an acrylic monomer having an epoxy group, a carboxyl group, or a hydroxyl group, or a mixture thereof,
(b)具有单官能基的压克力单体，(b) acrylic monomers with monofunctional groups,
(c)烯型单体，(c) ethylenic monomers,
(d)含羟基压克力短侧链的压克力分散剂，该压克力分散剂具有C8-36烷酯基压克力短侧链，及(d) an acrylic dispersant containing a hydroxyl acrylic short side chain, the acrylic dispersant has a C 8-36 alkyl ester group acrylic short side chain, and
(e)可与所述羟基反应而形成交联的胺基树脂，该胺基树脂包括烷基完全或部分醚化的三聚氰胺-甲醛树脂，(e) amine-based resins capable of reacting with said hydroxyl groups to form crosslinks, the amine-based resins comprising melamine-formaldehyde resins with fully or partially etherified alkyl groups,
在以脂肪族烃为主的溶剂中分散共聚而得非水分散系统(NAD)，并实质交联而得。Non-aqueous dispersion system (NAD) is obtained by dispersion copolymerization in aliphatic hydrocarbon-based solvent, and obtained by substantial cross-linking.
此压克力微凝胶为饱和的压克力共聚物，分子量大约在2,000至100,000范围内，优选在4,000至40,000的范围内。所述的C8-36烷酯基压克力短侧链优选为C12-18烷酯基压克力短侧链。The acrylic microgel is a saturated acrylic copolymer with a molecular weight in the range of approximately 2,000 to 100,000, preferably in the range of 4,000 to 40,000. The C 8-36 alkyl ester acrylic short side chain is preferably a C 12-18 alkyl ester acrylic short side chain.
本文中的压克力(Acrylic)单体及压克力(Acrylics)指丙烯酸、甲基丙烯酸、丙烯酸酯类、甲基丙烯酸酯类等具有单官能基或多官能基的单体、以及由这些单体共聚而得到的聚合物。Acrylic (Acrylic) monomers and Acrylics (Acrylics) herein refer to acrylic acid, methacrylic acid, acrylates, methacrylates, etc. A polymer obtained by copolymerizing monomers.
所述的具有环氧基的压克力单体为丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯。The acrylic monomer with epoxy group is glycidyl acrylate or glycidyl methacrylate.
所述的具有羧基的压克力单体为丙烯酸或甲基丙烯酸。The acrylic monomer with carboxyl group is acrylic acid or methacrylic acid.
所述的具有羟基的压克力单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、或甲基丙烯酸羟丙酯。The acrylic monomer with hydroxyl group is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate.
所述的单官能基的压克力单体为丙烯酸或甲基丙烯酸的C1-8烷基酯或环烷基酯。The monofunctional acrylic monomer is C 1-8 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid.
所述的烯型单体为苯乙烯、丙烯、马来酐、苯二乙烯、或醋酸乙烯酯。The ethylenic monomer is styrene, propylene, maleic anhydride, styrene-diethylene, or vinyl acetate.
所述的胺基树脂为烷基完全或部分醚化的三聚氰胺-甲醛树脂，优选为C1-4烷基完全或部分醚化的三聚氰胺-甲醛树脂。含有胺基树脂，尤其是烷基完全或部分醚化的三聚氰胺-甲醛树脂，具有改质的功能，使得压克力微凝胶树脂组合物的分散性更好，在与胺基树脂或封住型异氰酸树脂一起制成涂料组合物时，可增进分散与储存稳定性。The amino resin is a melamine-formaldehyde resin with fully or partially etherified alkyl groups, preferably a melamine-formaldehyde resin with fully or partially etherified C 1-4 alkyl groups. Amino-based resins, especially melamine-formaldehyde resins that are fully or partially etherified with alkyl groups, have the function of modifying, making the acrylic microgel resin composition better dispersible. When mixed with amine-based resins or sealed When used together with isocyanate resin to make coating composition, it can improve dispersion and storage stability.
本发明的压克力微凝胶树脂组合物中含羟基压克力短侧链的压克力分散剂是由具有羧基或羟基的压克力单体、单官能性C1-36烷酯基短侧链的压克力单体、及烯型单体，以溶液聚合法共聚，而得到的压克力树脂溶液。其中具有羧基的压克力单体为丙烯酸或甲基丙烯酸。具有羟基的压克力单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、或甲基丙烯酸羟丙酯。单官能性C1-36烷酯基短侧链的压克力单体为丙烯酸或甲基丙烯酸的C1-36烷基酯或环烷基酯，优选为丙烯酸或甲基丙烯酸的C1-18烷基酯或环烷基酯。烯型单体为苯乙烯、丙烯、马来酐、苯二乙烯、或醋酸乙烯酯。The acrylic dispersant containing hydroxyl acrylic short side chain in the acrylic microgel resin composition of the present invention is made of acrylic monomer with carboxyl or hydroxyl, monofunctional C 1-36 alkyl ester group The acrylic resin solution obtained by copolymerizing short-chain acrylic monomers and ethylenic monomers by solution polymerization. Among them, the acrylic monomer with carboxyl group is acrylic acid or methacrylic acid. The acrylic monomer having a hydroxyl group is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, or hydroxypropyl methacrylate. The acrylic monomer of monofunctional C 1-36 alkyl ester short side chain is C 1-36 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid, preferably C 1-36 acrylic acid or methacrylic acid 18 Alkyl or cycloalkyl esters. The ethylenic monomer is styrene, propylene, maleic anhydride, styrenediethylene, or vinyl acetate.
本发明的压克力微凝胶树脂组合物上的C8-36烷酯基短侧链可溶于以脂肪族烃为主的溶剂，而微凝胶上包括分散剂分子等其它部分则不溶于该以脂肪族烃为主的溶剂。The C 8-36 alkyl ester group short side chain on the acrylic microgel resin composition of the present invention is soluble in solvents based on aliphatic hydrocarbons, while other parts including dispersant molecules and the like are insoluble on the microgel in the aliphatic hydrocarbon-based solvent.
本发明的压克力微凝胶树脂组合物中，以脂肪族烃为主的溶剂占压克力微凝胶树脂组合物总重量的约25至95重量％，较佳为约35至80重量％，更佳为约40至70重量％。In the acrylic microgel resin composition of the present invention, the solvent based on aliphatic hydrocarbon accounts for about 25 to 95% by weight of the total weight of the acrylic microgel resin composition, preferably about 35 to 80% by weight %, more preferably about 40 to 70% by weight.
本发明的压克力微凝胶树脂组合物为乳液状，干燥后为白色微细粉末。The acrylic microgel resin composition of the present invention is in the form of emulsion, and becomes white fine powder after drying.
本发明的压克力微凝胶树脂组合物中，含羟基压克力短侧链的压克力分散剂的含量占压克力微凝胶树脂组合物固体份的约3至75重量％，较佳为5至40重量％。其中，存在具有C8-36烷酯基压克力短侧链的重复单元，占该含羟基压克力短侧链的压克力分散剂固体份的约20至80重量％，较佳为30至75重量％。具有羟基压克力短侧链的重复单元，占该含羟基压克力短侧链的压克力分散剂固体份的约3至50重量％，较佳为5至40重量％。该含羟基压克力短侧链的压克力分散剂固体份的酸值为约0.4至150mgKOH/g，较佳为1.0至100mgKOH/g。具有C1-7烷酯基压克力短侧链的重复单元与烯型单体重复单元，总和占该含羟基压克力短侧链的压克力分散剂固体份的约3至70重量％，较佳为5至40重量％。其中参与非水分散系(NAD)微凝胶聚合反应的该胺基树脂，其含量为该压克力微凝胶树脂组合物固体份的约0.1至30重量％，较佳为0.5至20重量％。In the acrylic microgel resin composition of the present invention, the content of the acrylic dispersant containing short acrylic hydroxyl chains 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 are repeating units with C 8-36 alkyl ester group acrylic short side chains, accounting for about 20 to 80% by weight of the acrylic dispersant containing hydroxyl acrylic short side chains, preferably 30 to 75% by weight. The repeating units with short hydroxyl acrylic side chains account for about 3 to 50% by weight, preferably 5 to 40% by weight, of the solid content of the acrylic dispersant containing short hydroxyl acrylic side chains. The solid content of the acrylic dispersant containing short hydroxyl acrylic side chains has an acid value of about 0.4 to 150 mgKOH/g, preferably 1.0 to 100 mgKOH/g. The repeating unit with C 1-7 alkyl ester group acrylic short side chain and the repeating unit of ethylenic monomer account for about 3 to 70 weight of the acrylic dispersant solid part of the acrylic dispersant containing hydroxyl acrylic short side chain %, preferably 5 to 40% by weight. Wherein the amino resin participating in the non-aqueous dispersion (NAD) microgel polymerization reaction, its content 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 %.
本发明的压克力微凝胶树脂组合物中，该具有环氧基的压克力单体的用量，为该压克力微凝胶树脂组合物固体份的约0.2至15重量％，较佳为0.5至10重量％。该具有羟基的压克力单体的用量，为该压克力微凝胶树脂组合物固体份的约2至60重量％，较佳为5至50重量％。该压克力微凝胶树脂组合物固体份的酸值为约0.4至150mgKOH/g，较佳为1.0至100mgKOH/g。该单官能基的压克力单体的用量，为该压克力微凝胶树脂组合物固体份的约2至55重量％，较佳为5至40重量％。该烯型单体的用量，为该压克力微凝胶树脂组合物固体份的约0.2至40重量％，较佳为1.0至30重量％。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% by weight of the solid content of the acrylic microgel resin composition, which is relatively Preferably it is 0.5 to 10% by weight. The amount of the acrylic monomer having a hydroxyl group is about 2 to 60% by weight, preferably 5 to 50% by weight, of the solid content of the acrylic microgel resin composition. The solid content of the acrylic microgel resin composition has an acid value of about 0.4 to 150 mgKOH/g, preferably 1.0 to 100 mgKOH/g. The amount of the monofunctional acrylic monomer is about 2 to 55% by weight, preferably 5 to 40% by weight, of the solid content of the acrylic microgel resin composition. The ethylenic monomer is used in an amount of about 0.2 to 40% by weight, preferably 1.0 to 30% by weight, of the solid content of the acrylic microgel resin composition.
本发明的压克力微凝胶树脂组合物中，当包括具有羟基的压克力单体重复单元时，该微凝胶内部交联是由压克力单体重复单元的羟基与胺基树脂的-NHCH2OR或-NHCH2OH交联反应所形成；当包括具有环氧基与羧基的压克力单体重复单元时，该微凝胶内部交联是由压克力单体重复单元的环氧基与羧基交联反应所形成。In the acrylic microgel resin composition of the present invention, when the acrylic monomer repeating unit having a hydroxyl group is included, the internal crosslinking of the microgel is formed by the hydroxyl group of the acrylic monomer repeating unit and the amino resin The -NHCH 2 OR or -NHCH 2 OH crosslinking reaction is formed; when the acrylic monomer repeating unit with epoxy and carboxyl groups is included, the internal crosslinking of the microgel is formed by the acrylic monomer repeating unit It is formed by the cross-linking reaction of epoxy group and carboxyl group.
本发明的压克力微凝胶树脂组合物，无论是液态或粉末态，均可单独与包括烷基完全或部分醚化的三聚氰胺-甲醛树脂的胺基树脂均匀混合。该混合物经烘烤可交联硬化；其固体份混合比为约0.02至100，较佳为0.05至20。The acrylic microgel resin composition of the present invention, no matter in liquid or powder state, can be uniformly mixed with amine-based resins including melamine-formaldehyde resins whose alkyl groups are fully or partially etherified. The mixture can be cross-linked and hardened after being baked; the solid content mixing ratio is about 0.02-100, preferably 0.05-20.
本发明还提供了一种含压克力微凝胶树脂组合物的压克力透明涂料组合物，其中包括：The present invention also provides an acrylic transparent coating composition containing acrylic microgel resin composition, comprising:
(a)含羟基及羧基压克力共聚物，(a) acrylic copolymers containing hydroxyl and carboxyl groups,
(b)可溶解(a)的压克力共聚物的有机溶剂，(b) an organic solvent capable of dissolving the acrylic copolymer of (a),
(c)如上述的本发明的压克力微凝胶树脂组合物，及(c) the acrylic microgel resin composition of the present invention as described above, and
(d)可与羟基反应而形成交联的胺基树脂、封住型异氰酸树脂、或其混合物。(d) Amino resins, blocked isocyanate resins, or mixtures thereof capable of reacting with hydroxyl groups to form crosslinks.
上述本发明的含压克力微凝胶树脂组合物的压克力透明涂料组合物中，该含羟基及羧基压克力共聚物、该压克力微凝胶树脂组合物、与上述成分(d)的混合物，可经烘烤交联硬化；其中压克力与胺基树脂(若包括封住型异氰酸树脂时，则为胺基树脂与异氰酸树脂的总和)的固体份混合比为约0.02至100，较佳为0.05至20。而其中含羟基及羧基压克力共聚物与压克力微凝胶树脂组合物，可以任何比例混合。In the above-mentioned acrylic transparent coating composition containing acrylic microgel resin composition of the present invention, the acrylic copolymer containing hydroxyl and carboxyl groups, the acrylic microgel resin composition, and the above-mentioned components ( The mixture of d) can be cross-linked and hardened by baking; wherein the acrylic is mixed with the solid content of the amino resin (if the blocked type isocyanic acid resin is included, it is the sum of the amino resin and the isocyanic acid resin) The ratio is about 0.02 to 100, preferably 0.05 to 20. Wherein, the acrylic copolymer containing hydroxyl group and carboxyl group and the acrylic microgel resin composition can be mixed in any proportion.
本发明还提供了一种含压克力微凝胶树脂组合物的压克力着色涂料组合物；其中包括：The present invention also provides an acrylic coloring coating composition containing an acrylic microgel resin composition; including:
(a)含羟基及羧基压克力共聚物，(a) acrylic copolymers containing hydroxyl and carboxyl groups,
(b)可溶解(a)的压克力共聚物的有机溶剂，(b) an organic solvent capable of dissolving the acrylic copolymer of (a),
(c)如上述的本发明的压克力微凝胶树脂组合物，(c) as above-mentioned acrylic microgel resin composition of the present invention,
(d)可与羟基反应而形成交联的胺基树脂、封住型异氰酸树脂、或其混合物，(d) Amino resins, blocked isocyanate resins, or mixtures thereof, capable of reacting with hydroxyl groups to form crosslinks,
(e)色浆，及(e) colorants, and
(f)涂料添加剂。(f) Coating additives.
上述含压克力微凝胶树脂组合物的压克力着色涂料组合物中，该含羟基及羧基压克力共聚物、该压克力微凝胶树脂组合物、与上述成分(d)的混合物，可经烘烤交联硬化；其中压克力与该胺基树脂(若包括封住型异氰酸树脂时，则为胺基树脂与异氰酸树脂的总合)的固体份混合比为约0.02至100，较佳为0.05至20。而其中该含羟基及羧基压克力共聚物与该压克力微凝胶树脂组合物，可以任何比例混合。In the above-mentioned acrylic colored coating composition containing acrylic microgel resin composition, the acrylic copolymer containing hydroxyl group and carboxyl group, the acrylic microgel resin composition, and the above component (d) The mixture can be cross-linked and hardened by baking; the solid content mixing ratio of acrylic to the amino resin (if the blocked isocyanic acid resin is included, it is the total of the amino resin and the isocyanic acid resin) It is about 0.02 to 100, preferably 0.05 to 20. Wherein the acrylic copolymer containing hydroxyl and carboxyl groups and the acrylic microgel resin composition can be mixed in any proportion.
本发明又再提供了一种含压克力微凝胶树脂组合物的压克力银粉漆涂料组合物，其中包括：The present invention provides a kind of acrylic silver powder paint coating composition containing acrylic microgel resin composition again, comprising:
(a)含羟基及羧基压克力共聚物，(a) acrylic copolymers containing hydroxyl and carboxyl groups,
(b)可溶解(a)的压克力共聚物之有机溶剂，(b) an organic solvent that can dissolve the acrylic copolymer of (a),
(c)如上述的本发明的压克力微凝胶树脂组合物，(c) as above-mentioned acrylic microgel resin composition of the present invention,
(d)可与羟基反应而形成交联的胺基树脂、封住型异氰酸树脂、或其混合物，(d) Amino resins, blocked isocyanate resins, or mixtures thereof, capable of reacting with hydroxyl groups to form crosslinks,
(e)金属粉浆，及(e) metal powder paste, and
(f)涂料添加剂。(f) Coating additives.
上述含压克力微凝胶树脂组合物的压克力银粉漆涂料组合物中，含羟基及羧基压克力共聚物、压克力微凝胶树脂组合物、与上述成分(d)的混合物，可经烘烤交联硬化；其中压克力与该胺基树脂(若包括封住型异氰酸树脂时，则为胺基树脂与异氰酸树脂的总合)的固体份混合比为约0.02至100，较佳为0.05至100。其中该含羟基及羧基压克力共聚物与该压克力微凝胶树脂组合物，可以任何比例混合。In the above-mentioned acrylic silver paint coating composition containing acrylic microgel resin composition, a mixture of acrylic copolymer containing hydroxyl and carboxyl groups, acrylic microgel resin composition, and the above-mentioned component (d) , can be cross-linked and hardened by baking; wherein the solid content mixing ratio of acrylic to the amino resin (if the blocked isocyanic acid resin is included, it is the sum of the amino resin and the isocyanic acid resin) is About 0.02 to 100, preferably 0.05 to 100. Wherein the acrylic copolymer containing hydroxyl and carboxyl groups and the acrylic microgel resin composition can be mixed in any proportion.
本发明的压克力微凝胶树脂组合物的制造方法，为先利用传统溶液聚合法，制备出本发明所公开的独特分散剂；然后通过公知的分散共聚合法，制备微凝胶。传统溶液聚合法可参照E.H.Riddle著“Monomeric AcrylicEsters”(1954)(Reinhold)第40～48页范例及说明。分散共聚合法则可参照K.E.J.Barrett著“Dispersion Polymerization in Organic Media”(1975)(John Wiley &Sons)第234～37页范例及说明。The manufacturing method of the acrylic microgel resin composition of the present invention is to first prepare the unique dispersant disclosed in the present invention by traditional solution polymerization method; then prepare the microgel by the known dispersion copolymerization method. For the traditional solution polymerization method, please refer to the examples and explanations on pages 40-48 of E.H. Riddle's "Monomeric Acrylic Esters" (1954) (Reinhold). Dispersion copolymerization rules can be referred to K.E.J.Barrett "Dispersion Polymerization in Organic Media" (1975) (John Wiley & Sons) page 234-37 examples and descriptions.
通过本领域内公知的方法，可将本发明的压克力微凝胶树脂组合物应用于压克力透明涂料组合物、压克力着色涂料组合物、压克力银粉漆涂料组合物。涂料组合物的配制，可参照美国专利第4391858号“涂覆方法(CoatingProcess)”(1983)所公开的方法。By methods known in the art, the acrylic microgel resin composition of the present invention can be applied to acrylic transparent coating compositions, acrylic colored coating compositions, and acrylic silver powder paint coating compositions. The preparation of the coating composition can refer to the method disclosed in US Patent No. 4391858 "Coating Process (Coating Process)" (1983).
本发明所提供的含压克力微凝胶树脂组合物的涂料组合物含有较少的VOC，粘度却不增加，具有优异的物性，尤其具有所需的流变性质，可将该类压克力涂料组合物以本领域中公知的方法，例如：喷涂、刷涂、辊涂、淋涂等施用于金属、汽车、木器、陶瓷等物品表面。在银粉漆涂料组合物方面的应用中，更能使组合物中的金属粉浆均匀分布，达到所欲之效果。例如，对涂膜福特映像度的测定，即说明了金属粉浆的分散状态。The coating composition containing the acrylic microgel resin composition provided by the present invention contains less VOC, does not increase the viscosity, has excellent physical properties, especially has the required rheological properties, and can make this type of acrylic The power coating composition is applied to the surface of metals, automobiles, woodware, ceramics and the like by methods known in the art, such as: spraying, brushing, roller coating, flow coating, etc. In the application of the silver powder paint coating composition, the metal powder slurry in the composition can be evenly distributed to achieve the desired effect. For example, the determination of the Ford image of the coating film shows the dispersion state of the metal powder slurry.
具体实施方式Detailed ways
为让本发明的目的、特征、和优点能更明显易懂，下文通过具体实施方式作详细说明如下，其中所述及的“份”除另有说明外，均为重量份。In order to make the purpose, features, and advantages of the present invention more comprehensible, specific implementation methods are described in detail below, and the "parts" mentioned herein are all parts by weight unless otherwise specified.
实施例1含羟基的完全压克力共聚物分散剂(代号D-1)的合成The synthesis of embodiment 1 hydroxyl-containing complete acrylic copolymer dispersant (code name D-1)
将288.6份二甲苯、32.0份丁醇、120.0份甲基丙烯酸甲酯、264.0份甲基丙烯酸十二烷基酯、91.2份甲基丙烯酸2-羟乙基酯、4.8份甲基丙烯酸及12.0份过氧化苯酰的烯型单体混合物，进料于500ml四颈瓶中，在通入氮气及定速搅拌下，反应器于115℃反应290分钟，冷却下料，即得淡黄色澄清透明溶液，代号D-1。该溶液固体份为57.1重量％，重量平均分子量＝12,000，分子量分布＝1.8。288.6 parts of xylene, 32.0 parts of butanol, 120.0 parts of methyl methacrylate, 264.0 parts of dodecyl methacrylate, 91.2 parts of 2-hydroxyethyl methacrylate, 4.8 parts of methacrylic acid and 12.0 parts The ethylenic monomer mixture of benzoyl peroxide is fed into a 500ml four-necked bottle. Under the nitrogen gas and constant speed stirring, the reactor is reacted at 115°C for 290 minutes, and the material is cooled to obtain a light yellow clear and transparent solution. , codenamed D-1. The solution had a solid content of 57.1% by weight, a weight average molecular weight of 12,000, and a molecular weight distribution of 1.8.
实施例2含羟基的完全压克力共聚物分散剂(代号D-2)的合成The synthesis of embodiment 2 hydroxyl-containing complete acrylic copolymer dispersant (code name D-2)
将108.10份乙酸丁酯、12.3份丁醇、33.6份甲基丙烯酸甲酯、108.1份甲基丙烯酸十八烷基酯(其中含35％甲基丙烯酸十六烷基酯)、36.2份甲基丙烯酸2-羟乙基酯、2.7份甲基丙烯酸及4.2份过氧化苯酰的烯型单体混合物，进料于500ml四颈瓶中，在通入氮气及定速搅拌下，反应器于100℃反应410分钟，冷却下料，即得淡黄色澄清透明溶液，代号D-2。该溶液固体份为59.4重量％，重量平均分子量＝17,600，分子量分布＝2.0。108.10 parts of butyl acetate, 12.3 parts of butanol, 33.6 parts of methyl methacrylate, 108.1 parts of octadecyl methacrylate (which contains 35% cetyl methacrylate), 36.2 parts of methacrylic acid 2-Hydroxyethyl ester, 2.7 parts of methacrylic acid and 4.2 parts of ethylenic monomer mixture of benzoyl peroxide are fed into a 500ml four-necked bottle, and the reactor is heated at 100°C under nitrogen gas and constant speed stirring. After reacting for 410 minutes, cooling and discharging, a light yellow clear and transparent solution was obtained, code-named D-2. The solution had a solid content of 59.4% by weight, a weight average molecular weight of 17,600, and a molecular weight distribution of 2.0.
实施例3含羟基的完全压克力共聚物分散剂(代号D-3)的合成The synthesis of embodiment 3 hydroxyl-containing complete acrylic copolymer dispersants (code name D-3)
将108.1份乙酸丁酯、12.0份丁醇、33.3份甲基丙烯酸甲酯、108.1份甲基丙烯酸十八烷基酯、36.7份甲基丙烯酸2-羟乙基酯、2.7份甲基丙烯酸及4.2份过氧化苯酰的烯型单体混合物，进料于500ml四颈瓶中，在通入氮气及定速搅拌下，反应器于100℃反应361分钟，冷却下料，即得淡黄色澄清透明溶液，代号D-3。该溶液固体份为59.9重量％，重量平均分子量＝13,600，分子量分布＝2.3。108.1 parts of butyl acetate, 12.0 parts of butanol, 33.3 parts of methyl methacrylate, 108.1 parts of octadecyl methacrylate, 36.7 parts of 2-hydroxyethyl methacrylate, 2.7 parts of methacrylic acid and 4.2 One part of ethylenic monomer mixture of benzoyl peroxide is fed into a 500ml four-necked bottle, and under nitrogen gas and constant speed stirring, the reactor is reacted at 100°C for 361 minutes, and the material is cooled to obtain light yellow, clear and transparent Solution, code-named D-3. The solution had a solid content of 59.9% by weight, a weight average molecular weight of 13,600, and a molecular weight distribution of 2.3.
实施例4压克力微凝胶树脂组合物(代号DG-1)的制备The preparation of embodiment 4 acrylic microgel resin composition (code name DG-1)
将145.2份Exxon公司之IsoparC、35.0份二甲苯、70.0份D-1、20.1份苯乙烯、50.0份甲基丙烯酸甲酯、24.2份丙烯酸2-羟乙基酯、4.0份甲基丙烯酸缩水甘油酯、2.0份甲基丙烯酸、及1.7份过氧化苯酰的烯型单体混合物，进料于500ml四颈瓶中，在通入氮气及搅拌下，反应器于100℃反应385分钟，冷却下料，即得低粘度白色悬浮溶液，为压克力非水分散系微凝胶，代号DG-1。该溶液固体份为42.2重量％。该溶液干燥后，呈白色微细粉末。145.2 parts of Exxon's Isopar C, 35.0 parts of xylene, 70.0 parts of D-1, 20.1 parts of styrene, 50.0 parts of methyl methacrylate, 24.2 parts of 2-hydroxyethyl acrylate, 4.0 parts of methacrylic acid shrink Glycerides, 2.0 parts of methacrylic acid, and 1.7 parts of ethylenic monomer mixture of benzoyl peroxide are fed into a 500ml four-necked bottle. Under nitrogen gas and stirring, the reactor is reacted at 100°C for 385 minutes, cooled The material is cut to obtain a low-viscosity white suspension solution, which is acrylic non-aqueous dispersion microgel, code-named DG-1. The solid content of the solution was 42.2% by weight. After drying, the solution is white fine powder.
取65.0份DG-1，与30.0份氰胺公司的Cymel1158、3.5份Exxon公司的IsoparE混合，得固体份52.1重量％的混合物，为含压克力非水分散系微凝胶的涂料组合物，代号DGM-1，其Brookfield粘度(20℃)为98cps，而可供喷涂型工业烤漆配料应用。然而，DG-1静置2周后，即逐渐形成絮凝沉积，说明其储存分散性不足。Get 65.0 parts of DG-1, mix with 30.0 parts of Cymel® 1158 of Cymel Corporation, 3.5 parts of Isopar® E of Exxon Corporation to obtain a mixture of 52.1% by weight of solids, which is a non-aqueous dispersion microgel containing acrylic The coating composition, code-named DGM-1, has a Brookfield viscosity (20°C) of 98 cps, and can be used as a spray-on industrial baking paint compounding application. However, after DG-1 stood still for 2 weeks, it gradually formed flocculation deposits, indicating that its storage dispersibility was insufficient.
实施例5压克力微凝胶树脂组合物(代号DG-2)的制备The preparation of embodiment 5 acrylic microgel resin composition (code name DG-2)
将120.1份Exxon公司的IsoparC、60.2份Exxon公司的IsoparE、67.4份的D-2、10.0份氰胺公司的Cymel1158、27.0份苯乙烯、32.1份甲基丙烯酸甲酯、35.7份甲基丙烯酸2-羟乙基酯、4.1份甲基丙烯酸缩水甘油酯、2.0份甲基丙烯酸、及1.7份过氧化苯酰的烯型单体混合物，进料于500ml四颈瓶中，在通入氮气及搅拌下，反应器于95℃反应395分钟，冷却下料，即得低粘度白色悬浊溶液，为压克力非水分散系微凝胶，代号DG-2。该溶液固体份为42.7重量％，Brookfield粘度(25℃，60rpm)为20.3cps。DG-2静置110天后，容器中仅有少量可分散絮凝沉积，说明其储存分散性优。溶剂干燥后，呈白色微细粉末。120.1 parts of Isopar® C of Exxon Company, 60.2 parts of Isopar® E of Exxon Company, 67.4 parts of D-2, 10.0 parts of Cymel® 1158 of Cymelamide Company, 27.0 parts of styrene, 32.1 parts of methyl methacrylate, 35.7 parts Parts of 2-hydroxyethyl methacrylate, 4.1 parts of glycidyl methacrylate, 2.0 parts of methacrylic acid, and 1.7 parts of ethylenic monomer mixture of benzoyl peroxide are fed in a 500ml four-necked bottle, in Introduce nitrogen and stir, react in the reactor at 95°C for 395 minutes, cool and discharge, and obtain a low-viscosity white suspension solution, which is acrylic non-aqueous dispersion microgel, code-named DG-2. The solid content of the solution was 42.7% by weight, and the Brookfield viscosity (25° C., 60 rpm) was 20.3 cps. After DG-2 stood still for 110 days, there was only a small amount of dispersible flocculation deposits in the container, indicating that its storage dispersibility is excellent. After the solvent is dried, it becomes white fine powder.
取72.0份DG-2，与25.5份Cymel1158混合，得固体份52.2重量％的混合物，为含压克力非水分散系微凝胶的涂料组合物，代号DGM-2，其Brookfield粘度(25℃，60rpm)为210cps，细度＜0.5μm，而可供喷涂型工业烤漆配料应用。Get 72.0 parts of DG-2, mix with 25.5 parts of Cymel 1158, obtain the mixture of 52.2% by weight of solids, be the coating composition that contains acrylic non-aqueous dispersion system microgel, code name DGM-2, its Brookfield viscosity ( 25°C, 60rpm) is 210cps, fineness <0.5μm, and can be used as a spray-on industrial baking varnish compounding application.
实施例6压克力微凝胶树脂组合物(代号DG-3)的制备The preparation of embodiment 6 acrylic microgel resin composition (code name DG-3)
将120.1份Exxon公司的IsoparC、60.1份Exxon公司的IsoparE、67.3份的D-3、10.0份氰胺公司的Cymel1158、27.7份苯乙烯、32.0份甲基丙烯酸甲酯、35.0份甲基丙烯酸2-羟乙基酯、4.0份甲基丙烯酸缩水甘油酯、2.0份甲基丙烯酸、及1.7份过氧化苯酰的烯型单体混合物，进料于500ml四颈瓶中，在通入氮气及搅拌下，反应器于95℃反应335分钟，冷却下料，即得低粘度白色悬浊溶液，为压克力非水分散系微凝胶，代号DG-3。该溶液固体份为41.5重量％，Brookfield粘度(25℃，60rpm)为21.5cps。DG-3静置100天后，容器中仅有少量可分散絮凝沉积，说明其储存分散性优。溶剂干燥后，呈白色微细粉末。120.1 parts of Isopar® C of Exxon Company, 60.1 parts of Isopar® E of Exxon Company, 67.3 parts of D-3, 10.0 parts of Cymel® 1158 of cyanamide company, 27.7 parts of styrene, 32.0 parts of methyl methacrylate, 35.0 parts Parts of 2-hydroxyethyl methacrylate, 4.0 parts of glycidyl methacrylate, 2.0 parts of methacrylic acid, and 1.7 parts of ethylenic monomer mixture of benzoyl peroxide are fed in a 500ml four-necked bottle, in Introduce nitrogen and stir, react in the reactor at 95°C for 335 minutes, cool and discharge, and obtain a low-viscosity white suspension solution, which is acrylic non-aqueous dispersion microgel, code-named DG-3. The solid content of the solution was 41.5% by weight, and the Brookfield viscosity (25° C., 60 rpm) was 21.5 cps. After DG-3 stood still for 100 days, there was only a small amount of dispersible flocculation deposits in the container, indicating that its storage dispersibility is excellent. After the solvent is dried, it becomes white fine powder.
取70.0份DG-3，与28.0份Cymel1158混合，得固体份52.2重量％的混合物，为含压克力非水分散系微凝胶的涂料组合物，代号DGM-3，其Brookfield粘度(25℃，60rpm)为1020cps，细度＜0.5μm，而可供喷涂型工业烤漆配料应用。Get 70.0 parts of DG-3, mix with 28.0 parts of Cymel 1158, obtain the mixture of 52.2% by weight of solids, be the coating composition that contains acrylic non-aqueous dispersion system microgel, code name DGM-3, its Brookfield viscosity ( 25°C, 60rpm) is 1020cps, fineness <0.5μm, and can be used for spraying industrial baking paint ingredients.
实施例7高固体份汽车银粉漆的制造The manufacture of embodiment 7 high solid content automotive silver powder paint
取14.65份含羟基高固体份压克力树脂(固体份74.0重量％)、6.14份增稠型含羟基压克力树脂(固体份60.0重量％)、34.31份DG-2(来自实施例5)、3.93份烤漆湿润剂MA、14.36份三聚氰胺树脂MB-29667、6.69份交联硬化剂I346-30、15.12份银浆与4.79份烤漆溶剂R-104-03等混合，可配制成分散性良好的银粉漆，为含压克力微凝胶的涂料组合物。其喷涂粘度(No.4福特杯，25℃)为15.8秒，固体份27.3重量％。烤漆膜20°光泽度为92，60°光泽度为101；福特映像度为1，色差ΔE(Minolta 10°/光源D65)为1.8至2.2。Get 14.65 parts of hydroxyl-containing high-solid acrylic resin (solid content 74.0% by weight), 6.14 parts of thickening type 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 varnish wetting agent MA, 14.36 parts of melamine resin MB-29667, 6.69 parts of cross-linking hardener I346-30, 15.12 parts of silver paste and 4.79 parts of baking paint solvent R-104-03, etc., can be prepared into a well-dispersed The silver powder paint is a paint composition containing acrylic microgel. Its spray viscosity (No. 4 Ford Cup, 25° C.) was 15.8 seconds, and its solid content was 27.3% by weight. The 20° gloss of the baking paint film is 92, and the 60° gloss is 101; the Ford image degree is 1, and the color difference ΔE (Minolta 10°/light source D65) is 1.8 to 2.2.
实施例8高固体份汽车银粉漆的制造The manufacture of embodiment 8 high solid automotive silver powder paint
取15.50份含羟基高固体份压克力树脂(固体份74.0重量％)、6.50份增稠型含羟基压克力树脂(固体份60.0重量％)、30.50份的DG-3(来自实施例6)、4.15份烤漆湿润剂MA、15.20份三聚氰胺树脂MB-29667、7.08份交联硬化剂I346-30、16.00份银浆与5.07份烤漆溶剂R-104-03等混合，可配制成分散性良好的银粉漆，为含压克力微凝胶的涂料组合物。其喷涂粘度(No.4福特杯，20.5℃)为14.2秒，固体份29.5重量％。烤漆膜表面良好，20°光泽度为93，60°光泽度为102；福特映像度为6，色差ΔE(Minolta 10°/光源D65)为0.4至1.2。Get 15.50 parts of hydroxyl-containing high-solid acrylic resin (solid content 74.0% by weight), 6.50 parts of thickening type hydroxyl-containing acrylic resin (solid content 60.0% by weight), 30.50 parts of DG-3 (from Example 6 ), 4.15 parts of baking varnish wetting agent MA, 15.20 parts of melamine resin MB-29667, 7.08 parts of crosslinking hardener I346-30, 16.00 parts of silver paste and 5.07 parts of baking varnish solvent R-104-03, etc., can be formulated to have good dispersion The silver powder paint is a coating composition containing acrylic microgel. Its spray viscosity (No. 4 Ford Cup, 20.5° C.) was 14.2 seconds, and its solid content was 29.5% by weight. The surface of the baked paint film is good, the 20° gloss is 93, and the 60° gloss is 102; the Ford image is 6, and the color difference ΔE (Minolta 10°/light source D65) is 0.4 to 1.2.
由上述实施例可知，以部分或全部丁烷醚化的三聚氰胺-甲醛树脂(例如Cymel1158)，结合含其它反应性官能基的不饱和单体(例如甲基丙烯酸、甲基丙烯酸缩水甘油酯等)，可合成分散性及储存稳定性良好的微凝胶非水分散系统，且与三聚氰胺-甲醛树脂硬化剂相溶性更佳；使用Cymel1158代替完全甲烷醚化的三聚氰胺-甲醛树脂(例如Cymel303)时，则无须使用高沸点(高于140℃)溶剂，且无须于微凝胶非水分散系统合成过程后期提高反应温度以完成Cymel303的交联反应，故可显著简化制造方法；及使用Cymel1158与含羟侧基压克力树脂分散剂的稍后交联作用，可避免NAD过早凝集，提高NAD的分散稳定性，且有助于与三聚氰胺-甲醛树脂硬化剂的兼容性，而具高度的实用性。As can be seen from the foregoing examples, melamine-formaldehyde resins (such as Cymel® 1158) that are partly or fully etherified with butane, combined with unsaturated monomers (such as methacrylic acid, glycidyl methacrylate) that contain other reactive functional groups etc.), can synthesize microgel non-aqueous dispersion system with good dispersibility and storage stability, and have better compatibility with melamine-formaldehyde resin hardener; Cymel® 303), there is no need to use a high boiling point (higher than 140 ° C) solvent, and it is not necessary to increase the reaction temperature in the late stage of the synthesis process of the microgel non-aqueous dispersion system to complete the crosslinking reaction of Cymel® 303, so the production can be significantly simplified Method; and use Cymel 1158 and later cross-linking of acrylic resin dispersant containing hydroxyl side group, can avoid premature aggregation of NAD, improve the dispersion stability of NAD, and contribute to the combination with melamine-formaldehyde resin hardener Compatibility, and a high degree of practicality.
以上本发明公开了较佳实施例，然而并非用以限定本发明。在不脱离本发明的精神和范围内，所作的更动与润饰，均在本发明的保护范围内。因此本发明的保护范围应以权利要求书所界定的范围为准。The above disclosures of the present invention disclose preferred embodiments, but are not intended to limit the present invention. Without departing from the spirit and scope of the present invention, changes and modifications made are within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the scope defined in the claims.
Claims (35)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006013061A1 (en) * | 2004-08-03 | 2006-02-09 | Imperial Chemical Industries Plc | Low voc coatings and paints |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006013061A1 (en) * | 2004-08-03 | 2006-02-09 | Imperial Chemical Industries Plc | Low voc coatings and paints |
| RU2395549C2 (en) * | 2004-08-03 | 2010-07-27 | Империал Кемикал Индастриз ПЛС | Protective coatings and paints with low content of volatile organic compounds |
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