CN117801158A - Organosilicon modified acrylic resin, preparation method and application thereof - Google Patents
Organosilicon modified acrylic resin, preparation method and application thereof Download PDFInfo
- Publication number
- CN117801158A CN117801158A CN202311788373.5A CN202311788373A CN117801158A CN 117801158 A CN117801158 A CN 117801158A CN 202311788373 A CN202311788373 A CN 202311788373A CN 117801158 A CN117801158 A CN 117801158A
- Authority
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- China
- Prior art keywords
- acrylic resin
- monomer
- modified acrylic
- water
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 114
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 114
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 238000000576 coating method Methods 0.000 claims abstract description 48
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000839 emulsion Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- -1 acrylic ester Chemical class 0.000 claims description 17
- 238000004945 emulsification Methods 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000001804 emulsifying effect Effects 0.000 claims description 14
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- 239000013530 defoamer Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- WAVDSLLYAQBITE-UHFFFAOYSA-N (4-ethenylphenyl)methanamine Chemical compound NCC1=CC=C(C=C)C=C1 WAVDSLLYAQBITE-UHFFFAOYSA-N 0.000 claims description 9
- ANRPYDCTHDLWGE-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;3-oxobutanoic acid Chemical compound CC(=O)CC(O)=O.CC(=C)C(=O)OCCO ANRPYDCTHDLWGE-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000002480 mineral oil Substances 0.000 claims description 6
- 235000010446 mineral oil Nutrition 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- 229920005646 polycarboxylate Polymers 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- YLIMHFXLIKETBC-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCC[Na] YLIMHFXLIKETBC-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 229920001220 nitrocellulos Polymers 0.000 abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 86
- 230000000052 comparative effect Effects 0.000 description 26
- 238000000465 moulding Methods 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 9
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 description 9
- 238000003825 pressing Methods 0.000 description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 7
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- BKPCSYKXYHOPNR-UHFFFAOYSA-N 4-(octadecylamino)-4-oxobutanoic acid Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCC(O)=O BKPCSYKXYHOPNR-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 5
- 238000007723 die pressing method Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005269 aluminizing Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CDQRKPZMCHTTPH-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)(=O)NC(CCC(=O)O)=O Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)NC(CCC(=O)O)=O CDQRKPZMCHTTPH-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001514 detection method 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
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to an organosilicon modified acrylic resin, a preparation method and application thereof, and relates to the field of acrylic resins. The organosilicon modified acrylic resin comprises the following raw materials in percentage by mass: 5-15% of acrylic monomer; 5-15% of methacrylate monomer; 3-8% of cross-linking agent monomer; 3-8% of organic silicon monomer; 1.5-5% of emulsifying agent; 1 to 2.5 percent of initiator; the balance of water; the organosilicon monomer is one or more of vinyl trimethoxy silane, vinyl triethoxy silane and (3-glycidoxypropyl) trimethoxy silane. The method can solve the difficult problem that the laser color layer coating needs three materials of acrylic resin, curing agent and nitrocotton to be matched, and avoids the harm of solvent type acrylic acid to human body and environment.
Description
Technical Field
The invention relates to the field of acrylic resin, in particular to an organosilicon modified acrylic resin, a preparation method and application thereof.
Background
The hot stamping printing of the electric aluminum is a special printing process different from the traditional printing process of ink printing, and when the electric aluminum hot stamping foil is used, the electric aluminum hot stamping foil is required to be used. The electrochemical aluminum stamping foil comprises a PET base film, a separating layer, a coloring information layer, an aluminum plating layer and a hot melt adhesive layer, wherein the coloring information layer is a main body for forming the electrochemical aluminum stamping foil and mainly comprises synthetic resin, the synthetic resin is directly coated on the surface of the separating layer or the base film after being dissolved and formed, and the coloring information layer of a laser product also needs to be processed through a mould pressing link. Holographic images with rainbow dynamic and three-dimensional effects can be transferred to a polyester film substrate with a specific resin coating through mould pressing, and when the images are transferred to the surface of a commodity package, the commodity obtains a laser effect.
The laser color layer of the electrochemical aluminum is required to be formed into a film and has good toughness, and the molding and vacuum aluminizing and thermoprinting processes need the temperature resistance of 140-170 ℃, so that the continuous molding can be ensured and the plate cannot be adhered. The existing laser color layer coating generally adopts solvent-type acrylic resin, and needs to be matched with a curing agent, nitrocotton and the like, wherein the acrylic resin is used as main resin, the color spreading performance is good, and the curing agent and the nitrocotton mainly provide the functions of temperature resistance and plate adhesion prevention.
When the laser color layer coating formed by matching solvent type acrylic resin, curing agent and nitrocotton is adopted, the selection and proportioning difficulty of the three materials is high, and the effects of clear pattern, qualified brightness and no sticking to the plate after mould pressing can be achieved only by strictly controlling the types and the dosage; meanwhile, the solvent type acrylic resin is prepared by adopting solvents such as toluene, butanone and the like, and the solvents can cause harm to human bodies and the environment.
Disclosure of Invention
The application provides an organosilicon modified acrylic resin, a preparation method and application thereof, solves the problem that three materials of acrylic resin, a curing agent and nitrocotton are required to be matched for laser color layer coating, and avoids the harm of solvent type acrylic acid to human body and environment.
In a first aspect, the present application provides an organosilicon modified acrylic resin, which adopts the following technical scheme:
the organosilicon modified acrylic resin comprises the following raw materials in percentage by mass:
5-15% of acrylic monomer;
5-15% of methacrylate monomer;
3-8% of cross-linking agent monomer;
3-8% of organic silicon monomer;
1.5-5% of emulsifying agent;
1 to 2.5 percent of initiator;
the balance of water;
wherein, the organic silicon monomer is one or more of vinyl trimethoxy silane, vinyl triethoxy silane and (3-glycidoxypropyl) trimethoxy silane.
By adopting the technical scheme, the organosilicon monomer is added to crosslink with the acrylic ester monomer, the methacrylic ester monomer and the crosslinking agent monomer, the organosilicon monomer has heat resistance and anti-adhesion, the acrylic resin formed by adding the post-crosslinking has good heat resistance, and the prepared laser color layer coating is softened and deformed under high-temperature die pressing but is not adhered to a die pressing plate, so that good laser effect is achieved. The acrylic resin which is more stable and easier to form a film can be prepared by using the acrylic monomer as a soft monomer and the methacrylic monomer as a structural framework. The acrylic resin can be used as a main resin, has good color development and molding property, and also has the functions of temperature resistance and sticking prevention. Therefore, when the acrylic resin is used for preparing the laser color layer coating, the laser color layer coating does not need to be matched with a curing agent or nitrocotton, and the difficult problem of matching of three materials is solved.
Most of the existing laser color layer coating is an oily system, most of the application is solvent-type acrylic resin, and the use of the solvent-type acrylic resin can cause harm to human bodies and the environment.
Optionally, the organosilicon monomer is modified (3-glycidoxypropyl) trimethoxysilane, and the modified (3-glycidoxypropyl) trimethoxysilane is prepared from the following raw materials in parts by weight:
35-55 parts of (3-glycidoxypropyl) trimethoxysilane;
13-20 parts of 4-vinylbenzylamine;
1-3 parts of a catalyst;
70-85 parts of solvent.
By adopting the technical scheme, the silane containing the epoxy group is modified by using the 4-vinylbenzylamine in advance, and the ring-opening reaction of the amino group and the epoxy group occurs under the action of the catalyst, so that the benzene ring is introduced into the organosilicon monomer, the introduction of the benzene ring further improves the molecular weight of the monomer, and the rigidity and toughness of the acrylic resin are enhanced, thereby being more beneficial to mould pressing.
Optionally, the cross-linking agent monomer is a mixture of methacrylic acid and acetoacetic acid ethylene glycol methacrylate, wherein the mass ratio of the methacrylic acid to the acetoacetic acid ethylene glycol methacrylate is (1.2-1.4) (0.8-1.1).
By adopting the technical scheme, the short-chain and long-chain crosslinking agent monomers are compounded and used, the functional groups with different carboxyl and amide bonds are used for crosslinking with other monomers, the curing of the acrylic resin is promoted by the compounded crosslinking agent monomers, the film forming toughness of the acrylic resin is improved, patterns with different degrees can be pressed on a molding link, the patterns are not adhered at a higher temperature, and continuous molding is facilitated.
Optionally, the acrylic ester monomer is selected from one or more of butyl acrylate, isooctyl acrylate, dodecyl acrylate and lauryl acrylate.
By adopting the technical scheme, the acrylic ester monomer is selected as the soft monomer, and the adhesive has the characteristic of being convenient for film formation.
Optionally, the methacrylate monomer is selected from one or more of n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate and dimethylaminoethyl methacrylate.
By adopting the technical scheme, the methacrylate monomer is selected as the structural framework, so that the methacrylate monomer can be easily copolymerized with other monomers, and the synthesized acrylic resin has better chemical stability.
Optionally, the emulsifier is selected from one or more of n-octyl sodium sulfate, dibutyl sodium sulfosuccinate, sodium sulfosuccinate mono-octadecyl amide sulfonate and polyoxyethylene nonylphenol ether.
By adopting the technical scheme, the monomer is stably dispersed in water through the emulsification of the emulsifier, so that the mechanical stability of the emulsion is kept without layering, and the crosslinking reaction is facilitated.
In a second aspect, the present application provides a method for preparing an organosilicon modified acrylic resin, comprising the steps of:
pre-emulsification: adding a proper amount of water and an emulsifying agent, stirring for 5-10min to wait for the emulsifying agent to dissolve, sequentially adding an acrylic monomer, a methacrylic monomer and a crosslinking agent monomer, emulsifying for 0.5-1h, sampling, checking and observing whether layering is carried out for 0.5h to obtain a pre-emulsion, and dividing the pre-emulsion into three parts, namely 15% -20%, 60% -70% and 10% -25% respectively;
seed polymerization: adding a proper amount of water and an emulsifying agent, stirring and heating to 70-75 ℃, stopping heating, adding a proper amount of an initiating agent and 15-20% of pre-emulsion, and performing seed polymerization to obtain a polymerization solution;
and (3) dropwise adding reaction: part of initiator is dissolved by water and is synchronously dripped into the polymerization solution with 60 to 70 percent of pre-emulsion, the dripping time is controlled to be 1.5 to 2.5 hours, the dripping temperature is 85 to 90 ℃, after the dripping is finished, the organosilicon monomer is added into the final 10 to 25 percent of pre-emulsion, the mixture is uniformly stirred, the mixture is continuously dripped into the polymerization solution, the dripping time is controlled to be 0.5 to 1 hour, and the temperature is controlled to be 80 to 85 ℃;
and (3) heat preservation: adding the rest initiator into the polymerization solution 15min after the dripping is finished, and preserving the temperature for 1-2h at 85-90 ℃;
and (3) cooling and neutralizing: after the heat preservation is finished, cooling to 60 ℃, adding neutralizer ammonia water or diethanolamine for neutralization, and detecting that the pH value reaches 7.5-8.5;
and (3) discharging and packaging: when the temperature is reduced to 50 ℃, the finished product is obtained by filtering and packing.
By adopting the technical scheme, the monomer is emulsified into the pre-emulsified liquid with a certain concentration by water before the polymerization reaction through pre-emulsification, so that compared with a direct polymerization method, the polymerization residue can be reduced, and the performance of the acrylic resin can be improved.
Optionally, when the organosilicon monomer is modified (3-glycidoxypropyl) trimethoxysilane, the preparation of the modified (3-glycidoxypropyl) trimethoxysilane comprises the following steps:
adding a solvent into a reaction kettle, adding (3-glycidoxypropyl) trimethoxysilane, 4-vinylbenzylamine and a catalyst under stirring, heating to 75-80 ℃, reacting for 2-3h, removing the solvent by reduced pressure rectification, cleaning and drying to obtain the modified (3-glycidoxypropyl) trimethoxysilane.
In a third aspect, the application provides an aqueous laser color layer coating, which comprises the following raw materials in parts by weight: 38-40 parts of any of the organic silicon modified acrylic resin suitable for the water-based laser color layer; 1-3 parts of a defoaming agent; 2-5 parts of wetting dispersant; 1-2 parts of a molding aid; 60-75 parts of absolute ethyl alcohol; 20-25 parts of water.
By adopting the technical scheme: the organosilicon modified acrylic resin has good color spreading property, good temperature resistance and good anti-sticking property, directly plays the roles of solvent type acrylic resin, curing agent and nitrocotton, is directly used for preparing the water-based laser color layer coating, and has good laser effect.
Optionally, the defoamer is one or more of aqueous mineral oil defoamer and aqueous molecular-level defoamer; the wetting dispersant is one or more of aqueous alkyne diol dispersants and aqueous polycarboxylate dispersants.
In summary, the present application has the following beneficial effects:
1. the organosilicon monomer is added to crosslink with acrylic ester monomer, methacrylic ester monomer and crosslinking agent monomer, the organosilicon monomer has heat resistance and anti-adhesion, the acrylic resin formed by adding after-crosslinking has good heat resistance, and the prepared laser color layer coating is softened and deformed under high-temperature mould pressing but is not adhered to a mould pressing plate, so that good laser effect is achieved. The acrylic resin which is more stable and easier to form a film can be prepared by using the acrylic monomer as a soft monomer and the methacrylic monomer as a structural framework. The acrylic resin can be used as a main resin, has good color development and molding property, and also has the functions of temperature resistance and sticking prevention. Therefore, when the acrylic resin is used for preparing the laser color layer coating, the laser color layer coating does not need to be matched with a curing agent or nitrocotton, and the difficult problem of matching of three materials is solved.
Most of the existing laser color layer coating is an oily system, most of the application is solvent-type acrylic resin, and the use of the solvent-type acrylic resin can cause harm to human bodies and the environment.
2. The silane containing epoxy groups is modified by using 4-vinylbenzylamine in advance, and the amino groups and the epoxy groups undergo ring-opening reaction under the action of a catalyst, so that benzene rings are introduced into the organosilicon monomer, the molecular weight of the monomer is further improved by introducing the benzene rings, the rigidity and toughness of the acrylic resin are enhanced, and the molding is facilitated.
Drawings
FIG. 1 is an apparent view of a laser pattern using comparative example 1;
FIG. 2 is an apparent diagram of a laser pattern using comparative example 2;
FIG. 3 is an apparent diagram of a laser pattern using comparative example 3;
FIG. 4 is an apparent view of a laser pattern of application example 1;
FIG. 5 is a laser beam paint prepared in application example 1;
FIG. 6 shows the electrochemical aluminum produced in application example 1.
Detailed Description
The present application will be described in further detail with reference to examples 1 to 9, comparative examples 1 to 3, application examples 1 to 9, and application comparative examples 1 to 3.
Examples
Example 1
Preparation of organosilicon modified acrylic resin pre-emulsification: adding 35kg of water into a pre-emulsifying kettle, starting stirring, adding 1.5kg of sodium salt of succinic acid mono-octadecyl amide sulfonate and 0.5kg of nonylphenol polyoxyethylene ether, stirring for 5min to completely dissolve the sodium salt of succinic acid mono-octadecyl amide sulfonate and nonylphenol polyoxyethylene ether, sequentially pumping 10kg of butyl acrylate, 12kg of n-butyl methacrylate and 5kg of hydroxypropyl acrylate into the pre-emulsifying kettle, waiting for emulsification for 0.5h, sampling and observing, wherein the pre-emulsifying liquid is milk-like and the emulsification succeeds if no layering occurs for 0.5h, layering indicates that the combination of the emulsifying agent fails, and obtaining pre-emulsifying liquid, wherein the pre-emulsifying liquid is divided into three parts, namely 20 parts of the first part, 60 parts of the second part and 20 parts of the third part;
seed polymerization: adding 20kg of water, 0.5kg of sodium salt of succinic acid mono-octadecanoyl amide sulfonate and 0.5kg of nonylphenol polyoxyethylene ether into a reaction kettle, stirring and heating, stopping heating after the heating reaches 70 ℃, adding 1kg of sodium persulfate, adding a first 20% pre-emulsion into the reaction kettle, starting seed polymerization, starting timing when blue light begins to appear in the reaction kettle, and finishing seed polymerization after 0.5 hour to obtain a polymerization solution;
and (3) dropwise adding reaction: dissolving 0.5kg of sodium persulfate with 7kg of water, and synchronously dripping the sodium persulfate and the second 60% of the pre-emulsion into the polymerization solution for 2 hours at the temperature of 85 ℃, adding 6kg of vinyltrimethoxysilane into the third 20% of the pre-emulsion after dripping, uniformly stirring, dripping the pre-emulsion added with vinyltrimethoxysilane into the polymerization solution for 0.5 hours at the temperature of 85 ℃;
and (3) heat preservation: adding 0.5kg of sodium persulfate into the polymerization solution 15min after the dripping is finished, and preserving the temperature at 85 ℃ for 1.5h;
and (3) cooling and neutralizing: after the heat preservation is finished, cooling to 60 ℃, adding neutralizer ammonia water for neutralization, and detecting that the pH value reaches 7.5;
and (3) discharging and packaging: when the temperature is reduced to 50 ℃, the finished product is obtained by filtering and packing.
Example 2
Preparation of organosilicon modified acrylic resin pre-emulsification: adding 46.5kg of water into a pre-emulsifying kettle, starting stirring, adding 0.7kg of sodium n-octyl sulfate and 0.3kg of dibutyl sodium sulfosuccinate, stirring for 10min to completely dissolve the sodium n-octyl sulfate and the dibutyl sodium sulfosuccinate, sequentially pumping 5kg of tributyl acrylate, 5kg of lauryl methacrylate and 3kg of methacrylic acid into the pre-emulsifying kettle, waiting for emulsification for 0.5h, sampling and observing, wherein the pre-emulsifying liquid is milk-like and the emulsification succeeds if no layering occurs for 0.5h, layering indicates that the combination of the emulsifying agent fails, obtaining pre-emulsifying liquid, dividing the pre-emulsifying liquid into three parts, namely 15 parts of the first part, 60 parts of the second part and 25 parts of the third part;
seed polymerization: adding 30kg of water, 0.3kg of n-octyl sodium sulfate and 0.2kg of dibutyl sodium sulfosuccinate into a reaction kettle, stirring and heating, stopping heating after the heating reaches 70 ℃, adding 0.5kg of potassium persulfate, adding a first 15% pre-emulsion into the reaction kettle, starting seed polymerization, starting timing when blue light begins to appear in the reaction kettle, and finishing seed polymerization after 0.5 hour to obtain a polymerization solution;
and (3) dropwise adding reaction: dissolving 0.2kg of potassium persulfate with 5kg of water, synchronously dripping the solution and the second 60% of pre-emulsion into the polymerization solution, controlling the dripping time to be 1.5h, dripping at 85 ℃, adding 3kg of (3-glycidoxypropyl) trimethoxysilane into the third 25% of pre-emulsion after dripping, uniformly stirring, dripping the pre-emulsion with the (3-glycidoxypropyl) trimethoxysilane into the polymerization solution, and dripping for 1h and 80 ℃;
and (3) heat preservation: adding 0.3kg of potassium persulfate into the polymerization solution 15min after the dripping is finished, and preserving the temperature at 85 ℃ for 1h;
and (3) cooling and neutralizing: after the heat preservation is finished, cooling to 60 ℃, adding a neutralizing agent diethanolamine for neutralization, and detecting that the pH value reaches 8; and (3) discharging and packaging: when the temperature is reduced to 50 ℃, the finished product is obtained by filtering and packing.
Example 3
Preparation of organosilicon modified acrylic resin pre-emulsification: 26kg of water is added into a pre-emulsifying kettle, stirring is started, 2kg of sodium n-octyl sulfate and 1kg of nonylphenol polyoxyethylene ether are added, stirring is carried out for 10min to completely dissolve the sodium n-octyl sulfate and the nonylphenol polyoxyethylene ether, 10kg of butyl acrylate, 5kg of isooctyl acrylate, 9kg of methyl methacrylate, 6kg of allyl methacrylate and 8kg of acetoacetic acid ethylene glycol methacrylate are sequentially pumped into the pre-emulsifying kettle, emulsification is waited for 1h, sampling observation is carried out, the pre-emulsion is milk-like, emulsification is successful if no layering is carried out for 0.5h, layering indicates that the combination of the emulsifier fails, the pre-emulsion is divided into three parts, the first part is 20%, the second part is 70% and the third part is 10%;
seed polymerization: adding 15.5kg of water, 1kg of sodium n-octyl sulfate and 1kg of nonylphenol polyoxyethylene ether into a reaction kettle, stirring and heating, stopping heating after the heating reaches 75 ℃, adding 1.5kg of ferrous sulfate, adding a first 20% pre-emulsion into the reaction kettle, starting seed polymerization, starting timing when blue light begins to appear in the reaction kettle, and finishing seed polymerization after 0.5 hour to obtain a polymerization solution;
and (3) dropwise adding reaction: dissolving 0.6kg of ferrous sulfate with 5kg of water, synchronously dripping the solution into the polymerization solution with the second 70% of the pre-emulsion for 2.5h at 90 ℃, adding 5kg of vinyltriethoxysilane and 3kg of vinyltrimethoxysilane into the third 10% of the pre-emulsion after dripping, uniformly stirring, dripping the pre-emulsion with the vinyltriethoxysilane and the vinyltrimethoxysilane into the polymerization solution for 1h at 80 ℃;
and (3) heat preservation: adding 0.4kg of ferrous sulfate into the polymerization solution 15min after the dripping is finished, and preserving heat for 2h at 90 ℃;
and (3) cooling and neutralizing: after the heat preservation is finished, cooling to 60 ℃, adding neutralizer ammonia water for neutralization, and detecting that the pH value reaches 8.5;
and (3) discharging and packaging: when the temperature is reduced to 50 ℃, the finished product is obtained by filtering and packing.
Example 4
Preparation of organosilicon modified acrylic resin
This embodiment differs from embodiment 1 in that: the raw material of the organosilicon modified acrylic resin adopts 6kg of modified (3-glycidoxypropyl) trimethoxy silane which is used for replacing vinyl trimethoxy silane in the dropwise addition reaction.
The preparation method of the organosilicon modified acrylic resin suitable for the water-based laser color layer is the same as that of the example 1.
The preparation method of the modified (3-glycidoxypropyl) trimethoxysilane comprises the following steps: 8kg of dimethyl sulfoxide is added into a reaction kettle, stirring is started, 3.5kg of (3-glycidoxypropyl) trimethoxysilane, 1.3kg of 4-vinylbenzylamine and 0.05kg of stannous octoate are added, the reaction kettle is heated to 80 ℃ for 3 hours, the dimethyl sulfoxide is removed through reduced pressure rectification, and the reaction kettle is cleaned and dried to obtain the modified (3-glycidoxypropyl) trimethoxysilane.
Example 5
Preparation of organosilicon modified acrylic resin
This embodiment differs from embodiment 1 in that: the raw material of the organosilicon modified acrylic resin adopts 6kg of modified (3-glycidoxypropyl) trimethoxy silane which is used for replacing vinyl trimethoxy silane in the dropwise addition reaction.
The preparation method of the organosilicon modified acrylic resin suitable for the water-based laser color layer is the same as that of the example 1.
The preparation method of the modified (3-glycidoxypropyl) trimethoxysilane comprises the following steps: 9.5kg of dimethyl sulfoxide is added into a reaction kettle, stirring is started, 5.5kg of (3-glycidoxypropyl) trimethoxysilane, 2kg of 4-vinylbenzylamine and 0.1kg of stannous octoate are added, the mixture is heated to 75 ℃ for 2 hours, the dimethyl sulfoxide is removed through reduced pressure rectification, and the mixture is washed and dried to obtain the modified (3-glycidoxypropyl) trimethoxysilane.
Example 6
Preparation of organosilicon modified acrylic resin
This embodiment differs from embodiment 1 in that: the raw materials of the organosilicon modified acrylic resin are 3kg of methacrylic acid and 2kg of acetoacetic acid ethylene glycol methacrylate, which are used for replacing 5kg of hydroxypropyl acrylate in pre-emulsification.
The preparation method of the organosilicon modified acrylic resin suitable for the water-based laser color layer is the same as that of the example 1.
Example 7
Preparation of organosilicon modified acrylic resin
This embodiment differs from embodiment 1 in that: the raw materials of the organosilicon modified acrylic resin are 2.8kg of methacrylic acid and 2.2kg of acetoacetic acid ethylene glycol methacrylate, which are used for replacing 5kg of hydroxypropyl acrylate in pre-emulsification.
The preparation method of the organosilicon modified acrylic resin suitable for the water-based laser color layer is the same as that of the example 1.
Example 8
Preparation of organosilicon modified acrylic resin
This embodiment differs from embodiment 1 in that: the raw materials of the organosilicon modified acrylic resin are 4kg of methacrylic acid and 1kg of acetoacetic acid ethylene glycol methacrylate, which are used for replacing 5kg of hydroxypropyl acrylate in pre-emulsification.
The preparation method of the organosilicon modified acrylic resin suitable for the water-based laser color layer is the same as that of the example 1.
Example 9
Preparation of organosilicon modified acrylic resin
This embodiment differs from embodiment 1 in that: 6kg of modified (3-glycidoxypropyl) trimethoxysilane is selected as a raw material of the organosilicon modified acrylic resin and is used for replacing vinyl trimethoxysilane in the dropwise addition reaction; 2.8kg of methacrylic acid and 2.2kg of ethylene glycol acetoacetate methacrylate were chosen for use in the pre-emulsification instead of 5kg of hydroxypropyl acrylate.
The preparation method of the organosilicon modified acrylic resin suitable for the water-based laser color layer is the same as that of the example 1.
The preparation method of the modified (3-glycidoxypropyl) trimethoxysilane comprises the following steps: 9.5kg of dimethyl sulfoxide is added into a reaction kettle, stirring is started, 5.5kg of (3-glycidoxypropyl) trimethoxysilane, 2kg of 4-vinylbenzylamine and 0.1kg of stannous octoate are added, the mixture is heated to 75 ℃ for 2 hours, the dimethyl sulfoxide is removed through reduced pressure rectification, and the mixture is washed and dried to obtain the modified (3-glycidoxypropyl) trimethoxysilane.
Comparative example
Comparative example 1
Preparation of organosilicon modified acrylic resin
This comparative example differs from example 1 in that: the raw materials of the acrylic resin are 10kg of butyl acrylate, 12kg of n-butyl methacrylate, 5kg of hydroxypropyl acrylate, 2kg of sodium salt of succinic acid mono-octadecyl amide sulfonate, 1kg of nonylphenol polyoxyethylene ether, 2kg of sodium persulfate and 68kg of water, and no organic silicon monomer is added.
The preparation method of the organosilicon modified acrylic resin suitable for the water-based laser color layer is the same as that of the example 1.
Comparative example 2
Preparation of organosilicon modified acrylic resin
This comparative example differs from example 1 in that: the raw materials of the acrylic resin are 10kg of butyl acrylate, 12kg of n-butyl methacrylate, 6kg of vinyl trimethoxy silane, 2kg of sodium salt of succinic acid mono-octadecyl amide sulfonate, 1kg of nonylphenol polyoxyethylene ether, 2kg of sodium persulfate and 67kg of water, and no crosslinking agent monomer is added.
The preparation method of the organosilicon modified acrylic resin suitable for the water-based laser color layer is the same as that of the example 1.
Comparative example 3
Preparation of organosilicon modified acrylic resin
This comparative example differs from example 1 in that: the raw materials of the acrylic resin are 10kg of butyl acrylate, 12kg of n-butyl methacrylate, 10kg of hydroxypropyl acrylate, 2kg of vinyl trimethoxysilane, 2kg of sodium salt of succinic acid mono-octadecyl amide sulfonate, 1kg of nonylphenol polyoxyethylene ether, 2kg of sodium persulfate and 61kg of water.
The preparation method of the organosilicon modified acrylic resin suitable for the water-based laser color layer is the same as that of the example 1.
Application example
Application example 1
Preparation of water-based laser color layer coating
38kg of the organosilicon modified acrylic resin which is suitable for the water-based laser color layer and is prepared in the embodiment 1, 1kg of the water-based mineral oil defoamer, 2kg of the water-based alkyne diol dispersant, 60kg of absolute ethyl alcohol and 25kg of water are added into a reaction kettle, and the mixture is stirred until the mixture is dissolved and mixed, so that the water-based laser color layer coating is obtained.
Wherein, the aqueous mineral oil defoamer selects Surfynol DF220;
the waterborne alkyne diol dispersant is Di high Dispers 740W.
Application example 2
Preparation of water-based laser color layer coating
42kg of the organosilicon modified acrylic resin applicable to the aqueous laser color layer prepared in the example 2, 3kg of the aqueous mineral oil defoamer, 5kg of the aqueous alkyne diol dispersant, 75kg of absolute ethyl alcohol and 35kg of water are added into a reaction kettle, and stirred until dissolved and mixed, thus obtaining the aqueous laser color layer coating.
Wherein, the aqueous mineral oil defoamer selects Surfynol DF220;
the waterborne alkyne diol dispersant is Di high Dispers 740W.
Application example 3
Preparation of water-based laser color layer coating
40kg of the organosilicon modified acrylic resin applicable to the aqueous laser color layer prepared in the example 3, 2kg of the aqueous molecular-grade defoamer, 5kg of the aqueous polycarboxylate dispersant, 70kg of absolute ethyl alcohol and 30kg of water are added into a reaction kettle, and stirred until dissolved and mixed, thus obtaining the aqueous laser color layer coating.
Wherein, the aqueous molecular-level defoamer is selected from Surfynol DF-110L;
the aqueous polycarboxylate dispersant is selected from Santopulaceae SN-DISPERSANT 5040.
Application example 4
Preparation of water-based laser color layer coating
The difference between the present application example and application example 1 is that the source of the organosilicon modified acrylic resin suitable for the aqueous laser color layer is different.
An organosilicon modified acrylic resin suitable for use in aqueous laser color layers was prepared from example 4.
Application example 5
Preparation of water-based laser color layer coating
The difference between the present application example and application example 1 is that the source of the organosilicon modified acrylic resin suitable for the aqueous laser color layer is different.
An organosilicon modified acrylic resin suitable for use in aqueous laser color layers was prepared from example 5.
Application example 6
Preparation of water-based laser color layer coating
The difference between the present application example and application example 1 is that the source of the organosilicon modified acrylic resin suitable for the aqueous laser color layer is different.
An organosilicon modified acrylic resin suitable for use in aqueous laser color layers was prepared from example 6.
Application example 7
Preparation of water-based laser color layer coating
The difference between the present application example and application example 1 is that the source of the organosilicon modified acrylic resin suitable for the aqueous laser color layer is different.
An organosilicon modified acrylic resin suitable for use in aqueous laser color layers was prepared from example 7.
Application example 8
Preparation of water-based laser color layer coating
The difference between the present application example and application example 1 is that the source of the organosilicon modified acrylic resin suitable for the aqueous laser color layer is different.
An organosilicon modified acrylic resin suitable for use in aqueous laser color layers was prepared from example 8.
Application example 9
Preparation of water-based laser color layer coating
The difference between the present application example and application example 1 is that the source of the organosilicon modified acrylic resin suitable for the aqueous laser color layer is different.
An organosilicon modified acrylic resin suitable for use in aqueous laser color layers was prepared from example 9.
Comparative examples of application
Comparative example 1 was used
Preparation of water-based laser color layer coating
The difference between the present application example and application example 1 is that the source of the organosilicon modified acrylic resin suitable for the aqueous laser color layer is different.
An organosilicon modified acrylic resin suitable for use in an aqueous laser color layer was prepared from comparative example 1.
Comparative example 2 was used
Preparation of water-based laser color layer coating
The difference between the present application example and application example 1 is that the source of the organosilicon modified acrylic resin suitable for the aqueous laser color layer is different.
An organosilicon modified acrylic resin suitable for use in an aqueous laser color layer was prepared from comparative example 2.
Comparative example 3 was used
Preparation of water-based laser color layer coating
The difference between the present application example and application example 1 is that the source of the organosilicon modified acrylic resin suitable for the aqueous laser color layer is different.
An organosilicon modified acrylic resin suitable for use in an aqueous laser color layer was prepared from comparative example 3.
Performance detection
1. The aqueous laser color layer coating materials prepared in application examples 1-7 and application comparative examples 1-3 were coated on PET base film with release coating prepared from 1.1kg of aqueous wax (20% solids content), 12kg of purified water, 15kg of ethanol, and a coating weight of 0.044g/m 2 Coating speed is 100m/min;
the coating weight of the water-based laser color layer coating is 1.1g/m 2 The coating speed is 80m/min, and the materials are put into an oven for drying, and the drying parameters are as follows: 1 region 90 ℃,2 region 110 ℃,3 region 130 ℃,4 region 145 ℃, 5 region 140 ℃ to obtain a laser color layer;
the laser color layer is molded, and the molding process is as follows: the starting temperature is 140 ℃, the temperature is gradually increased to 170 ℃, and the machine speed is gradually increased from 5m/min to 50m/min;
and (3) aluminizing on the laser color layer after the die pressing is finished to form an aluminized layer, wherein the OD value of the aluminized layer is 1.7, finally coating an adhesive, and drying to form an adhesive layer to obtain the electrochemical aluminum.
1. Adhesion performance test: the electric aluminum in each application example and the application comparative example is hot stamped on a PET sheet, the adhesion performance of the laser color layer is tested by adopting a 3M810 adhesive tape, and the falling area of the laser color layer is detected.
2. High temperature resistance: whether the hot stamping is discolored or not at 180 ℃ and the hot stamping time delay is 0.4s.
3. Laser pattern definition: after the paint layer, the release layer and the substrate film in the sample provided in the example are separated, the pattern definition of the non-adhered part of the paint layer is observed and evaluated, wherein the 1 level is clear pattern without impurity points, the 2 level is clear pattern with little impurity points, the 3 level is slightly blurred pattern, and the 4 level is obvious pattern blurring.
4. Molding brightness: visual observation was performed.
5. Sticking condition: visual observation was performed.
6. Molding length (m): in the processing process, the equipment does not stop, does not carry out other actions such as manual wiping, and the like, and simultaneously meets the meter number of brightness requirements.
1. Results of Performance test
Analysis of results:
the difference between the application comparative example 1 and the application example 1 is that the organosilicon modified acrylic resin used in the laser color layer coating is different, and the organosilicon monomer is not added in the organosilicon modified acrylic resin selected in the application comparative example 1, and the data in the table show that the organosilicon monomer-added acrylic resin can fully utilize the heat resistance and the anti-sticking property of organosilicon, realize the laser effect with clear pattern and high brightness, and can keep the die pressing at high temperature without color change and sticking.
The difference between the application of the comparative example 2 and the application example 1 is that the organosilicon modified acrylic resin used in the laser color layer coating is different, and the organosilicon modified acrylic resin selected in the application of the comparative example 2 is not added with a cross-linking agent monomer, and the bonding and the adhesion of the laser color layer and the base material can be realized by the acrylic resin added with the cross-linking monomer, so that the cross-linking film forming of the acrylic resin is realized, and the temperature resistance of the acrylic resin is facilitated.
The difference between the application of comparative example 3 and the application of example 1 is that the organosilicon modified acrylic resin used in the laser color layer coating is different, wherein the blending amount of the crosslinking agent monomer and the organosilicon monomer in the acrylic resin is changed, and the data in the combination table shows that the laser effect after the molding is not obvious and the expected product cannot be obtained after the blending amount of the crosslinking agent monomer and the organosilicon complex is changed.
The difference between application example 4 and application example 1 is that the organosilicon modified acrylic resin used in the laser color layer coating is different, the raw material of application example 4 selects modified (3-glycidoxypropyl) trimethoxysilane as organosilicon monomer, and the combination data shows that the benzene ring is introduced to facilitate mold pressing, thereby facilitating continuous mold pressing of the coating.
The difference between application example 5 and application example 1 is that the organosilicon modified acrylic resin used in the laser color layer coating is different, 3kg of methacrylic acid and 2kg of acetoacetic acid methacrylic acid glycol ester are selected as the raw materials of application example 5 to be compounded to be used as a cross-linking agent monomer, and the data in the table shows that the film forming toughness of the acrylic resin is improved, the laser effect is obvious, and the molding length of the coating is increased.
The difference between application example 6 and application example 4 is that the organosilicon modified acrylic resin used in the laser color layer coating is different, and compared with application example 5, application example 6 changes the compounding ratio of methacrylic acid and acetoacetic acid methacrylic acid glycol ester, so that the performance enhancement effect on the acrylic resin is reduced, and the continuous molding performance is reduced.
The embodiments of this embodiment are all preferred embodiments of the present application, and are not intended to limit the scope of the present application, in which like parts are denoted by like reference numerals. Therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (10)
1. The organic silicon modified acrylic resin is characterized by comprising the following raw materials in percentage by mass:
5-15% of acrylic monomer;
5-15% of methacrylate monomer;
3-8% of cross-linking agent monomer;
3-8% of organic silicon monomer;
1.5-5% of emulsifying agent;
1 to 2.5 percent of initiator;
the balance of water;
wherein, the organic silicon monomer is one or more of vinyl trimethoxy silane, vinyl triethoxy silane and (3-glycidoxypropyl) trimethoxy silane.
2. The organic silicon modified acrylic resin according to claim 1, wherein the organic silicon monomer is modified (3-glycidoxypropyl) trimethoxysilane, and the modified (3-glycidoxypropyl) trimethoxysilane is prepared from the following raw materials in parts by weight:
35-55 parts of (3-glycidoxypropyl) trimethoxysilane;
13-20 parts of 4-vinylbenzylamine;
0.5-1 part of catalyst;
80-95 parts of solvent.
3. The silicone-modified acrylic resin according to claim 1, wherein: the cross-linking agent monomer is a mixture of methacrylic acid and acetoacetic acid ethylene glycol methacrylate, wherein the mass ratio of the methacrylic acid to the acetoacetic acid ethylene glycol methacrylate is (1.2-1.4) (0.8-1.1).
4. The silicone-modified acrylic resin according to claim 1, wherein: the acrylic ester monomer is one or more of butyl acrylate, isooctyl acrylate, dodecyl acrylate and lauryl acrylate.
5. The silicone-modified acrylic resin according to claim 1, wherein: the methacrylate monomer is one or more of n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate and dimethylaminoethyl methacrylate.
6. The silicone-modified acrylic resin according to claim 1, wherein: the emulsifier is one or more of n-octyl sodium sulfate, dibutyl sodium sulfosuccinate, sodium sulfosuccinate mono-octadecyl amide sulfonate and polyoxyethylene nonylphenol ether.
7. A method for preparing the organosilicon modified acrylic resin, which is used for preparing the organosilicon modified acrylic resin according to claims 1-6, comprising the following steps:
pre-emulsification: adding a proper amount of water and an emulsifying agent, stirring for 5-10min to wait for the emulsifying agent to dissolve, sequentially adding an acrylic monomer, a methacrylic monomer and a crosslinking agent monomer, emulsifying for 0.5-1h, sampling, checking and observing whether layering is carried out for 0.5h to obtain a pre-emulsion, and dividing the pre-emulsion into three parts, namely 15% -20%, 60% -70% and 10% -25% respectively;
seed polymerization: adding a proper amount of water and an emulsifying agent, stirring and heating to 70-75 ℃, stopping heating, adding a proper amount of an initiating agent and 15-20% of pre-emulsion, and performing seed polymerization to obtain a polymerization solution;
and (3) dropwise adding reaction: part of initiator is dissolved by water and is synchronously dripped into the polymerization solution with 60 to 70 percent of pre-emulsion, the dripping time is controlled to be 1.5 to 2.5 hours, the dripping temperature is 85 to 90 ℃, after the dripping is finished, the organosilicon monomer is added into the final 10 to 25 percent of pre-emulsion, the mixture is uniformly stirred, the mixture is continuously dripped into the polymerization solution, the dripping time is controlled to be 0.5 to 1 hour, and the temperature is controlled to be 80 to 85 ℃;
and (3) heat preservation: adding the rest initiator into the polymerization solution 15min after the dripping is finished, and preserving the temperature for 1-2h at 85-90 ℃;
and (3) cooling and neutralizing: after the heat preservation is finished, cooling to 60 ℃, adding neutralizer ammonia water or diethanolamine for neutralization, and detecting that the pH value reaches 7.5-8.5;
and (3) discharging and packaging: when the temperature is reduced to 50 ℃, the finished product is obtained by filtering and packing.
8. The method for preparing an organosilicon modified acrylic resin according to claim 7, wherein when the organosilicon monomer is modified (3-glycidoxypropyl) trimethoxysilane, the preparation of the modified (3-glycidoxypropyl) trimethoxysilane comprises the following steps:
adding a solvent into a reaction kettle, adding (3-glycidoxypropyl) trimethoxysilane, 4-vinylbenzylamine and a catalyst under stirring, heating to 75-80 ℃, reacting for 2-3h, removing the solvent by reduced pressure rectification, cleaning and drying to obtain the modified (3-glycidoxypropyl) trimethoxysilane.
9. The water-based laser color layer coating is characterized by comprising the following raw materials in parts by weight: 38-42 parts of the organic silicon modified acrylic resin suitable for the water-based laser color layer, which is prepared by any one of claims 1-6; 1-3 parts of a defoaming agent; 2-5 parts of wetting dispersant; 60-75 parts of absolute ethyl alcohol; 25-35 parts of water.
10. The aqueous laser color layer coating according to claim 9, wherein: the defoamer is one or more of aqueous mineral oil defoamer and aqueous molecular-level defoamer; the wetting dispersant is one or more of aqueous alkyne diol dispersants and aqueous polycarboxylate dispersants.
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