WO2022148399A1 - 一种氨基树脂醇酸消光漆 - Google Patents
一种氨基树脂醇酸消光漆 Download PDFInfo
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- WO2022148399A1 WO2022148399A1 PCT/CN2022/070523 CN2022070523W WO2022148399A1 WO 2022148399 A1 WO2022148399 A1 WO 2022148399A1 CN 2022070523 W CN2022070523 W CN 2022070523W WO 2022148399 A1 WO2022148399 A1 WO 2022148399A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- amino resin
- alkyd
- acrylate
- etherified
- resin
- Prior art date
Links
- 239000003973 paint Substances 0.000 title claims abstract description 59
- 229920003180 amino resin Polymers 0.000 title claims abstract description 46
- 229920000180 alkyd Polymers 0.000 title claims abstract description 40
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- -1 alkyl benzoguanamine Chemical compound 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 7
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 7
- 239000004359 castor oil Substances 0.000 claims abstract description 7
- 235000019438 castor oil Nutrition 0.000 claims abstract description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 7
- 239000004640 Melamine resin Substances 0.000 claims description 20
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 7
- 229920006305 unsaturated polyester Polymers 0.000 claims description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 3
- 150000007974 melamines Chemical class 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 239000006224 matting agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JIHOVGXINXMLLR-UHFFFAOYSA-N 2-n-phenyl-1,3,5-triazine-2,4,6-triamine Chemical class NC1=NC(N)=NC(NC=2C=CC=CC=2)=N1 JIHOVGXINXMLLR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- PFVDCMIRGITIHB-UHFFFAOYSA-N benzene 1,3,5-triazine-2,4,6-triamine Chemical compound N1=C(N)N=C(N)N=C1N.C1=CC=CC=C1 PFVDCMIRGITIHB-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
Definitions
- the invention belongs to the field of chemical coatings, in particular to an amino resin alkyd matte paint.
- Automotive interior materials are mainly composed of instrument panels, door panels, pillars, seats, ceilings, sun visors, side walls and other components.
- environmental protection recycling odor, haze, high and low temperature resistance, aging resistance, weather resistance, etc.
- the appearance of these parts has a common characteristic, the surface has decorative patterns, and the brightness tends to be extinct.
- a certain matting agent is generally added to the varnish, and the varnish containing the matting agent is coated on the surface of the substrate, and the paint film formed by the varnish is cured and shrunk after the matting agent It can be distributed on the surface of the paint film to reduce the reflection of incident light to achieve a matting effect.
- the matting effect of the paint film is related to the solid content of the paint.
- the solvent-based ink has a low solid content and a large degree of shrinkage of the paint film, which makes it easier to form a matte surface.
- the paint film has almost no shrinkage, and it is difficult to form a paint with a matting effect. membrane.
- the purpose of the present invention is to provide an amino resin alkyd matte paint to form a matte film with good matte effect on the surface of the substrate.
- an amino resin alkyd matte paint Calculated by mass percentage, its raw materials include: 30-50% of acrylate polymerized monomers, 15-30% of etherified alkyl benzene melamine resin, hydrogenated Castor oil 4-12%, polyhydroxyalkyl aliphatic carboxylic acid 4-10%.
- the amino resin obtained by polycondensing the etherified alkyl benzene melamine by grafting the triazine ring of the etherified melamine with the benzene ring has good extinction and hardness.
- the etherified alkyl benzene melamine The resin has low polarity and has good miscibility with a variety of alkyd resins.
- the etherified alkyl benzene melamine resin is used as the amino resin component to be coordinated with the alkyd resin, and the amino resin alkyd matte paint thus compounded has good matting property and fast drying.
- the paint film has good matting, high hardness and excellent weather resistance, not easy to yellow, suitable for outdoor use.
- the polycondensation monomer of the etherified alkyl benzene melamine resin is etherified alkyl benzene melamine, and the number of carbon atoms included in the main carbon chain of the etherified alkyl group on the etherified alkyl benzene melamine is not low. on 10. Therefore, the network structure with the etherified alkyl benzene substituted melamine as the crosslinking center is relatively concentrated, and the matting paint containing the network structure can form a dense paint film.
- the number of carbon atoms included in the main carbon chain of the etherified alkyl group on the etherified alkyl benzene-substituted melamine is 4-10.
- the length of the etherified alkyl group is within the above-mentioned range, so that the steric hindrance effect on the polysubstituted triazine ring is alleviated, so that the polymerization reaction can proceed smoothly.
- the triazine ring and the benzene ring in the etherified alkyl benzene melamine belong to the hard segment, while the etherified alkyl group belongs to the soft segment.
- the polyhydroxyalkyl aliphatic carboxylic acid is dimethylol butyric acid.
- the acrylate polymerizable monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. at least one.
- the acrylate polymerization monomers include 10-20 parts of butyl methacrylate and 15-25 parts of ethyl acrylate.
- the raw material further includes 5-10% of hydroxy acrylate in terms of mass percentage.
- organic tin accounts for 0.2-0.5%
- persulfate accounts for 0.2-0.8%
- aromatic hydrocarbon solvent accounts for 10-20%
- drier accounts for 0.02% ⁇ 0.1%
- leveling agent accounts for 1.5 ⁇ 2.5%.
- the aromatic hydrocarbon solvent is xylene.
- the present embodiment is a preparation example of the etherified alkyl benzene-substituted melamine resin.
- the raw material formula of the etherified alkyl benzene-substituted melamine resin involved in Examples 2 to 4 is shown in Table 1, and its production process is as follows:
- Urea-formaldehyde resin, melamine resin and the butylated phenyl melamine resin prepared in Example 1 were respectively used as the amino resin shown in Table 2, prepared according to the raw material formula shown in Table 2, and prepared three kinds according to the following steps.
- Air is introduced into the cross-linked polyester and hydroquinone is added dropwise to block further cross-linking polymerization of the cross-linked polyester, and the temperature is naturally cooled;
- the three amino resin alkyd paints prepared in this example were diluted to a viscosity of 80,000 mPa s, and then prepared by using the above three amino resin alkyd matting paints according to the national standard "GB/T1727 General Preparation Method for Paint Films". Coating sample. Then, use the coating film sample to test the gloss, the test standard of gloss is GB/T9754-88, and the angle of 60° is selected for measurement. The test results are shown in Table 3.
- the three amino resin alkyd paints have good quick-drying and workability.
- the amino resin alkyd paint prepared by etherified benzoic melamine resin as the amino resin component has excellent matting properties, and the glossiness of the paint film formed by it is lower than 10°.
- the four etherified benzoic melamine resins prepared in Example 1 were respectively used as the amino resin components, and the materials were prepared according to the raw material formulations shown in Table 2 in Example 2, and the amino resin alkyd was prepared according to the methods provided in Example 2.
- the step of painting is to make paint, and the prepared paint is amino resin alkyd matte paint.
- the 4 kinds of amino resin alkyd matt paints obtained in this example were respectively diluted to a viscosity of 80000mPa s, and then the above 4 kinds of amino resin alkyd matt paints were respectively used according to the national standard "GB/T1727 General Preparation Method of Paint Films". Preparation of coating samples. Then use the coating sample to test the relevant properties.
- the relevant test standards are as follows: pencil hardness, QZTB J00013A-2016; flexibility, GB/T1731-79; adhesion, GB/T1720-79; abrasion resistance, GB/T15102 -94; Gloss, GB/T9754-88, measured at an angle of 60°.
- the test results are shown in Table 4.
- the 4 amino resin alkyd matt paints prepared in this example all have good coating effects.
- the length of the main carbon chain increases, and the mechanical properties such as hardness, flexibility, adhesion and abrasion resistance of the paint film formed by the amino resin alkyd matt paint have been optimized.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
本发明提供一种氨基树脂醇酸消光漆，按照质量百分比计算，其原料包括：丙烯酸酯聚合单体30～50％、醚化烷基苯代三聚氰胺树脂15～30％、氢化蓖麻油4～12％、多羟烷基脂肪族羧酸4～10％。利用苯环接枝醚化三聚氰胺的三嗪环，以由此形成的醚化烷基苯代三聚氰胺缩聚而成的氨基树脂具有良好的消光性和硬度，另一方面，醚化烷基苯代三聚氰胺树脂极性较低，与多种醇酸树脂有着良好的混溶性。本发明采用醚化烷基苯代三聚氰胺树脂作为氨基树脂组分，使之与醇酸树脂相配合，由此复配而成的氨基树脂醇酸消光漆具备良好的消光性和干燥快速，其所形成的漆膜具备良好的消光性、较高的硬度以及优异的耐候性，不易黄变，适于户外使用。
Description
本发明属于化工涂料领域，具体地，涉及一种氨基树脂醇酸消光漆。
汽车内饰材料主要由仪表板、门板、立柱、座椅、顶棚、遮阳板、侧围等部件组成。随着人们环保意识的增强，对汽车内饰材料的内在品质，如环保回收、气味、雾度、耐高、低温、耐老化、耐候性等要求越来越严格。这些部件外观都有一个共同的特性，表面有装饰性的花纹，光亮度都趋向于消光。
目前，为了在基材表面营造消光的效果，一般在光油中添加一定的消光剂，将含有消光剂的光油涂装于基材表面，光油所形成的漆膜在固化收缩后消光剂可以分布在漆膜表面，减少入射光线的反射以达到消光效果。但漆膜消光效果与涂料的固含量有关，溶剂型油墨固含量低，漆膜收缩程度大，更易形成消光表面，而UV光油固含量高，漆膜几乎无收缩，难以形成具有消光效果漆膜。若需要形成光泽度较小的超哑光漆膜，则需要在UV光油中添加较高比例的消光剂，易导致UV光油固化速度降低，同时在生产过程中，易因消光剂分布不均匀或漆膜厚度不均匀导致漆膜光泽度不稳定，不能获得均匀的消光漆膜。此外涂层中的消光剂含量过高易导致漆膜表面的硬度、耐磨性能降低，且漆膜触感不明显，无法满足客户对于深消光、高耐磨、耐刮擦、耐化学品、耐候、耐UV的漆膜的需求。
发明内容
本发明的目的在于提供一种氨基树脂醇酸消光漆，以在基材表面形成消光效果好的哑光膜。
根据本发明的一个方面，提供一种氨基树脂醇酸消光漆，按照质量百分比计算，其原料包括：丙烯酸酯聚合单体30～50％、醚化烷基苯代三聚氰胺树脂15～30％、氢化蓖麻油4～12％、多羟烷基脂肪族羧酸4～10％。利用苯环接枝醚化三聚氰胺的三嗪环，以由此形成的醚化烷基苯代三聚氰胺缩聚而成的氨基树脂具有良好的消光性和硬度，另一方面，醚化烷基苯代三聚氰胺树脂极性较低，与多种醇酸树 脂有着良好的混溶性。本发明采用醚化烷基苯代三聚氰胺树脂作为氨基树脂组分使之与醇酸树脂向配合，由此复配而成的氨基树脂醇酸消光漆具备良好的消光性和干燥快速，其所形成的漆膜具备良好的消光性、较高的硬度以及优异的耐候性，不易黄变，适于户外使用。
优选地，醚化烷基苯代三聚氰胺树脂的缩聚单体为醚化烷基苯代三聚氰胺，醚化烷基苯代三聚氰胺上的醚化烷基的主碳链所包括的碳原子个数不低于10。由此，以醚化烷基苯代三聚氰胺作为交联中心的网状结构相对集中，含有该网状结构的消光漆能够形成致密的漆膜。
优选地，醚化烷基苯代三聚氰胺上的醚化烷基的主碳链所包括的碳原子个数为4～10。使醚化烷基的长度位于上述范围内，缓和了多取代三嗪环上的位阻效应，使聚合反应能够顺利进行。另一方面，醚化烷基苯代三聚氰胺中的三嗪环和苯环属于硬段，而醚化烷基属于软段，通过增长醚化烷基的链长，增加醚化烷基苯代三聚氰胺中软段的比例，以提高漆料的可施工性。
优选地，多羟烷基脂肪族羧酸为二羟甲基丁酸。
优选地，丙烯酸酯聚合单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯中的至少一种。
优选地，按照质量份数计算，丙烯酸酯聚合单体包括甲基丙烯酸丁酯10～20份、丙烯酸乙酯15～25份。
优选地，按照质量百分比计算，其原料还包括羟基丙烯酸酯5～10％。羟基丙烯酸酯具有C＝C双键和COOR酯基双官能团，能够参与多种聚合反应，提高成膜性物质的交联度。
优选地，上述氨基树脂醇酸消光漆，按照以下方法制备：S1.在氮气气氛下，利用有机锡催化醚化烷基苯代三聚氰胺树脂、氢化蓖麻油和多羟烷基脂肪族羧酸在芳烃溶剂中交联聚合，生成预聚体；S2.向预聚体中添加羟基丙烯酸酯，使羟基丙烯酸酯与预聚体进行共聚，生成端基为C＝C的不饱和聚酯；S3.利用过硫酸盐引发不饱和聚酯和丙烯酸聚合单体发生聚合反应，生成交联聚酯；S4.向交联聚酯中滴加阻聚剂，阻断交联聚酯的进一步交联聚合；S5.向S4制得的浆料中添加催干剂和流平剂，混匀，过筛。
优选地，在上述氨基树脂醇酸消光漆的原料中，按照质量百分比计算，有机锡占0.2～0.5％、过硫酸盐占0.2～0.8％、芳烃溶剂占10～20％、催干剂占0.02～0.1％、流平剂占1.5～2.5％。
优选地，芳烃溶剂为二甲苯。
为了使本技术领域的人员更好地理解本发明方案，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。
实施例1
本实施例为醚化烷基苯代三聚氰胺树脂的制备实施例，实施例2～4中所涉及的醚化烷基苯代三聚氰胺树脂的原料配方如表1所示，其生产过程如下：
本实施例所制备的醚化烷基苯代三聚氰胺树脂的配方如表1所示，其生产的过程如下：
S1.根据表1备料；
S2.将甲醛、脂肪醇放入反应釜中，搅拌下加入碳酸镁、苯代三聚氰胺；
S3.搅匀后升温，并回流3小时；
S4.加入苯酐，调整pH至4.4～4.5，再回流2小时；
S5.加入二甲苯，搅匀后静置，分出水层；
S6.常压回流出水，知道104℃以上，树脂对200号油漆溶剂油容忍度为1∶4；
S7.蒸出过量脂肪醇，调整黏度，冷却过滤。
表1醚化烷基苯代三聚氰胺树脂的原料配方(质量份数)
采用不同种类的脂肪醇按照上述方法所制得的醚化烷基苯代三聚氰胺树脂所对应的聚合单体结构如下：(树脂种类，对应的聚合单体)
甲醚化苯代三聚氰胺树脂，
乙醚化苯代三聚氰胺树脂，
丙醚化苯代三聚氰胺树脂，
丁醚化苯代三聚氰胺树脂，
实施例2
1.制备氨基树脂醇酸漆
分别采用脲醛树脂、密胺树脂和实施例1所制备的丁醚化苯代三聚氰胺树脂作为表2中所示的氨基树脂，按照表2所示的原料配方备料，并按照以下步骤分别制备三种以不同种类的氨基树脂作为原料的氨基树脂醇酸漆：
S1.在氮气气氛下，向二甲苯中添加氨基树脂、氢化蓖麻油、二羟甲基丁酸和二月桂酸二丁基锡，在80℃下反应2小时，氨基树脂、氢化蓖麻油、二羟甲基丁酸在二月桂酸二丁基锡的催化下聚合，生成预聚体；
S2.向预聚体中添加丙烯酸羟乙酯，继续保温2小时，丙烯酸羟乙酯与预聚体进行共聚，生成端基为C＝C的不饱和聚酯；
S3.搅拌含有上述不饱和聚酯的反应液，向其中加入甲基丙烯酸丁酯和丙烯酸乙酯，然后加入过硫酸钾，引发不饱和聚酯和甲基丙烯酸丁酯、丙烯酸乙酯发生聚合反应，继续保温1.5小时，生成交联聚酯；
S4.向交联聚酯中通入空气并滴加对苯二酚，阻断交联聚酯的进一步交联聚合，自然降温；
S5.向S4制得的浆料中添加催干剂和流平剂，混匀，过筛。
表2氨基树脂醇酸漆的原料配方
2.制备涂膜及涂膜性能测试
分别将本实施例制得的3种氨基树脂醇酸漆稀释至粘度达到80000mPa·s，然后按国家标准《GB/T1727漆膜一般制备法》，分别采用上述3种氨基树脂醇酸消光漆制备涂膜样板。随后，利用涂膜样板进行光泽度的测试，光泽度的测试标准为GB/T9754-88，选用60°角度测定。测试结果如表3所示，三种氨基树脂醇酸漆都具备较好的快干性和施工性，相对于分别采用脲醛树脂、密胺树脂作为氨基组分的氨基树脂醇酸漆，采用丁醚化苯代三聚氰胺树脂作为氨基树脂组分制得的氨基树脂醇酸漆具备优良的消光性质，其所形成的漆膜的光泽度低于10°。
表3氨基树脂醇酸漆的涂装性能
实施例3
1.氨基树脂醇酸消光漆的制备
分别采用实施例1所制备的4种醚化苯代三聚氰胺树脂作为氨基树脂组分，根据实施例2中的表2所示的原料配方备料，并按照实施例2中提供的制备氨基树脂醇酸漆的步骤制漆，所制得的漆料为氨基树脂醇酸消光漆。
2.制备涂膜及涂膜性能测试
分别将本实施例制得的4种氨基树脂醇酸消光漆稀释至粘度达到80000mPa·s，然后按国家标准《GB/T1727漆膜一般制备法》，分别采用上述4种氨基树脂醇酸消光漆制备涂膜样板。随后利用涂膜样板进行相关性能的测试，相关的测试标准如下：铅笔硬度，QZTB J00013A-2016；柔韧性，GB/T1731-79；附着力，GB/T1720-79；耐磨性，GB/T15102-94；光泽度，GB/T9754-88，选用60°角度测定。
测试结果如表4所示，本实施例所制备的4中氨基树脂醇酸消光漆都具备良好的涂装效果，随着用于醚化苯代三聚氰胺树脂的聚合单体中的醚化烷基的主碳链长度增加，氨基树脂醇酸消光漆所形成的漆膜的硬度、柔韧性、附着力以及耐磨性等机械性能都得到了优化。
表4氨基树脂醇酸消光漆的性能测试
以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。
Claims (10)
- 一种氨基树脂醇酸消光漆，其特征在于，按照质量百分比计算，其原料包括：丙烯酸酯聚合单体30～50％、醚化烷基苯代三聚氰胺树脂15～30％、氢化蓖麻油4～12％、多羟烷基脂肪族羧酸4～10％。
- 如权利要求1所述氨基树脂醇酸消光漆，其特征在于：所述醚化烷基苯代三聚氰胺树脂的聚合单体为醚化烷基苯代三聚氰胺，所述醚化烷基苯代三聚氰胺上的醚化烷基的主碳链所包括的碳原子个数不低于10。
- 如权利要求2所述氨基树脂醇酸消光漆，其特征在于：所述醚化烷基苯代三聚氰胺上的醚化烷基的主碳链所包括的碳原子个数为4～10。
- 如权利要求1所述氨基树脂醇酸消光漆，其特征在于：所述多羟烷基脂肪族羧酸为二羟甲基丁酸。
- 如权利要求1所述氨基树脂醇酸树脂，其特征在于：所述丙烯酸酯聚合单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯中的至少一种。
- 如权利要求5所述氨基树脂醇酸树脂，其特征在于：按照质量份数计算，所述丙烯酸酯聚合单体包括甲基丙烯酸丁酯10～20份、丙烯酸乙酯15～25份。
- 如权利要求1所述氨基树脂醇酸消光漆，其特征在于：按照质量百分比计算，其原料还包括羟基丙烯酸酯5～10％。
- 如权利要求7所述氨基树脂醇酸消光漆，其特征在于，按照以下方法制备：S1.在氮气气氛下，利用有机锡催化所述醚化烷基苯代三聚氰胺树脂、所述氢化蓖麻油和所述多羟烷基脂肪族羧酸在芳烃溶剂中交联聚合，生成预聚体；S2.向所述预聚体中添加所述羟基丙烯酸酯，使所述羟基丙烯酸酯与所述预聚体进行共聚，生成端基为C＝C的不饱和聚酯；S3.利用过硫酸盐引发所述不饱和聚酯和所述丙烯酸聚合单体发生聚合反应，生成交联聚酯；S4.向所述交联聚酯中滴加阻聚剂，阻断所述交联聚酯的进一步交联聚合；S5.向所述S4制得的浆料中添加催干剂和流平剂，混匀，过筛。
- 如权利要求8所述氨基树脂醇酸消光漆，其特征在于，在其原料中，按照质量百分比计算，所述有机锡占0.2～0.5％、所述过硫酸盐占0.2～0.8％、所述芳烃溶剂占10～20％、所述催干剂占0.02～0.1％、所述流平剂占1.5～2.5％。
- 如权利要求9所述氨基树脂醇酸消光漆，其特征在于：所述芳烃溶剂为二甲苯。
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