CN116829356A - Laminate and method for producing same - Google Patents
Laminate and method for producing same Download PDFInfo
- Publication number
- CN116829356A CN116829356A CN202280013231.9A CN202280013231A CN116829356A CN 116829356 A CN116829356 A CN 116829356A CN 202280013231 A CN202280013231 A CN 202280013231A CN 116829356 A CN116829356 A CN 116829356A
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- Prior art keywords
- laminate
- resin composition
- formula
- group
- drying
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000010410 layer Substances 0.000 claims abstract description 107
- 239000011342 resin composition Substances 0.000 claims abstract description 105
- 238000001035 drying Methods 0.000 claims abstract description 91
- 239000002344 surface layer Substances 0.000 claims abstract description 83
- -1 acryl Chemical group 0.000 claims abstract description 71
- 239000003960 organic solvent Substances 0.000 claims abstract description 55
- 238000009835 boiling Methods 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000011156 evaluation Methods 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229920005992 thermoplastic resin Polymers 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 9
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 4
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 238000003856 thermoforming Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000005641 methacryl group Chemical group 0.000 claims description 3
- 238000012360 testing method Methods 0.000 abstract description 17
- 230000007613 environmental effect Effects 0.000 abstract description 13
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 14
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 14
- 239000004926 polymethyl methacrylate Substances 0.000 description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 13
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 13
- 229920005668 polycarbonate resin Polymers 0.000 description 11
- 239000004431 polycarbonate resin Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 9
- 239000004417 polycarbonate Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 239000013557 residual solvent Substances 0.000 description 6
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical group C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000007603 infrared drying Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- 229920005497 Acrypet® Polymers 0.000 description 1
- 102100024452 DNA-directed RNA polymerase III subunit RPC1 Human genes 0.000 description 1
- 101000689002 Homo sapiens DNA-directed RNA polymerase III subunit RPC1 Proteins 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- 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
- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
Abstract
The present invention provides a laminate having improved coating film adhesion after environmental test. More specifically, provided is a laminate comprising at least a base layer and a surface layer provided on the surface of the base layer, wherein the surface layer is formed by coating a resin composition containing an organic solvent (A) having a boiling point of less than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or more and a mass ratio A:B in the range of 3:7 to 7:3, drying the resin composition in at least a first drying oven at a temperature in the range of 90 to 120 ℃ and then drying the resin composition in a second drying oven at a temperature in the range of 100 to 140 ℃, wherein the resin composition contains a (meth) acryl polymer (C) having a (meth) acrylic equivalent weight of 200 to 600g/eq and a weight average molecular weight of 5,000 ～ 200,000, and wherein the evaluation result of film adhesion of the surface layer is 0, which is determined by the evaluation method of JIS K5600-5-6.
Description
Technical Field
The present invention relates to a laminate having improved adhesion of a coating film after environmental test and a method for producing the laminate.
Background
Conventionally, resin film laminates having a coating layer (hereinafter also referred to as "surface layer") have been used in various fields (see patent document 1). For example, such a laminate of resin films is used for a front panel, a back panel, an automobile interior part, and the like of a mobile device.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2017-508828
Disclosure of Invention
Technical problem to be solved by the invention
The surface layer protecting the surface of the laminate of resin films requires hardness and high scratch resistance to some extent or more. On the other hand, in order to produce a laminate having a desired shape, excellent moldability is required for the resin films constituting the respective layers. Moreover, in the resin composition used for producing the laminate, particularly the surface layer thereof, it is difficult to satisfy all of these different properties.
Accordingly, the present invention provides a laminate which can produce a hard coat layer having excellent scratch resistance and high hardness when cured and which is improved in film adhesion after environmental test, and a method for producing the laminate.
Technical scheme for solving technical problems
The present inventors have conducted intensive studies in order to solve the above-mentioned problems. The result shows that: by using a plurality of solvents having a predetermined boiling point and setting a certain range of drying conditions in the production of a laminate having at least a base material layer and a surface layer, the adhesion of the coating film after environmental test can be effectively improved. The present invention has been completed based on these findings and further repeated studies.
That is, the present invention includes the following modes.
<1> a laminate comprising at least a base layer and a surface layer provided on the surface of the base layer,
the surface layer is formed by coating a resin composition containing an organic solvent (A) having a boiling point of less than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or higher and having a mass ratio A:B in the range of 3:7 to 7:3, drying the resin composition in at least a first drying oven at a temperature in the range of 90 to 120 ℃ and then drying the resin composition in a second drying oven at a temperature in the range of 100 to 140 ℃,
the resin composition contains a (meth) acryl polymer (C) having a (meth) acrylic equivalent weight of 200 to 600g/eq and a weight average molecular weight of 5,000 ～ 200,000,
the film adhesion of the surface layer was evaluated as 0 according to the evaluation method of JIS K5600-5-6.
<2> the laminate according to <1>, wherein the (meth) acryl polymer (C) comprises a repeating unit represented by the following formula (I),
in the formula (I), m is an alkylene group having 1 to 4 carbon atoms or a single bond, n is an alkyl group having 1 to 4 carbon atoms or hydrogen, p is a single bond or an alkylene group having 1 or 2 carbon atoms, and q is an alkyl group having 1 to 12 carbon atoms or hydrogen which may contain at least one substituent selected from the group consisting of an epoxy group, a hydroxyl group, an acryl group and a methacryl group.
<3> the laminate according to <2>, wherein in the above formula (I), m is an alkylene group having 1 or 2 carbon atoms, n is an alkyl group having 1 or 2 carbon atoms, p is a single bond or a methylene group, and q is an alkyl group having 1 to 6 total carbon atoms or hydrogen which may contain at least one substituent selected from the group consisting of a glycidyl group, a hydroxyl group and an acryl group.
<4> the laminate according to <3>, wherein in the formula (I), m is methylene, n is methyl, p is a single bond, and q is methyl, alkyl having 5 or less carbon atoms including glycidyl (epoxy) or alkyl having 8 or less carbon atoms including hydroxy and acryl.
<5> the laminate according to <2>, wherein the (meth) acryl polymer (C) contains at least any one of the repeating units represented by the following formulas (II-a), (II-b) and (II-C),
<6> the laminate according to <5>, wherein the repeating unit of the formula (II-a) is 30 to 85 mol%, the repeating unit of the formula (II-b) is 5 to 30 mol% and the repeating unit of the formula (II-c) is 10 to 40 mol% based on the total mole number of the repeating unit of the formula (II-a), the repeating unit of the formula (II-b) and the repeating unit of the formula (II-c).
<7> the laminate according to <5>, wherein the molar ratio of the repeating unit of the formula (II-a), the repeating unit of the formula (II-b) and the repeating unit of the formula (II-c) is 4.5 to 5.5:1.5 to 2.5:2.5 to 3.5.
<8> the laminate according to any one of <1> to <7>, wherein the (meth) acryl polymer (C) further comprises a pentaerythritol-based polyfunctional acrylate compound.
<9> the laminate according to <8>, wherein the pentaerythritol-based polyfunctional acrylate compound is at least one selected from pentaerythritol tetraacrylate represented by the following formula (III-a), dipentaerythritol hexaacrylate represented by the formula (III-b) and pentaerythritol triacrylate,
<10> the laminate according to <8> or <9>, wherein the content of the pentaerythritol-based polyfunctional acrylate compound is 70 mass% or less based on the total mass of the resin composition.
<11> the laminate according to any one of <1> to <10>, wherein the resin composition is a radiation curable resin composition.
<12> the laminate according to any one of <1> to <11>, wherein the resin composition further contains a photopolymerization initiator.
<13> the laminate according to any one of <1> to <12>, wherein the base layer contains a thermoplastic resin.
<14> the laminate according to any one of <1> to <13>, wherein the laminate is a decorative sheet.
<15> a molded article obtained by thermoforming the laminate according to any one of <1> to <14 >.
<16> a method for producing the laminate according to any one of <1> to <15>, comprising:
a step 1 of coating a surface of a base material layer with a resin composition containing a radiation curable resin and an organic solvent to obtain a coated article; and
a step 2 of drying the obtained coated article to form a surface layer on the surface of the base material layer,
the laminate has at least a base material layer and a surface layer,
the resin composition contains an organic solvent (A) having a boiling point of less than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or more and a mass ratio A:B in the range of 3:7 to 7:3,
the resin composition contains a (meth) acryl polymer (C) having a (meth) acrylic equivalent weight of 200 to 600g/eq and a weight average molecular weight of 5,000 ～ 200,000,
the film adhesion of the surface layer was evaluated as 0 according to the evaluation method of JIS K5600-5-6.
<17> the method according to <16>, wherein at least two drying ovens are used in the above step 2, and the drying oven temperature of the last drying oven is higher than the drying oven temperature of the first drying oven.
<18> the method according to <16> or <17>, wherein at least two drying ovens capable of heating the coated article to 60 ℃ or higher are used in the step 2, the drying oven temperature of the first drying oven is in the range of 90 to 120 ℃, and the drying oven temperature of the second drying oven is in the range of 100 to 140 ℃.
<19> the method for producing a laminate according to any one of <16> to <18>, wherein the thickness of the base layer is 0.1mm to 1.0mm, and the thickness of the layer of the resin composition applied to the surface of the base layer is 1.0 μm to 10 μm.
Effects of the invention
The present invention can provide a laminate for a molded article which is free from the characteristics required for the laminate for a molded article such as moldability, scratch resistance, hardness, adhesion and the like, and which is effectively improved in coating film adhesion after environmental test. The laminate of the present invention has such excellent characteristics, and therefore can provide a molded article having effectively improved adhesion of a coating film after environmental test. Such a molded article is suitable for applications such as automobile interior trim and housings of electronic devices. The present invention also provides a method for producing a laminate which effectively improves adhesion of a coating film after environmental test, and a molded article obtained from the laminate.
Drawings
Fig. 1 is a cross-sectional view showing an example of a laminate 10 including a base layer 30 and a surface layer 20 provided on the surface of the base layer 30.
Detailed Description
The inventors of the present invention have conducted intensive studies on the production of molded articles using a laminate, and have found that the adhesion of a coating film of a laminate after an environmental test can be effectively improved. Then, the inventors of the present invention conducted repeated trial and error, and found that: the present invention has been completed because the initial drying temperature after coating is a factor that reduces the adhesion of the coating film.
The present invention is described in detail below. However, the present invention is not limited to the following embodiments, and may be implemented with any modification within the scope having the effects of the present invention.
1. Laminate body
The structure of the laminate 10 of the present invention is shown in fig. 1, for example. That is, the laminate 10 of the present invention includes at least a base material layer 30 and a surface layer 20 (fig. 1) provided on the surface of the base material layer 30. In a preferred embodiment of the present invention, the laminate is a laminate for molding. The laminate 10 of the present invention may further include other layers such as a masking layer on the surface of the surface layer 20 on the side not in contact with the base material layer 30. In the embodiment of the present invention, the evaluation result of the film adhesion of the surface layer 20 in the laminate 10, which is determined according to the evaluation method of JIS K5600-5-6, is 0.
In one embodiment of the present invention, the laminate of the present invention comprises at least a base material layer and a surface layer provided on the surface of the base material layer,
the surface layer is formed by coating a resin composition containing an organic solvent (A) having a boiling point of less than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or higher and having a mass ratio A:B in the range of 3:7 to 7:3, drying the resin composition in at least a first drying oven at a temperature in the range of 90 to 120 ℃ and then drying the resin composition in a second drying oven at a temperature in the range of 100 to 140 ℃,
The resin composition contains a (meth) acryl polymer (C) having a (meth) acrylic equivalent weight of 200 to 600g/eq and a weight average molecular weight of 5,000 ～ 200,000,
the film adhesion of the surface layer 20 was evaluated as 0 according to the evaluation method of JIS K5600-5-6.
1.1 substrate layer
In the laminate 10 of the present invention, the base layer 30 may be composed of 1 layer or 2 or more layers. In one embodiment of the present invention, the base material layer 30 may be constituted of, for example, a first resin layer 31 and a second resin layer 32 (fig. 1).
In the laminate 10 of the present invention, the base layer 30 contains a resin, more preferably a thermoplastic resin. The type of thermoplastic resin is not particularly limited, and various resins such as acrylic resins such as Polycarbonate (PC) resin, polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cyclic Olefin Copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane (Cellophane), and aromatic polyamide can be used. Of these alternatives, the thermoplastic resin of the substrate layer preferably contains at least a polycarbonate resin. In a preferred embodiment of the present invention, the substrate layer contains a thermoplastic resin.
The type of the polycarbonate resin contained in the base layer is not particularly limited as long as it is a polycarbonate resin comprising a- [ O-R-OCO ] -unit (R is an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and has a linear structure or a branched structure) containing a carbonate bond in a molecular main chain, and is preferably a polycarbonate having a bisphenol skeleton or the like, and particularly preferably a polycarbonate having a bisphenol a skeleton or a bisphenol C skeleton. As the polycarbonate resin, a mixture or copolymer of bisphenol a and bisphenol C can be used. The hardness of the base material layer can be improved by using a bisphenol C-based polycarbonate resin, for example, a polycarbonate resin having only bisphenol C, a polycarbonate resin of a mixture or copolymer of bisphenol C and bisphenol a.
The polycarbonate resin preferably has a viscosity average molecular weight of 15,000 ～ 40,000, more preferably 20,000 ～ 35,000, and still more preferably 22,500 ～ 25,000.
The acrylic resin contained in the base layer is not particularly limited, and examples thereof include a homopolymer of various (meth) acrylates such as polymethyl methacrylate (PMMA) and Methyl Methacrylate (MMA), and a copolymer of PMMA and MMA with one or more other monomers, and a mixture of a plurality of these resins may be further mentioned. Among them, preferred are (meth) acrylates having a cyclic alkyl structure and having low birefringence, low hygroscopicity and excellent heat resistance. Examples of the above (meth) acrylic resins include, but are not limited to, ACRYPET (manufactured by mitsubishi Yang Zhushi), DELPET (manufactured by asahi chemical corporation), and PARAPET (manufactured by colali corporation).
When a product obtained by laminating the acrylic resin on the surface layer of the polycarbonate resin is used as the base material layer, the hardness of the surface layer of the base material layer can be improved. In one embodiment of the present invention, the laminate 10 is composed of, for example, a first resin layer 31 and a second resin layer 32 (fig. 1), the first resin layer 31 being an acrylic resin layer, and the second resin layer 32 being a Polycarbonate (PC) resin layer. In such an embodiment of the present invention, the surface layer 20 is laminated on the PMMA layer side surface of the base material layer 30 having the polymethyl methacrylate (PMMA) resin layer 31 and the Polycarbonate (PC) resin layer 32 (fig. 1).
The base material layer may contain an additive as a component other than the thermoplastic resin. For example, at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, a flame retardant aid, an ultraviolet absorber, a mold release agent, and a colorant, and the like may be used. In addition, antistatic agents, fluorescent brighteners, antifogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like may be added to the base layer.
The base layer preferably contains 80 mass% or more of a thermoplastic resin, more preferably 90 mass% or more, and particularly preferably 95 mass% or more of a thermoplastic resin. The thermoplastic resin of the base layer preferably contains 80 mass% or more of a polycarbonate resin, more preferably 90 mass% or more, and particularly preferably 95 mass% or more of a polycarbonate resin.
The thickness of the base material layer is not particularly limited, but is preferably 0.1mm to 1.0mm. The thickness of the base material layer is, for example, 0.2mm to 0.8mm or 0.3mm to 0.7mm. In a more preferred embodiment of the present invention, the thickness of the base material layer is 0.1mm to 1.0mm.
1.2 surface layer
The surface layer 20 of the present invention is provided by applying a resin composition to the surface of the base material layer 30 and drying the composition. When the base material layer 30 is composed of a plurality of layers, for example, a first resin layer 31 and a second resin layer 32 (fig. 1), the surface layer 20 is laminated on the surface of the base material layer 30 having the first resin layer 31 and the second resin layer 32 on the side of the first resin layer 31 (fig. 1).
< resin composition >
The resin composition used for the surface layer of the present invention contains the (meth) acryl polymer (C) and an organic solvent.
(meth) acryl Polymer (C)
In an embodiment of the present invention, the (meth) acryl polymer (C) has a (meth) acrylic equivalent weight of 200 to 600 g/eq. The (meth) acrylic acid equivalent of the (meth) acryl polymer is preferably 200 to 500g/eq, more preferably 220 to 450g/eq, still more preferably 250 to 400g/eq.
In addition, in an embodiment of the present invention, the (meth) acryl polymer (C) has a weight average molecular weight of 5,000 ～ 200,000. The weight average molecular weight of the (meth) acryl polymer is preferably 10,000 ～ 150,000, more preferably 15,000 ～ 100,000, and further preferably 20,000 ～ 50,000.
The value of the weight average molecular weight can be measured based on the descriptions in paragraphs [0061] to [0064] of Japanese patent application laid-open No. 2007-179018. The details of the measurement method are as follows.
TABLE 1
Conditions for measuring weight average molecular weight
| Device and method for controlling the same | "Aliance" manufactured by Waters corporation " |
| Column | Shodex K-850L (2 roots) manufactured by Shodex electric Co., ltd |
| Detector for detecting a target object | UV detector: 254nm |
| Eluent (eluent) | Chloroform (chloroform) |
That is, first, a calibration curve showing the relationship between the elution time and the molecular weight of the polycarbonate was prepared by a general calibration method using polystyrene as a standard polymer. Then, the elution profile (chromatogram) of the polycarbonate was measured under the same conditions as those in the case of the calibration profile described above. The weight average molecular weight (Mw) was calculated from the elution time (molecular weight) of the polycarbonate and the peak area (molecular number) of the elution time. The weight average molecular weight is represented by the following formula (a), where Ni means the number of molecules having a molecular weight Mi.
Mw＝∑(NiMi 2 )/∑(NiMi)····(A)
In this specification, (meth) acrylic acid includes any of acrylic acid and methacrylic acid.
As described above, the resin composition containing the (meth) acryl polymer (C) having a predetermined range of (meth) acrylic equivalent weight and weight average molecular weight is excellent in tack free before curing and scratch resistance after curing, and can also be easily subjected to curing reaction and polymerization reaction.
In one embodiment of the present invention, the (meth) acryl polymer (C) contained in the resin composition used for the surface layer preferably has a repeating unit represented by the following formula (I).
Wherein in formula (I), m is an alkylene group having 1 to 4 carbon atoms or a single bond, n is an alkyl group having 1 to 4 carbon atoms or hydrogen, p is a single bond or an alkylene group having 1 or 2 carbon atoms, and q is an alkyl group having 1 to 12 carbon atoms or hydrogen which may contain at least one substituent selected from the group consisting of an epoxy group, a hydroxyl group, an acryl group and a methacryl group.
In one embodiment of the present invention, the (meth) acryl polymer (C) more preferably contains a repeating unit in which m in the above formula (I) is an alkylene group having 1 or 2 carbon atoms, n is an alkyl group having 1 or 2 carbon atoms, p is a single bond or a methylene group, and q is an alkyl group having 1 to 6 total carbon atoms which may contain at least any one substituent of a glycidyl group, a hydroxyl group and an acryl group, or hydrogen.
For example, in the above formula (I), m is methylene, n is methyl, p is a single bond, q is methyl, alkyl having 5 or less carbon atoms containing glycidyl (epoxy) group, alkyl having 8 or less carbon atoms containing hydroxyl and acryl group, or the like.
In one embodiment of the present invention, specific examples of the repeating unit that can be contained in the (meth) acryl polymer (C) include repeating units represented by the following formulas (II-a), (II-b) and (II-C).
In one embodiment of the present invention, in the (meth) acryl polymer (C), the repeating unit of the formula (II-a) is 30 to 85 mol%, more preferably 40 to 80 mol% based on the total mole number of the repeating unit of the formula (II-a), the repeating unit of the formula (II-b) and the repeating unit of the formula (II-C). The repeating units of the formula (II-b) are preferably 5 to 30 mol%, more preferably 10 to 25 mol%, based on the total mole number. The repeating units of the formula (II-c) are preferably 10 to 40 mol%, more preferably 10 to 35 mol%, based on the total mole number. In a preferred embodiment of the present invention, the repeating unit of formula (II-a) is 30 to 85 mol%, the repeating unit of formula (II-b) is 5 to 30 mol%, and the repeating unit of formula (II-c) is 10 to 40 mol%, based on the total mole number of the repeating unit of formula (II-a), the repeating unit of formula (II-b) and the repeating unit of formula (II-c). In a more preferred embodiment of the present invention, the repeating unit of formula (II-a) is 40 to 80 mol%, the repeating unit of formula (II-b) is 10 to 25 mol%, and the repeating unit of formula (II-c) is 10 to 35 mol%, based on the total mole number of the repeating unit of formula (II-a), the repeating unit of formula (II-b) and the repeating unit of formula (II-c).
In one embodiment of the present invention, the molar ratio of the repeating unit of the formula (II-a), the repeating unit of the formula (II-b) and the repeating unit of the formula (II-c) is preferably 4.5 to 5.5:1.5 to 2.5:2.5 to 3.5, for example, 5:2:3.
In one embodiment of the present invention, the (meth) acryl polymer (C) may be added with a polyfunctional acrylate compound having a plurality of acrylate groups. The polyfunctional acrylate compound having a plurality of acrylate groups which can be added to the (meth) acryl polymer (C) preferably contains 3 or more acrylate groups. In a preferred embodiment of the present invention, the multifunctional acrylate compound having a plurality of acrylate groups which may be added to the (meth) acryl polymer (C) may be a pentaerythritol-based multifunctional acrylate compound. In a preferred embodiment of the present invention, the (meth) acryl polymer (C) further comprises a pentaerythritol-based multifunctional acrylate compound. Examples of the polyfunctional acrylate compound having a plurality of acrylate groups include pentaerythritol tetraacrylate represented by the following formula (III-a), dipentaerythritol hexaacrylate represented by the formula (III-b), pentaerythritol triacrylate, and the like. In a preferred embodiment of the present invention, the pentaerythritol-based multifunctional acrylate compound is one or more selected from pentaerythritol tetraacrylate represented by the following formula (III-a), dipentaerythritol hexaacrylate represented by the formula (III-b), and pentaerythritol triacrylate.
In one embodiment of the present invention, the polyfunctional acrylate compound having a plurality of acrylate groups which can be added to the (meth) acryl polymer (C) preferably contains 70 mass% or less, more preferably 50 mass% or less based on the total mass of the (meth) acryl polymer. In a preferred embodiment of the present invention, the pentaerythritol-based polyfunctional acrylate compound is contained in an amount of 70 mass% or less based on the total mass of the resin composition. In a more preferred embodiment of the present invention, the pentaerythritol-based polyfunctional acrylate compound is contained in an amount of 50 mass% or less based on the total mass of the resin composition. By adding the polyfunctional acrylate compound to the resin composition in this way and reacting with the acryl group, glycidyl group (epoxy group) and hydroxyl group contained in the side chain of the (meth) acryl polymer, a surface film having higher scratch resistance can be formed.
< organic solvent >
The resin composition used for the surface layer contains an organic solvent as a diluting solvent. In an embodiment of the present invention, the resin composition used for the surface layer contains, as a diluent solvent, an organic solvent (a) having a boiling point of less than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or higher. In the present specification, the boiling point means a boiling point at 1 atmosphere.
In the embodiment of the present invention, the boiling point of the organic solvent (A) having a boiling point lower than 120℃may be, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃ or the like. In the embodiment of the present invention, the boiling point of the organic solvent (a) having a boiling point lower than 120 ℃ may be, for example, 40 ℃ or more and lower than 120 ℃, 45 ℃ or more and lower than 120 ℃, 50 ℃ or more and lower than 120 ℃, 55 ℃ or more and lower than 120 ℃, 60 ℃ or more and lower than 120 ℃, 65 ℃ or more and lower than 120 ℃, 70 ℃ or more and lower than 120 ℃, 75 ℃ or more and lower than 120 ℃, 80 ℃ or more and lower than 120 ℃, 85 ℃ or more and lower than 120 ℃, 90 ℃ or more and lower than 120 ℃, 95 ℃ or more and lower than 120 ℃, 100 ℃ or more and lower than 120 ℃, 105 ℃ or more and lower than 120 ℃, 110 ℃ or more and lower than 120 ℃, 111 ℃ or more and lower than 120 ℃, 112 ℃ or more and lower than 120 ℃, 113 ℃ or more and lower than 120 ℃, 114 ℃ or more and lower than 115 ℃ or more and lower than 120 ℃, 116 ℃ or more and lower than 120 ℃, 117 ℃ or more and lower than 120 ℃, 118 ℃ or more and lower than 120 ℃, 119 ℃ or more and lower than 120 ℃. In the embodiment of the present invention, the boiling point of the organic solvent (a) having a boiling point of less than 120 ℃ may be preferably 40 ℃ or more and less than 120 ℃, more preferably 65 ℃ or more and less than 120 ℃, still more preferably 90 ℃ or more and less than 120 ℃.
Examples of the organic solvent (A) having a boiling point of less than 120℃which can be used in the present invention include, but are not limited to, methyl isobutyl ketone (MIBK, boiling point: 116 ℃), acetone (boiling point: 56 ℃), isopropyl alcohol (boiling point: 83 ℃), methyl ethyl ketone (boiling point: 80 ℃), 2-butanol (boiling point: 100 ℃), toluene (boiling point: 111 ℃), and the like. The organic solvent (a) usable in the present invention may preferably be methyl isobutyl ketone (MIBK), isopropyl alcohol, methyl ethyl ketone, 2-butanol, toluene, more preferably methyl isobutyl ketone (MIBK), 2-butanol, toluene, still more preferably methyl isobutyl ketone (MIBK). In a preferred embodiment of the present invention, the organic solvent (a) is methyl isobutyl ketone (MIBK).
In an embodiment of the present invention, the organic solvent (B) having a boiling point of 120℃or higher may have a boiling point of 120℃or higher, 125℃130℃135℃140℃145℃150℃155℃160℃165℃170℃ 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, etc. In the embodiment of the present invention, the organic solvent (B) having a boiling point of 120 ℃ or more may have a boiling point of 120 ℃ or more and 250 ℃ or less, 120 ℃ or more and 245 ℃ or less, 120 ℃ or more and 240 ℃ or less, 120 ℃ or more and 235 ℃ or less, 120 ℃ or more and 230 ℃ or less, 120 ℃ or more and 225 ℃ or less, 120 ℃ or more and 220 ℃ or less, 120 ℃ or more and 215 ℃ or less, 120 ℃ or more and 210 ℃ or less, 120 ℃ or more and 205 ℃ or less, 120 ℃ or more and 200 ℃ or less, 120 ℃ or more and 195 ℃ or less, 120 ℃ or more and 190 ℃ or less, 120 ℃ or more and 185 ℃ or less, 120 ℃ or more and 180 ℃ or less, 120 ℃ or more and 175 ℃ or less, 120 ℃ or more and 170 ℃ or more, 165 ℃ or less, 120 ℃ or more and 160 ℃ or less, 120 ℃ or more and 155 ℃ or less, 150 ℃ or more, 150 ℃ or less, 120 ℃ or more and 140 ℃ or more and 125 ℃ or more, and 130 ℃ or more. In the embodiment of the present invention, the boiling point of the organic solvent (B) having a boiling point of 120 ℃ or higher may be preferably 120 ℃ or higher and 250 ℃ or lower, more preferably 120 ℃ or higher and 205 ℃ or lower, still more preferably 120 ℃ or higher and 160 ℃ or lower.
Examples of the organic solvent (B) having a boiling point of 120℃or higher which can be used in the present invention include cyclohexanone (boiling point: 155.6 ℃), methylcyclohexanol (174 ℃), methylcyclohexanone (163 ℃), phenylmethanol (205 ℃) and diethylene glycol monobutyl ether (230 ℃), but are not limited thereto. The organic solvent (B) usable in the present invention may be preferably cyclohexanone, methylcyclohexanol, or phenylmethanol, more preferably cyclohexanone, methylcyclohexanol, or methylcyclohexanol, and even more preferably cyclohexanone. In a preferred embodiment of the present invention, the organic solvent (B) is cyclohexanone.
In an embodiment of the present invention, the resin composition used for the surface layer contains an organic solvent (A) having a boiling point lower than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or higher, and A:B is in the range of 3:7 to 7:3. The above-mentioned resin composition of the present invention contains an organic solvent (A) having a boiling point of less than 120℃and an organic solvent (B) having a boiling point of 120℃or higher and has a mass ratio of, for example, 3:7, 3.5:7 (i.e., 1:2), 4:6, 5:5, 6:4, 7:3.5 (i.e., 2:1), 7:3.
The resin composition of the present invention contains an organic solvent (A) having a boiling point of less than 120℃and an organic solvent (B) having a boiling point of 120℃or higher, and the mass ratio may be, for example, 3:7 to 7:3, 3:7 to 7:3.5 (i.e., 2:1), 3:7 to 6:4, 3:7 to 5:5, 3:7 to 4:6, 3:7 to 3.5:7 (i.e., 1:2); 3.5:7 (i.e., 1:2) to 7:3, 3.5:7 (i.e., 1:2) to 7:3.5 (i.e., 2:1), 3.5:7 (i.e., 1:2) to 6:4, 3.5:7 (i.e., 1:2) to 5:5, 3.5:7 (i.e., 1:2) to 4:6; 4:6-7:3, 4:6-7:3.5 (i.e. 2:1), 4:6-6:4, 4:6-5:5; 5:5-7:3, 5:5-7:3.5 (i.e. 2:1), 5:5-6:4; 6:4-7:3, 6:4-7:3.5 (i.e. 2:1); 7:3.5 (i.e., 2:1) to 7:3.
In a preferred embodiment of the present invention, the above resin composition contains an organic solvent (A) having a boiling point of less than 120℃and an organic solvent (B) having a boiling point of 120℃or higher and may have a mass ratio of 3:7 to 7:3, 3:7 to 7:3.5 (i.e., 2:1), 3:7 to 6:4, 3:7 to 5:5; 3.5:7 (i.e., 1:2) to 7:3, 3.5:7 (i.e., 1:2) to 7:3.5 (i.e., 2:1), 3.5:7 (i.e., 1:2) to 6:4, 3.5:7 (i.e., 1:2) to 5:5; 4:6-7:3, 4:6-7:3.5 (i.e. 2:1), 4:6-6:4, 4:6-5:5.
In a preferred embodiment of the present invention, the resin composition used in the surface layer contains 30 to 50 mass% of the organic solvent (a) having a boiling point lower than 120 ℃ and 70 to 50 mass% of the organic solvent (B) having a boiling point of 120 ℃ or higher, based on the total mass of the diluent solvents in the resin composition.
In the present invention, the resin composition used in the surface layer contains the organic solvent (a) and the organic solvent (B) in the above-mentioned ratio, and thus, before curing, the resin composition is excellent in coatability, moldability and non-tackiness, and in a laminate obtained by coating the resin composition and drying, the coating film adhesion of the laminate after environmental test can be effectively improved in addition to high hardness and excellent scratch resistance.
< other Components in the resin composition >
The resin composition used for the surface layer preferably contains a leveling agent in addition to the (meth) acryl polymer (C) described above. As the leveling agent, for example, a fluorine-based additive, an organosilicon-based additive, or the like can be used.
Examples of the fluorine-containing additive include MEGAFACE RS-56, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90, FTERGENT 710FL, 220P, 208G, 601AD, 602A, 650A, 228P, FTERGENT, 240GFTX-218 (each of which is an oligomer containing a fluorine group and a UV-reactive group), and among these, FTERGENT 601AD is preferable.
Further, as the silicone-based additive, BYK-UV3500, BYK-UV3505 (each of which is an acryl-containing polyether-modified polydimethylsiloxane) manufactured by BYK Chemie, etc., may be used, and among these, BYK-UV3500, etc., is preferable.
The leveling agent is preferably contained in the resin composition used in the surface layer in an amount of 0.1 to 10 mass%, more preferably 0.5 to 7 mass%, and still more preferably 1 to 5 mass%, based on the total mass of the resin composition.
In one embodiment of the present invention, the resin composition used for the surface layer may be a curable resin composition. In a preferred embodiment of the present invention, the above-mentioned resin composition is a radiation curable resin composition. In one embodiment of the present invention, the radiation curable resin composition may be an energy ray curable resin composition or a thermosetting resin composition, and preferably has energy ray curability, and more preferably has ultraviolet curability. Therefore, the resin composition used for the surface layer preferably further contains a photopolymerization initiator. In a preferred embodiment of the present invention, the above resin composition further contains a photopolymerization initiator.
As the photopolymerization initiator, IRGACURE 184 (1-hydroxy-cyclohexyl-phenyl-ketone), IRGACURE 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-ONE), IRGACURE TPO (2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide), IRGACURE 819 (bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide), esacure ONE (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] acetone) oligomer, and the like are used, and IRGACURE TPO and the like are preferable from the viewpoint of heat resistance as the photopolymerization initiator.
The resin composition used in the surface layer contains, for example, 1 to 6 mass% of a photopolymerization initiator based on the total mass of the resin composition. The content of the photopolymerization initiator in the resin composition is more preferably 2% by mass or more and 5% by mass or less, and still more preferably 3% by mass or more and 4% by mass or less.
The resin composition used for the surface layer may further contain other additives, for example, at least 1 additive selected from the group consisting of heat stabilizers, antioxidants, flame retardants, flame retardant aids, ultraviolet absorbers, mold release agents, and colorants. Further, as long as the desired physical properties are not significantly impaired, antistatic agents, optical brighteners, antifogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, inorganic oxide nanoparticles, and the like may be added to the resin composition.
The resin composition used in the surface layer preferably contains 60 mass% or more, more preferably 80 mass% or more, and particularly preferably 90 mass% or more of the (meth) acryl polymer (C), the organic solvent (a) and the organic solvent (B).
Therefore, the content of the components other than the above-described main three-component (meth) acryl polymer (C), organic solvent (a) and organic solvent (B) in the resin composition is preferably less than 40 mass%, more preferably less than 20 mass%, particularly preferably less than 10 mass%.
< production of resin composition >
The resin composition used for the surface layer is produced by blending the above-mentioned (meth) acryl polymer (C), organic solvent (a), organic solvent (B) and other materials. For example, the resin composition is produced by mixing the components such as the (meth) acryl polymer using a drum.
< Properties of resin composition >
(i) Tack-free properties in the uncured state
In the present invention, the resin composition used for the surface layer is excellent in non-tackiness. Therefore, even if the uncured resin composition is brought into contact with another substance such as an operator's hand, the resin composition can maintain a predetermined shape and can be prevented from adhering to the surface of the contacted substance. In this way, after molding into a shape suitable for various applications using a resin composition excellent in non-tackiness, the cured processing can be easily performed. In addition, the resin composition in a state before curing can be stored or circulated in a predetermined shape.
(ii) Formability in uncured state (compressed air formability)
The resin composition used in the surface layer of the present invention is also excellent in moldability in an uncured state. The moldability of the resin composition can be evaluated, for example, as follows. That is, when the compressed air moldability is performed by applying the above-mentioned resin composition to the surface of the base material layer and drying the resin composition, and then heating the resulting coated article in a state of being placed on a mold having a convex portion, it can be evaluated whether or not the sheet-like resin composition is moderately extended with the convex portion and whether or not a crack is generated.
Although details are omitted, it was confirmed in such an evaluation test that: the resin composition used for the surface layer can be extended with the convex portion without generating cracks during the compressed air moldability.
1.3 method for producing laminate
A laminate including a base material layer was produced as follows.
< production of substrate layer >
First, a material such as a resin composition constituting a base material layer is processed into a layer (sheet) by a conventional method to produce the base material layer. For example, extrusion molding and casting molding are used. Examples of extrusion molding include: a method in which pellets, flakes, or powder of a resin composition used for a base layer are melted and kneaded by an extruder, extruded from a T die or the like, and the obtained semi-molten sheet is nipped by a roll, cooled, and solidified to form a sheet. The composition of the substrate layer is as described above. The substrate layer may be composed of a single layer or may be composed of a plurality of layers. In one embodiment of the present invention, the base material layer 30 may be constituted of, for example, a first resin layer 31 and a second resin layer 32 (fig. 1).
< formation of surface layer >
Then, the resin composition used for the surface layer prepared as described above is coated on the outer side surface of the base material layer having a single layer or a plurality of layers to form a surface layer. The composition and properties of the resin composition used for the surface layer are as described above.
In an embodiment of the present invention, the surface layer is formed by a method comprising the steps of: a step 1 of coating a surface of a base material layer with a resin composition containing a radiation curable resin and an organic solvent to obtain a coated article; and a step 2 of drying the obtained coated article to form a surface layer on the surface of the base material layer. Then, according to the method of the present invention, a laminate having an evaluation result of 0, which is determined by the evaluation method of JIS K5600-5-6, of the film adhesion of the surface layer of the laminate can be obtained.
In the present invention, as a method of applying the resin composition used for the surface layer to the substrate layer, gravure coating, die coating, curtain coating, bar coating (rod coating), bar coating, blade coating, doctor blade coating, dip coating, and the like can be used. An appropriate method can be selected from these methods according to the viscosity of the paint and the thickness of the coating layer. For example, when a coating material having a viscosity of 10 mPas is used to obtain a surface layer having a dry film thickness of 5. Mu.m, gravure coating suitable for low-viscosity film coating is preferably used.
In the present invention, as a method for drying the coated material, hot air drying, infrared drying, far infrared drying, drum heating drying, electromagnetic induction heating drying, and the like can be used. From the viewpoint of productivity and controllability, it is desirable to use hot air drying.
As a configuration of the hot air drying furnace used in the step of drying the coated material, it is desirable to have at least two or more working areas so that the temperature and the wind speed can be independently controlled. As the hot air supply method, a forward flow type, a reverse flow type, a slit nozzle type, or an oblique type, in which hot air is supplied in parallel to the transport direction of the substrate, or in which hot air is supplied perpendicular to the transport direction of the substrate, may be employed. As a substrate transport system in the drying furnace, a roll support system, a float system, or the like can be used. Further, an inactive drying zone may be provided between the coating step and the drying step in the drying furnace for the purpose of adjusting the appearance of the coated surface, the purpose of adjusting the pressure difference between the inside and outside of the drying furnace, and the like. In addition, a cooling zone or the like may be provided after passing through the drying oven.
In a preferred embodiment of the present invention, there can be provided a method for producing the laminate, the method comprising: a step 1 of coating a surface of a base material layer with a resin composition containing a radiation curable resin and an organic solvent to obtain a coated article; and a step 2 of drying the obtained coated article to form a surface layer on the surface of the base material layer, wherein the laminate has at least the base material layer and the surface layer, the resin composition contains an organic solvent (A) having a boiling point of less than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or more and a mass ratio A:B in the range of 3:7 to 7:3, the resin composition contains a (meth) acryl polymer (C) having a (meth) acrylic acid equivalent weight of 200 to 600g/eq and a weight average molecular weight of 5,000 ～ 200,000, and the evaluation result of film adhesion of the surface layer determined in accordance with the evaluation method of JIS K5600-5-6 is 0.
In one embodiment of the present invention, there may be at least two drying ovens used in the step 2. In a preferred embodiment of the present invention, at least two drying ovens may be used in the step 2, and the drying oven temperature of the last drying oven is higher than the drying oven temperature of the first drying oven.
In a preferred embodiment of the present invention, at least two drying ovens capable of heating the coated article to 60 ℃ or higher may be used in the step 2. In this embodiment, the drying furnace temperature of the first drying furnace may be in the range of 90 to 120 ℃, and the drying furnace temperature of the second drying furnace may be in the range of 100 to 140 ℃. In a more preferred embodiment of the present invention, in the step 2, at least two drying ovens capable of heating the coated article to 60 ℃ or higher may be used, and the drying oven temperature of the first drying oven is in the range of 90 to 120 ℃ and the drying oven temperature of the second drying oven is in the range of 100 to 140 ℃.
In a preferred embodiment of the present invention, in the step 2, at least two drying ovens capable of heating the coated article to 60 ℃ or higher may be used, and the drying oven temperature of the last drying oven is higher than the drying oven temperature of the first drying oven. In a more preferred embodiment of the present invention, in the step 2, at least two drying ovens capable of heating the coated article to 60 ℃ or higher, the first drying oven having a drying oven temperature in the range of 90 to 120 ℃ and the last drying oven having a drying oven temperature in the range of 100 to 140 ℃, may be used.
In a preferred embodiment of the present invention, the thickness of the base layer is 0.1 to 1.0mm, and the thickness of the layer of the resin composition applied to the surface of the base layer is 1.0 to 10. Mu.m.
A mask may be further attached to the surface of the laminate having the base material layer and the surface layer on the surface layer side.
< physical Properties of surface layer >
(i) Thickness of (L)
In the present invention, the thickness of the surface layer 20 is preferably 1.0 μm to 10 μm. The thickness of the surface layer is, for example, 2.0 μm to 8.0 μm or 3.0 μm to 7.0 μm.
(ii) Scratch resistance
When the surface layer is cured, high scratch resistance can be achieved. As described in detail later, when the laminate having the surface layer was cured, it was confirmed that the scratch resistance of the surface layer was superior to that of the PMMA resin (polymethyl methacrylate resin) and the lens resin after curing.
(iii) Hardness of
The cured surface layer has a high hardness. Specifically, JIS K5600-5-4 can be realized: 1999, pencil hardness of B or greater. The surface of the cured surface layer can have a pencil hardness of more preferably F or more, particularly preferably 2H or more.
(vi) Film adhesion
The surface layer obtained by curing the resin composition is also excellent in film adhesion to the base material layer. Specifically, after the resin composition was applied to the base material layer, UV curing as a pretreatment and environmental test were performed under the following conditions, and the adhesion of the coating film after the environmental test was evaluated.
< pretreatment: UV curing
UV irradiation device: COST-40 manufactured by GS Yuasa, inc
UV lamp (HAN 250 AL)
Cumulative light amount: 750mJ/cm 2 ( Ultraviolet integrating illuminometer: UVPF-A2/photoreceiver PD-365A2 manufactured by Kawasaki electric Co., ltd )
Peak intensity 250mW/cm 2 ( Ultraviolet integrating illuminometer: UVPF-A2/photoreceiver PD-365A2 manufactured by Kawasaki electric Co., ltd )
< environmental test >
The durability test was performed for 1,000 hours at 85 ℃/85% RH.
< test of adhesion of coating film >
According to JIS K5600-5-6: 1999, film adhesion test was performed.
The laminate of the present invention is produced according to JIS K5600-5-6: 1999, the evaluation result determined by the evaluation method is 0, and a better result than the evaluation results 1 to 5 can be obtained.
From the above-described properties of the surface layer obtained after curing, it was clear that the surface of the cured film on the surface layer side had excellent properties. That is, on the surface of the surface layer side of the cured film, a high pencil hardness is preferable in accordance with JIS K5600-5-4: 1999 is B or more, high scratch resistance, and excellent adhesion, for example, adhesion of class 0 according to the evaluation result of JIS K5600-5-6.
< physical Properties of laminate >
(i) Residual solvent amount
In one embodiment of the present invention, the amount of the residual solvent in the laminate can be 82mg/m 2 The following laminate. In an embodiment of the present invention, the amount of residual solvent in the laminate may be 82mg/m 2 The following is 80mg/m 2 Below, 75mg/m 2 The following, 70mg/m 2 The following is 65mg/m 2 Below, 60mg/m 2 The following is 55mg/m 2 Below, 50mg/m 2 Below, 45mg/m 2 The following 40 mg-m 2 Below, 35mg/m 2 Below, 30mg/m 2 Below, 25mg/m 2 The following, etc. In the present invention, the smaller the amount of residual solvent in the laminate, the better.
According to the method of the present invention, a laminate is obtained which comprises at least a base layer and a surface layer provided on the surface of the base layer, wherein the surface layer is formed by coating a resin composition containing an organic solvent (A) having a boiling point of less than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or more and a mass ratio A:B in the range of 3:7 to 7:3, drying the resin composition in at least a first drying oven at a temperature in the range of 90 to 120 ℃ and then drying the resin composition in a second drying oven at a temperature in the range of 100 to 140 ℃, wherein the resin composition contains a (meth) acryl polymer (C) having a (meth) acrylic equivalent weight of 200 to 600g/eq and a weight average molecular weight of 5,000 ～ 200,000, and wherein the evaluation result of the film adhesion of the surface layer determined by the evaluation method of JIS K5600-5-6 is 0.
(ii) Appearance (pinhole)
Visually evaluating whether pinholes were present or not by using transmitted light and reflected light, and measuring 0.06mm phi or more and 0.3mm 2 The pinholes are below 10/m 2 Defined as qualified, 10/m 2 The above definition is failed.
< cured film >
When the coated material is dried and cured, a laminate as a cured film is obtained. In attaching the mask, curing is performed after removing the mask. In a preferred embodiment of the present invention, the laminate is a cured film.
< molded article >
By thermoforming the laminate, a molded article can be obtained. In one embodiment of the present invention, a molded article obtained by thermoforming the laminate can be provided.
Examples
The present invention is more specifically illustrated by the following examples. However, the present invention is not limited to the following examples, and may be carried out with any modification within the scope of the present invention.
Example 1 ]
The mass ratio of MIBK to cyclohexanone was made 6:4 by mixing cyclohexanone and methyl isobutyl ketone (MIBK) in an ultraviolet curable acryl polymer (ART CURE RA-3602MI, manufactured by the Industrial Co., ltd.) and the solid content concentration was adjusted to 20 mass%. Further, IRGACURE 184 (3 mass% relative to the solid content) was added as a photopolymerization initiator to obtain a resin composition for use in the surface layer.
The resin composition used for the surface layer obtained as described above was coated on the PMMA side of a Polycarbonate (PC)/polymethyl methacrylate (PMMA) film as a base layer, to obtain a coated article.
The coating process was performed using a 120-wire gravure roll. Then, the coated material was dried at 90℃in the first drying furnace (referred to as "pre-drying furnace" in the following table) and at 120℃in the last drying furnace (referred to as "post-drying furnace" in the following table), whereby a drying step was performed, and a radiation curable resin layer of about 4 μm was formed as a surface layer on the PMMA side surface, to obtain a laminate. The obtained laminate was evaluated for film adhesion, the amount of residual solvent, and the presence or absence of pinholes. The evaluation results are shown in the following table.
< examples 2 to 7, comparative examples 1 to 14>
A laminate was obtained in the same manner as in example 1, except that the composition and the drying temperature shown in the following table were changed. The obtained laminate was evaluated for film adhesion, the amount of residual solvent, and the presence or absence of pinholes in the same manner as in example 1. The evaluation results are shown in the following table.
TABLE 2
As described above, the laminate of the present invention has excellent characteristics of effectively improving the adhesion of a coating film after environmental test without impairing the characteristics required for a laminate for a molded article such as moldability, scratch resistance, hardness, adhesion, and good appearance. Therefore, the laminate of the present invention is suitable for applications such as automobile interior trim and housings for electronic devices.
Symbol description
10: a laminate; 20: a surface layer; 30: a substrate layer; 31: a first resin layer; 32: and a second resin layer.
Claims (19)
1. A laminate, characterized in that:
which has at least a base material layer and a surface layer provided on the surface of the base material layer,
the surface layer is formed by coating a resin composition containing an organic solvent (A) having a boiling point of less than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or higher and having a mass ratio A:B in the range of 3:7 to 7:3, drying the resin composition in a temperature range of 90 to 120 ℃ in at least a first drying furnace, and drying the resin composition in a temperature range of 100 to 140 ℃ in a second drying furnace,
the resin composition contains a (meth) acryl polymer (C) having a (meth) acrylic equivalent weight of 200 to 600g/eq and a weight average molecular weight of 5,000 ～ 200,000,
the film adhesion of the surface layer was evaluated as 0 according to the evaluation method of JIS K5600-5-6.
2. The laminate of claim 1, wherein:
the (meth) acryl polymer (C) contains a repeating unit represented by the following formula (I),
in the formula (I), m is an alkylene group having 1 to 4 carbon atoms or a single bond, n is an alkyl group having 1 to 4 carbon atoms or hydrogen, p is a single bond or an alkylene group having 1 or 2 carbon atoms, and q is an alkyl group having 1 to 12 carbon atoms or hydrogen which may contain at least one substituent selected from the group consisting of an epoxy group, a hydroxyl group, an acryl group and a methacryl group.
3. The laminate of claim 2, wherein:
in the formula (I), m is an alkylene group having 1 or 2 carbon atoms, n is an alkyl group having 1 or 2 carbon atoms, p is a single bond or a methylene group, and q is an alkyl group having 1 to 6 carbon atoms or hydrogen in total which may contain at least one substituent selected from the group consisting of a glycidyl group, a hydroxyl group and an acryl group.
4. A laminate according to claim 3, wherein:
in the formula (I), m is methylene, n is methyl, p is a single bond, q is methyl, alkyl having 5 or less carbon atoms including glycidyl (epoxy) group, or alkyl having 8 or less carbon atoms including hydroxy and acryl group.
5. The laminate of claim 2, wherein:
the (meth) acryl polymer (C) contains at least any one of the repeating units represented by the following formulas (II-a), (II-b) and (II-C),
6. the laminate of claim 5, wherein:
the repeating unit of formula (II-a) is 30 to 85 mol%, the repeating unit of formula (II-b) is 5 to 30 mol%, and the repeating unit of formula (II-c) is 10 to 40 mol%, based on the total mole number of the repeating unit of formula (II-a), the repeating unit of formula (II-b) and the repeating unit of formula (II-c).
7. The laminate of claim 5, wherein:
the molar ratio of the repeating unit of formula (II-a), the repeating unit of formula (II-b) and the repeating unit of formula (II-c) is 4.5-5.5:1.5-2.5:2.5-3.5.
8. The laminate according to any one of claims 1 to 7, wherein:
the (meth) acryl polymer (C) further comprises a pentaerythritol-based polyfunctional acrylate compound.
9. The laminate of claim 8, wherein:
the pentaerythritol-based multifunctional acrylate compound is one or more selected from pentaerythritol tetraacrylate represented by the following formula (III-a), dipentaerythritol hexaacrylate represented by the formula (III-b) and pentaerythritol triacrylate,
10. the laminate of claim 8 or 9, wherein:
the content of the pentaerythritol-based polyfunctional acrylate compound is 70 mass% or less based on the total mass of the resin composition.
11. The laminate according to any one of claims 1 to 10, wherein:
the resin composition is a radiation curable resin composition.
12. The laminate according to any one of claims 1 to 11, wherein:
The resin composition further contains a photopolymerization initiator.
13. The laminate according to any one of claims 1 to 12, wherein:
the substrate layer contains a thermoplastic resin.
14. The laminate according to any one of claims 1 to 13, wherein:
the laminate is a decorative sheet.
15. A molded article characterized in that:
a molded article obtained by thermoforming the laminate according to any one of claims 1 to 14.
16. A method of manufacturing the laminate of any one of claims 1 to 15, comprising:
a step 1 of coating a surface of a base material layer with a resin composition containing a radiation curable resin and an organic solvent to obtain a coated article; and
a step 2 of drying the obtained coated article to form a surface layer on the surface of the base material layer,
the laminate has at least a base material layer and a surface layer,
the resin composition contains an organic solvent (A) having a boiling point of less than 120 ℃ and an organic solvent (B) having a boiling point of 120 ℃ or more and a mass ratio A:B in the range of 3:7 to 7:3,
the resin composition contains a (meth) acryl polymer (C) having a (meth) acrylic equivalent weight of 200 to 600g/eq and a weight average molecular weight of 5,000 ～ 200,000,
The film adhesion of the surface layer was evaluated as 0 according to the evaluation method of JIS K5600-5-6.
17. The method as recited in claim 16, wherein:
in the step 2, at least two drying ovens are used, and the drying oven temperature of the last drying oven is higher than the drying oven temperature of the first drying oven.
18. The method of claim 16 or 17, wherein:
in the step 2, at least two drying ovens capable of heating the coated article to 60 ℃ or higher are used, the temperature of the drying oven of the first drying oven is in the range of 90 to 120 ℃, and the temperature of the drying oven of the second drying oven is in the range of 100 to 140 ℃.
19. The method of any one of claims 16 to 18, wherein:
the thickness of the base material layer is 0.1mm to 1.0mm, and the thickness of the layer of the resin composition coated on the surface of the base material layer is 1.0 μm to 10 μm.
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| JP2021016807 | 2021-02-04 | ||
| JP2021-016807 | 2021-02-04 | ||
| PCT/JP2022/003714 WO2022168811A1 (en) | 2021-02-04 | 2022-02-01 | Multilayer body and method for producing same |
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| JP2003231218A (en) | 2002-02-06 | 2003-08-19 | Mitsubishi Rayon Co Ltd | Manufacturing method of photocurable sheet and manufacturing method of photocurable sheet and insert molded article |
| JP2012072327A (en) | 2010-09-29 | 2012-04-12 | Nippon Shokubai Co Ltd | Radical polymerizable group-containing urethane prepolymer, urethane (meth)acrylate, photocurable resin composition, hard coat film, and molded product |
| CA2932925C (en) | 2015-09-29 | 2016-12-06 | Yoshihumi Kominami | Coating resin composition |
| WO2018038101A1 (en) * | 2016-08-24 | 2018-03-01 | パナック株式会社 | Resin composition, uncured resin layer, resin film and production method therefor, and laminate production method |
| JP7172365B2 (en) | 2018-09-26 | 2022-11-16 | 大日本印刷株式会社 | Decorative sheet, decorative resin molded product, and method for producing the same |
| CN115335227A (en) | 2020-03-26 | 2022-11-11 | 三菱瓦斯化学株式会社 | Film insert molded article and method for producing film insert molded article |
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