WO2017110843A1 - 活性エネルギー線硬化型樹脂組成物、活性エネルギー線硬化型エマルジョン組成物及びコーティング剤組成物 - Google Patents
活性エネルギー線硬化型樹脂組成物、活性エネルギー線硬化型エマルジョン組成物及びコーティング剤組成物 Download PDFInfo
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- WO2017110843A1 WO2017110843A1 PCT/JP2016/088039 JP2016088039W WO2017110843A1 WO 2017110843 A1 WO2017110843 A1 WO 2017110843A1 JP 2016088039 W JP2016088039 W JP 2016088039W WO 2017110843 A1 WO2017110843 A1 WO 2017110843A1
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- acrylate
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
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- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- HUBKGVIIAXRGDJ-UHFFFAOYSA-N hexane-1,6-diol;oxirane Chemical compound C1CO1.OCCCCCCO HUBKGVIIAXRGDJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000006368 phosphonoyl group Chemical group [*:1]P([*:2])=O 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- JUYONNFUNDDKBE-UHFFFAOYSA-J tri(oct-2-enoyloxy)stannyl oct-2-enoate Chemical compound [Sn+4].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O JUYONNFUNDDKBE-UHFFFAOYSA-J 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- RVXKJRWBHPHVOV-UHFFFAOYSA-L zinc;oct-2-enoate Chemical compound [Zn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O RVXKJRWBHPHVOV-UHFFFAOYSA-L 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
Definitions
- the present invention relates to an active energy ray-curable resin composition, and more specifically, a coating film having excellent self-emulsifying properties with respect to an aqueous medium and excellent hardness and warm water resistance when coated on a substrate is obtained.
- the present invention relates to an active energy ray-curable resin composition.
- the present invention also comprises an active energy ray curable emulsion composition obtained by dispersing the active energy ray curable resin composition in an aqueous medium, and the active energy ray curable resin composition dispersed in an aqueous medium. It also relates to a coating agent composition.
- a urethane (meth) acrylate obtained by reacting a diol compound such as polyester diol or polyether diol, a diisocyanate compound such as isophorone diisocyanate or diphenylmethane diisocyanate, and a hydroxyl group-containing (meth) acrylate such as hydroxyethyl acrylate has been active.
- a diol compound such as polyester diol or polyether diol
- a diisocyanate compound such as isophorone diisocyanate or diphenylmethane diisocyanate
- a hydroxyl group-containing (meth) acrylate such as hydroxyethyl acrylate
- urethane (meth) acrylate Since such urethane (meth) acrylate is generally high in viscosity, it is diluted with an organic solvent or reactive diluent to adjust the viscosity, and then coated and UV-cured to form a coating film. To do. However, in the case of diluting with an organic solvent, it has become a problem under recent VOC regulations for air pollution, work environment, fire risk and the like. On the other hand, when diluting with a reactive diluent, a large amount of reactive diluent may be required to lower the viscosity, and there are problems such as difficulty in obtaining sufficient film properties.
- a polyfunctional urethane acrylate compound is used as the polyfunctional oligomer, and a urethane acrylate compound having a hydrophilic group and a hydrophobic group is used as the polyfunctional reactive surfactant.
- An active energy ray-curable emulsion composition (for example, see Patent Document 1) dispersed in an aqueous medium in the presence of a functional reactive surfactant has been proposed.
- the coating film adhesion to the plastic substrate is normal, and in addition, the appearance of the coating film is not only normal but also after being immersed in warm water. Although judged to be good with no change, there was a problem of not having satisfactory coating film adhesion from a practical viewpoint.
- the appearance of the coating does not change before and after the durability test, and the coating adhesion after the durability test is also evaluated under the same evaluation conditions as during normal times. When this is done, it is regarded as a practically important physical property index that there is no change in coating film adhesion.
- the general-purpose plastic base material includes a polycarbonate base material having higher heat resistance. An energy ray curable resin composition is required.
- an active energy ray-curable resin that is excellent in self-emulsifying property with respect to an aqueous medium and that can provide a coating film having excellent hardness and water resistance when coated on a substrate and cured.
- Composition, active energy ray-curable emulsion composition obtained by dispersing the active energy ray-curable resin composition in an aqueous medium, and coating agent composition obtained by dispersing the active energy ray-curable resin composition in an aqueous medium The purpose is to provide goods.
- the inventor of the present invention uses a urethane (meth) acrylate compound having an oxyalkylene structure in combination with an ethylenically unsaturated monomer having a specific structure, so An activity that is excellent in emulsifying properties, and has a high hardness when coated on a substrate and cured, and can obtain a cured coating film that is less likely to deteriorate the appearance of the coating film such as whitening or deteriorate the adhesion performance even after immersion in warm water. It discovered that an energy-beam curable resin composition was obtained, and completed this invention.
- the gist of the present invention is that the isocyanate group in the polyvalent isocyanate compound (a1) is a hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2) and an oxyalkylene group-containing compound represented by the following general formula (1) (an active energy comprising a urethane (meth) acrylate compound (A) formed by forming a urethane bond with a hydroxyl group of a3) and an ethylene oxide-modified trimethylolpropane tri (meth) acrylate (B) It exists in a wire curable resin composition.
- an active energy comprising a urethane (meth) acrylate compound (A) formed by forming a urethane bond with a hydroxyl group of a3
- X is an alkylene group
- Y is any one of a hydrogen atom, an alkyl group, a (meth) acryloyl group, an allyl group, and an acyl group
- n is an integer of 1 or more.
- an active energy ray-curable emulsion composition obtained by dispersing the active energy ray-curable resin composition in an aqueous medium, and the active energy ray-curable resin composition are dispersed in an aqueous medium.
- a coating agent composition is provided.
- the active energy ray-curable resin composition of the present invention is excellent in self-emulsifying property with respect to an aqueous medium, and can provide a coating film having excellent hardness and warm water resistance when coated on a substrate and cured.
- adhesives, adhesives, adhesives, inks, protective coatings, anchor coatings, hard coats, etc. It is very useful as various film forming materials such as coating agents, magnetic powder coating binders, sandblast coatings, plate materials, coating agents for optical film topcoats, metal deposition and sputtering films, and coating agents for glass modification.
- (meth) acryl means acryl or methacryl
- (meth) acryloyl means acryloyl or methacryloyl
- (meth) acrylate means acrylate or methacrylate.
- the active energy ray-curable resin composition of the present invention comprises a urethane (meth) acrylate compound (A) and an ethylene oxide-modified trimethylolpropane tri (meth) acrylate (B).
- the urethane (meth) acrylate compound (A) used in the present invention includes a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and an oxyalkylene group represented by the following general formula (1).
- a urethane (meth) acrylate compound comprising the containing compound (a3), wherein the isocyanate group in the polyvalent isocyanate compound (a1) is a hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2) and the following general formula (1 ) Is a urethane (meth) acrylate compound formed by forming a urethane bond with the hydroxyl group of the oxyalkylene group-containing compound (a3).
- the urethane (meth) acrylate compound (A) used in the present invention has a hydrophilic structural site derived from the oxyalkylene group-containing compound (a3) represented by the general formula (1) having hydrophilicity, Moreover, since it has a hydrophobic residue of the hydroxyl group-containing (meth) acrylate compound (a2), it plays a role as a surfactant.
- polyvalent isocyanate compound (a1) examples include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate.
- Polyisocyanates aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate Cycloaliphatic polyisocyanates such as tomethyl) cyclohexane; or trimer compounds or multimeric compounds of these polyisocyanates, allophanate polyisocyanates, burette polyisocyanates, water-dispersed polyisocyanates (for example, manufactured by Tosoh Corporation) ("Aquanate 100", "Aquanate 110", “Aquanate 200", “Aquanate 210", etc.).
- These polyvalent isocyanate compounds (a1) can be used singly or in
- alicyclic polyisocyanates are preferably used in terms of less yellowing of the cured coating film and less curing shrinkage, and in particular, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanato). Methyl) cyclohexane is more preferably used.
- Examples of the hydroxyl group-containing (meth) acrylate compound (a2) include, for example, a monofunctional hydroxyl group-containing (meth) acrylate compound, a bifunctional hydroxyl group-containing (meth) acrylate compound, and a tri- or more functional hydroxyl group-containing (meth) acrylate. And other hydroxyl group-containing (meth) acrylate compounds.
- Examples of monofunctional hydroxyl group-containing (meth) acrylate compounds include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, and 6-hydroxyhexyl (meth).
- hydroxyl groups such as (meth) acrylic acid hydroxyalkyl esters such as acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate (Meth) acrylate; secondary hydroxyl group-containing (meth) acrylate such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; Tertiary hydroxyl group-containing and dimethyl-2-hydroxyethyl (meth) acrylate (meth) acrylate.
- primary hydroxyl groups such as (meth) acrylic acid hydroxyalkyl esters such as acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth)
- Examples of the bifunctional hydroxyl group-containing (meth) acrylate compound include isocyanuric acid ethylene oxide-modified di (meth) acrylate, glycerol epichlorohydrin-modified 1,6-hexanediol di (meth) acrylate, and the like.
- Examples of the tri- or higher functional hydroxyl group-containing (meth) acrylate compound include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, and caprolactone-modified pentaerythritol tris.
- Other hydroxyl group-containing (meth) acrylate compounds include, for example, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxy. Examples thereof include propyl (meth) acrylate and caprolactone-modified 2-hydroxyethyl (meth) acrylate.
- These hydroxyl group-containing (meth) acrylate compounds (a2) can be used alone or in combination of two or more.
- a polyfunctional hydroxyl group-containing (meth) acrylate compound is preferable, particularly a trifunctional or more functional hydroxyl group-containing (meth) acrylate compound, more preferably pentaerythritol tri (meta).
- the oxyalkylene group-containing compound (a3) is represented by the following general formula (1) and can be used singly or in combination of two or more.
- X is an alkylene group
- Y is a hydrogen atom, an alkyl group, a (meth) acryloyl group, an allyl group, or an acyl group
- n is an integer of 1 or more.
- X in the general formula (1) is an alkylene group, and among them, an alkylene group having 1 to 10 carbon atoms is preferable from the viewpoint of excellent hydrophilicity, more preferably an ethylene group, a propylene group, a tetramethylene group or the like. An alkylene group having 1 to 4 carbon atoms, particularly an ethylene group is preferred.
- the oxyalkylene group-containing compound (a3) may be a homopolymer of the same oxyalkylene chain, or different oxyalkylene chains may be copolymerized randomly or in blocks. You may have done.
- n is an integer of 1 or more, preferably 3 to 300, particularly preferably 5 to 200, more preferably 5 to 100, and particularly preferably 6 to 50.
- n is an integer of 1 or more, preferably 3 to 300, particularly preferably 5 to 200, more preferably 5 to 100, and particularly preferably 6 to 50.
- Y in the general formula (1) is any one of a hydrogen atom, an alkyl group, a (meth) acryloyl group, an allyl group, and an acyl group, and among these, it is excellent in the balance between hydrophilicity and reactivity.
- a hydrogen atom, an alkyl group, and a (meth) acryloyl group are preferable, and a hydrogen atom is particularly preferable.
- the alkyl group those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms are usually used. Among these, a methyl group and an ethyl group are particularly preferable.
- acyl group examples include an acetyl group, an acetimidoyl group, a thioacetyl group, a benzenesulfonyl group, a phosphononitridoyl group, and a phosphonoyl group.
- an acetyl group is preferable.
- oxyalkylene group-containing compound (a3) examples include the following.
- Y is a hydrogen atom
- Y is an alkyl group, for example, polyethylene glycol monomethyl ether, polyethylene glycol lauryl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol nonylphenyl ether, polyethylene glycol tridecyl ether, polyethylene glycol oleyl ether, polyethylene glycol octylphenyl And polyethylene glycol derivatives such as ether and polyoxyethylene oleyl cetyl ether; polypropylene glycol derivatives such as polypropylene glycol monomethyl ether; and the like.
- Y is a (meth) acryloyl group
- polyethylene glycol derivatives such as polyethylene glycol mono (meth) acrylate
- polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate
- examples include poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, and the like.
- examples include polyethylene glycol derivatives such as polyethylene glycol monoallyl ether, polypropylene glycol derivatives such as polypropylene glycol monoallyl ether, polyethylene glycol-polypropylene glycol-monoallyl ether, and the like.
- Y is an acyl group
- examples thereof include polyethylene glycol derivatives such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, and the like.
- a polyethylene glycol derivative (a compound in which X in the formula (1) is an ethylene group) is preferable, and an ethylene oxide addition mole number (in the formula (1) is particularly preferable.
- a polyethylene glycol derivative having an addition mole number (value of n in the formula (1)) of 6 to 50 is preferred in that it has an excellent balance between hydrophilic groups and hydrophobic groups.
- Y is preferably a hydrogen atom, an alkyl group, or a (meth) acryloyl group, and particularly preferably a hydrogen atom.
- the weight average molecular weight of the oxyalkylene group-containing compound (a3) represented by the general formula (1) is usually preferably from 100 to 10,000, particularly from 200 to 6,000, more preferably from 400 to 3,000. Is preferred. If the weight average molecular weight is too small, a stable emulsified dispersion tends to be difficult to obtain, and if it is too large, the warm water resistance tends to decrease when a cured coating film is formed.
- the hydroxyl value of the oxyalkylene group-containing compound (a3) represented by the general formula (1) is usually preferably 2 to 560 mgKOH / g, particularly 10 to 280 mgKOH / g, more preferably 25 to 200 mgKOH / g. preferable. If the hydroxyl value is too small, the hot water resistance of the cured coating film tends to decrease, and if it is too large, the emulsion stability tends to decrease.
- the urethane (meth) acrylate compound (A) used in the present invention is obtained by reacting a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and an oxyalkylene group-containing compound (a3). Obtained by forming a urethane bond with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2) and the hydroxyl group of the polyoxyalkylene group-containing compound (a3), respectively, in the isocyanate group in the polyvalent isocyanate compound (a1). It is done.
- the polyvalent isocyanate compound (a1) when the polyvalent isocyanate compound (a1) has two isocyanate groups, one isocyanate group forms a urethane bond with the hydroxyl group of the oxyalkylene group-containing compound (a3), and the remaining one isocyanate group. It becomes a urethane (meth) acrylate compound in which the group forms a urethane bond with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2).
- the polyisocyanate compound (a1) has three isocyanate groups, one isocyanate group is a hydroxyl group of the oxyalkylene group-containing compound (a3) (or a hydroxyl group-containing (meth) acrylate compound (a2)).
- Urethane (meth) acrylate in which the remaining two isocyanate groups form a urethane bond with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2) (or oxyalkylene group-containing compound (a3)). It becomes a system compound.
- a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and an oxyalkylene group-containing compound (a3) are charged together.
- the method includes reacting the polyvalent isocyanate compound (a1) with the oxyalkylene group-containing compound (a3) and then reacting the hydroxyl group-containing (meth) acrylate compound (a2). From the viewpoint of shortening the production time, the method (b) is preferred.
- a catalyst for the purpose of promoting the reaction.
- a catalyst include dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin.
- Organometallic compounds such as tin octylate, zinc octenoate, tin octenoate, cobalt naphthenate, stannous chloride, stannic chloride; triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2 , 2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl-1,3-butanediamine, amine catalysts such as N-ethylmorpholine; bismuth System catalysts; and the like.
- the bismuth catalyst examples include inorganic bismuth compounds such as bismuth nitrate, bismuth bromide, bismuth iodide and bismuth sulfide; organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate; bismuth 2-ethylhexanoate, naphthenic acid Bismuth salt, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, di Examples include organic acid bismuth salts such as bismuth salicylate and bismuth digallate. Among these, dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are preferable.
- the reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C.
- the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
- the weight average molecular weight of the urethane (meth) acrylate compound (A) is usually preferably 500 to 50,000, particularly 750 to 20,000, and more preferably 1,000 to 10,000. preferable. If the weight average molecular weight is too small, the cured coating film tends to be brittle. If the weight average molecular weight is too large, the viscosity becomes high and difficult to handle, and the hardness of the cured coating film tends to decrease.
- the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and column: Shodex GPC KF- is used in high performance liquid chromatography (“Shodex GPC system-11 type” manufactured by Showa Denko KK). 806 L (exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 ⁇ m) It is measured by using three series.
- the viscosity of the urethane (meth) acrylate compound (A) is preferably 200 to 20,000 mPa ⁇ s, particularly 350 to 5,000 mPa ⁇ s, more preferably 500 to It is preferably 3,000 mPa ⁇ s. If the viscosity is too high, it tends to be difficult to uniformly disperse in an aqueous medium, and if it is too low, the self-emulsification performance tends to be low and the solution tends to be separated into layers. The viscosity is measured with an E-type viscometer.
- the content of the urethane (meth) acrylate compound (A) is the sum of the contents of the urethane (meth) acrylate compound (A) and ethylene oxide-modified trimethylolpropane tri (meth) acrylate (B) (( When the ethylenically unsaturated monomer (E) other than B) is contained, it is preferably 5 to 55% by weight (among the total of the contents of (A), (B) and (E)), particularly The amount is preferably 15 to 50% by weight, more preferably 23 to 45% by weight. When the content is too small, the stability of the emulsion tends to decrease, and when it is too large, the water resistance of the coating film tends to decrease.
- Examples of the ethylene oxide-modified trimethylolpropane tri (meth) acrylate (B) used in the present invention include ethoxylated trimethylolpropane triacrylate.
- ethoxylated trimethylolpropane triacrylate For example, “A-TMPT” manufactured by Shin-Nakamura Chemical Co., Ltd. -3EO “,” A-TMPT-9EO “,” AT-20E “,” AT-30E “,” Laromar LR-8863 “manufactured by BASF Japan Ltd.,” SR-454 “,” SR499 “,” made by Sartomer "
- Commercial products such as “SR502” can be used.
- the ethylene oxide-modified trimethylolpropane tri (meth) acrylate (B) content is preferably 40 to 1,500 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A).
- the amount is particularly preferably 50 to 1,300 parts by weight, more preferably 60 to 330 parts by weight, and particularly preferably 90 to 220 parts by weight. If the content is too small, the adhesiveness of the cured coating film tends to decrease, and if it is too large, the coating film tends to become brittle.
- the active energy ray-curable resin composition of the present invention contains a photopolymerization initiator (C) that initiates polymerization upon irradiation with active energy rays, and promotes curing when irradiated with active energy rays. This is preferable.
- the timing of addition of the photopolymerization initiator (C) is not particularly limited, and may be added before the active energy ray-curable resin composition is dispersed in water, or the active energy ray-curable resin composition is dispersed in water. It may be added after.
- Examples of the photopolymerization initiator (C) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ben such as ether Ins; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenz
- acetophenones and benzophenones are preferably used, and in particular, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-) Propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one is preferably used.
- auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid.
- Ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.
- a water-soluble or water-dispersible photopolymerization initiator from the viewpoint of exhibiting more functions in applications as a composition of an aqueous dispersion.
- a water-soluble or water-dispersible photopolymerization initiator C
- 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9-one methochloride manufactured by Octel Chemicals, “Quantacure QTX”
- 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one manufactured by BASF, “Irgacure 2959”
- 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (manufactured by BASF, “Irgacure 2959”)
- 1-hydroxy-cyclohexyl-phenyl- A water-soluble or water-dispersible photopolymerization initiator of a mixture of a ketone and benzophenone (manufactured by BASF, “Irgacure 500”) is suitable.
- the amount of the photopolymerization initiator (C) used is the sum of the components (A) and (B) (when the components (D) and (E) below are included, (A), (B), (D) and
- the total amount of component (E) is preferably 1 to 10 parts by weight, particularly preferably 1 to 8 parts by weight, and more preferably 2 to 6 parts by weight per 100 parts by weight. If the amount used is too small, the curing rate of curing by irradiation with active energy rays such as ultraviolet rays becomes extremely slow, and the intended cured coating film tends not to be obtained. If the amount used is too large, the curability is not improved, and the cured coating tends to cause yellowing.
- the active energy ray-curable resin composition of the present invention includes a urethane (meth) acrylate compound (D) other than the urethane (meth) acrylate compound (A), ethylene, as long as the effects of the present invention are not impaired.
- An ethylenically unsaturated monomer (E) other than the oxide-modified trimethylolpropane tri (meth) acrylate (B) may be contained.
- urethane (meth) acrylate compound (D) other than the urethane (meth) acrylate compound (A) for example, a polyvalent isocyanate compound (d1) and a hydroxyl group-containing (meth) acrylate compound (d2) are reacted.
- Urethane (meth) obtained by reacting a urethane (meth) acrylate compound (D1), a polyvalent isocyanate compound (d1), a hydroxyl group-containing (meth) acrylate compound (d2) and a polyol compound (d3)
- an acrylate compound (D2) is mentioned, in the present invention, the urethane (meth) acrylate compound (D1) is contained in a range that does not inhibit the adhesion of the cured coating film in terms of improving the coating film hardness. It is preferable to make it.
- only 1 type may be used for a urethane (meth) acrylate type compound (D), and 2 or more types may be used together.
- Examples of the polyvalent isocyanate compound (d1) include those similar to the above (a1), and an alicyclic polyisocyanate compound is preferably used in terms of less yellowing of the cured coating film and small curing shrinkage.
- isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane are more preferably used.
- Examples of the hydroxyl group-containing (meth) acrylate compound (d2) include those similar to the above (a2).
- the polyol compound (d3) may be, for example, a compound containing two or more hydroxyl groups.
- aliphatic polyol, alicyclic polyol, polyether polyol, polyester polyol, polycarbonate polyol, polyolefin examples thereof include a system polyol, a polybutadiene system polyol, a polyisoprene system polyol, a (meth) acrylic system polyol, and a polysiloxane system polyol.
- aliphatic polyols and alicyclic polyols are preferably used in terms of cost
- polyester-based polyols, polyether-based polyols, and polycarbonate-based polyols are preferably used in terms of versatility.
- the urethane (meth) acrylate compound (D) can be produced by reacting the above components by a known reaction means.
- a known reaction means is prepared by charging the polyisocyanate compound (d1) and the hydroxyl group-containing (meth) acrylate compound (d2) into a reactor all at once or separately. Can be produced by urethanization reaction.
- a polyol compound (d3) is further reacted in addition to the polyvalent isocyanate compound (d1) and the hydroxyl group-containing (meth) acrylate compound (d2).
- the polyol compound (d3) and the polyvalent isocyanate compound (d1) are reacted in advance.
- a method of producing the reaction product by reacting the hydroxyl group-containing (meth) acrylate compound (d2) with the obtained reaction product is useful in terms of stability of the urethanization reaction and reduction of by-products.
- the urethane (meth) acrylate compound (D) is obtained by terminating the reaction when the residual isocyanate group content in the reaction system is 0.5 wt% or less.
- a catalyst for the purpose of accelerating the reaction.
- the same catalyst as that used in the production of the urethane (meth) acrylate (A) is used.
- an organic solvent having no functional group that reacts with an isocyanate group for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic such as toluene and xylene Etc., organic solvents such as
- the reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C.
- the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
- the urethane (meth) acrylate compound (D) preferably has 2 to 20 ethylenically unsaturated groups from the viewpoint of increasing the crosslinking density and further improving the hardness of the cured coating film, 3 to 18 are particularly preferable, and 5 to 15 are more preferable. If the number of such ethylenically unsaturated groups is too large, the crosslinking density after curing becomes too high, and the shrinkage tends to decrease due to an increase in curing shrinkage. If it is too small, a sufficient crosslinking density cannot be obtained. There is a tendency that improvement of hardness in the film cannot be expected.
- the weight average molecular weight of the urethane (meth) acrylate compound (D) is preferably 500 to 30,000, particularly preferably 1,000 to 20,000, and still more preferably 1,500 to 10,000. 000.
- the weight average molecular weight is preferably 500 to 10,000, particularly preferably 800 to 8,000. More preferably, it is 1,000 to 5,000, particularly preferably 1,200 to 3,500.
- the weight average molecular weight is too high, the viscosity of the composition tends to increase and water dispersion tends to be difficult. If the weight average molecular weight is too low, the relative crosslink density increases, but the hardness of the cured coating film is improved. There is a tendency not to expect.
- said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, and can be measured by the method similar to the above.
- the viscosity of the urethane (meth) acrylate compound (D) at 60 ° C. is preferably 200 to 30,000 mPa ⁇ s, particularly preferably 500 to 15,000 mPa ⁇ s.
- the viscosity is measured with an E-type viscometer.
- the content of the urethane (meth) acrylate compound (D) is the urethane (meth) acrylate compound.
- the content is too large, the emulsification dispersibility becomes difficult, and the solution stability tends to be lowered or the adhesiveness tends to be impaired.
- an ethylenically unsaturated monomer (E) other than (B) inhibits coating film adhesion and solution stability of an aqueous solution. You may contain in the range which does not do.
- Examples of the ethylenically unsaturated monomer (E) include monofunctional monomers, bifunctional monomers, and trifunctional or higher monomers.
- Examples of the monofunctional monomer include styrene, vinyl toluene, chlorostyrene, ⁇ -methyl styrene, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (
- a Michael adduct of (meth) acrylic acid or 2- (meth) acryloyloxyethyl dicarboxylic acid monoester may be mentioned.
- Examples of the Michael adduct of (meth) acrylic acid include acrylic acid dimer, Examples include methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, and methacrylic acid tetramer.
- Examples of 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxy Examples include ethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, and the like. Furthermore, oligoester acrylate is also mentioned.
- bifunctional monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene.
- tri- or higher functional monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth).
- ethylenically unsaturated monomers (E) may be used alone or in combination of two or more. Further, the ethylenically unsaturated monomer (E) may be separately blended in the active energy ray-curable resin composition of the present invention, or a urethane (meth) acrylate compound (A) or urethane (meth). As a production raw material of the acrylate compound (D), a part of the acrylate compound (D) may be left in the system at the time of production.
- the content of the ethylenically unsaturated monomer (E) is 100% by weight of the urethane (meth) acrylate compound (A).
- the amount is preferably 60 parts by weight or less, particularly preferably 55 parts by weight or less, and still more preferably 50 parts by weight or less with respect to parts. If the content is too large, it is difficult to emulsify and disperse, and the solution stability tends to decrease.
- the active energy ray-curable resin composition of the present invention includes a tackifier, UV absorber, organic / inorganic filler plasticizer, antiseptic / antifungal agent, dispersant, wetting agent stabilizer, antifoaming agent, leveling agent.
- Additives such as additives, thixotropic agents, antioxidants, flame retardants, antistatic agents, reinforcing agents, matting agents, crosslinking agents, rust inhibitors, freeze-thaw stabilizers, pigments, colorants, thickeners, etc. You can also
- a conventionally known emulsifier for example, a surfactant having no polymerizable unsaturated group or a reactive surfactant having one polymerizable unsaturated group may be used in combination as appropriate.
- active energy ray-curable emulsion composition By dispersing the active energy ray-curable resin composition containing the urethane (meth) acrylate compound (A) and the ethylene oxide-modified trimethylolpropane tri (meth) acrylate (B) in an aqueous medium, the present invention.
- the active energy ray-curable emulsion composition is obtained and can be used as the coating agent composition of the present invention.
- aqueous medium water can be used, and a mixed solvent obtained by mixing water with a lower alcohol or the like can be used as long as the emulsion form of the present invention is not impaired.
- Examples of the method for producing the active energy ray-curable emulsion composition of the present invention include the following methods (1) to (4).
- a method in which the acrylate compound (D) and the ethylenically unsaturated monomer (E) are charged in a lump and usually stirred at 30 to 70 ° C., preferably 50 to 65 ° C.
- the urethane (meth) acrylate compound (A) dispersed in water is added dropwise and stirred.
- Method, (4) Ethylene oxide-modified trimethylolpropane tri (meth) acrylate (B) is dropped into the urethane (meth) acrylate compound (A) dispersed in water at room temperature, and usually stirred at room temperature to 40 ° C. how to.
- the production method of the active energy ray-curable emulsion composition of the present invention is not limited to these methods. In any method, when the photopolymerization initiator (C) is used, it is preferable to perform the mixing operation under light shielding or under a light source that does not cause cleavage of the photopolymerization initiator (C).
- the active energy ray-curable emulsion composition thus obtained preferably has a nonvolatile content concentration of 10 to 80% by weight from the viewpoint of coating workability, particularly 15 to 70% by weight, more preferably 20 to 65% by weight. Is preferred. If the concentration of the non-volatile content is too low, there is a tendency that repelling occurs on the substrate during coating, and if it is too high, the fluidity tends to be low and coating tends to be difficult.
- the particles of the obtained active energy ray-curable emulsion composition preferably have an average particle size of 1 to 1,000 nm, particularly 10 to 800 nm, and more preferably 20 to 600 nm. If the average particle size is too small, the viscosity of the active energy ray-curable emulsion composition tends to be large and difficult to handle. If it is too large, aggregation tends to occur and the emulsion stability tends to decrease. In addition, an average particle diameter is calculated
- the viscosity of the active energy ray-curable emulsion composition is preferably 1 to 5,000 mPa ⁇ s (20 ° C.), particularly 2 to 2,500 mPa ⁇ s (20 ° C.), more preferably 4 to It is preferably 1,500 mPa ⁇ s (20 ° C.). If the viscosity is too low, the control of the film thickness tends to be difficult, and if it is too high, handling becomes difficult and the coating workability tends to decrease. The viscosity is measured with a B-type viscometer.
- the active energy ray-curable emulsion composition used in the present invention is obtained.
- the emulsion composition is used as a curable resin composition (coating agent composition) for forming a coating film on various substrates, for example, It is effectively used as a top coat agent or an anchor coat agent for various base materials.
- the coating film is cured by irradiating active energy rays to form a cured coating film on the substrate. it can.
- the coating method is not particularly limited, and examples thereof include wet coating methods such as spray, shower, dipping, roll, spin, screen printing, and the like.
- Examples of various substrates include molded products (films, sheets, cups, etc.) made of polyolefin resins such as polyethylene, polypropylene, polycyclopentadiene, polycarbonates, polyesters, ABS resins, acrylic resins, metals, and glass. Is mentioned.
- polyolefin resins such as polyethylene, polypropylene, polycyclopentadiene, polycarbonates, polyesters, ABS resins, acrylic resins, metals, and glass. Is mentioned.
- active energy rays for example, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and ⁇ rays, electron beams, proton rays, neutron rays and the like can be used.
- Curing by ultraviolet irradiation is advantageous because of the availability of the irradiation device and the price.
- electron beam irradiation it can harden
- a light source that emits light in a wavelength range of 150 to 450 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an LED lamp, etc.
- a method of irradiating about 100 to 3,000 mJ / cm 2 . After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.
- composition obtained by the above preparation contains 69.4% of urethane acrylate (A-1) and contains ethylenically unsaturated monomer (E-1) (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate). 30.6%), and the weight average molecular weight was 2,500.
- Example 1 144.1 parts of resin composition containing urethane acrylate (A-1) obtained above (100 parts of urethane acrylate (A-1), 44.1 parts of ethylenically unsaturated compound (E-1)), ethoxy
- An active energy ray-curable resin composition containing 1296.8 parts of trimethylolpropane triacrylate (B-1) was prepared.
- the active energy ray-curable resin composition prepared above was stirred and mixed at 60 ° C., and 1440.9 parts of ion-exchanged water was added dropwise to the uniform resin solution while maintaining stirring at 60 ° C. to obtain an emulsified dispersion.
- the obtained emulsified dispersion was returned to room temperature, and 57.6 parts of photopolymerization initiator (C-1) and a leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow KL260”) were added thereto, and then uniformly To obtain an active energy ray-curable emulsion composition (non-volatile content: 50%).
- Example 2 to 5 An active energy ray curable resin composition was prepared in the same manner as in Example 1 except that the amount of each component was as shown in Table 1. Further, the active energy ray curable emulsion composition (nonvolatile content concentration 50%) was prepared. Got.
- Example 1 An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that ethoxylated trimethylolpropane triacrylate (B-1) was not contained and the amount of each component was as shown in Table 1. Furthermore, an active energy ray-curable emulsion composition (non-volatile content concentration 50%) was obtained.
- Example 4 The active energy was the same as in Example 4 except that the ethoxylated trimethylolpropane triacrylate (B-1) was not contained and the following hydrophilic monomers (E-2) to (E-4) were further contained.
- a line curable resin composition was prepared to obtain an active energy ray curable emulsion composition (non-volatile content: 50%).
- E-2 Acryloylmorpholine (KJ Chemicals, “ACMO”)
- E-3 Ethoxylated glycerol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-GLY-20E”)
- E-4 Ethoxylated pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “ATM-35E”)
- ⁇ Coating film adhesion> Apply the active energy ray-curable emulsion composition obtained above onto a polycarbonate substrate (manufactured by Nippon Test Panel Co., Ltd., standard test plate) using an applicator so that the film thickness after drying is 25 ⁇ m. Then, after drying at 60 ° C. for 10 minutes, using a high pressure mercury lamp 80W and one lamp, two passes of UV irradiation at a conveyor speed of 3.4 m / min from a height of 18 cm (accumulated dose 800 mJ / cm 2 ) And a cured coating film was formed. About the obtained cured coating film, the coating-film adhesiveness to a base material was evaluated by the cross-cut tape method according to JISK5400 (1990 edition).
- the coating-film external appearance of the obtained cured coating film was observed visually.
- evaluation criteria ⁇ ... 100/100 (all coating films are in close contact with the substrate after the test) The appearance of the coating film was transparent in visual observation.
- ⁇ ... 100/100 all coating films were in close contact with the substrate after the test) The visual appearance of the coating film was cloudy.
- ⁇ ... 99/100 to 0/100 After the test, the coating film peels from the substrate partially to completely peels off
- the active energy ray-curable resin compositions described in Examples 1 to 5 are compositions having self-emulsifying properties, and the emulsion composition has excellent solution stability and formed a cured coating film. It has excellent coating film hardness.
- the coating film adhesion to the base material during normal times and the hot water resistance are excellent.
- the coating film appearance after warm water immersion is cloudy, it is excellent in coating film adhesion to a base material during normal time and coating film adhesion after warm water immersion. I understand.
- an active energy ray-curable emulsion comprising the active energy ray-curable resin composition of Comparative Example 1 that does not contain ethylene oxide-modified trimethylolpropane tri (meth) acrylate (B), which is an ethylenically unsaturated compound having a specific structure.
- B ethylene oxide-modified trimethylolpropane tri (meth) acrylate
- ethylene oxide-modified trimethylolpropane triacrylate (B)
- it contains a hydrophilic monomer, acryloylmorpholine, an ethylene oxide adduct of glycerin triacrylate having a hydrophilic skeleton, and an ethylene oxide adduct of pentaerythritol.
- the active energy ray-curable emulsion compositions comprising the active energy ray-curable resin compositions of Comparative Examples 2 to 4 have solution stability, normal film adhesion when a cured film is formed, and film hardness. It was inferior to either hot water resistance, and could not satisfy all.
- the active energy ray-curable resin composition of the present invention is excellent in self-emulsifying property with respect to an aqueous medium, it is excellent in solution stability when emulsified and dispersed in an aqueous medium. In addition, it is excellent in hardness and hot water resistance of the coating film formed when it is coated on a substrate and cured, and even after immersion in warm water, deterioration of coating film appearance such as whitening and deterioration of adhesion performance are unlikely to occur.
- paints for example, paints, adhesives, adhesives, adhesives, inks, protective coatings, anchor coatings, hard coatings, magnetic powder coating binders, sandblasting coatings, printing materials, optical film top coatings It is very useful as various film forming materials, such as coating agents for metal, metal deposition and sputtering films, and coating agents for glass modification.
Abstract
Description
しかし、有機溶剤により希釈する場合には、大気汚染や作業環境、火災の危険性等に対する近年のVOC規制下において問題となるものであった。一方、反応性希釈剤により希釈する場合には、低粘度化に大量の反応性希釈剤を必要とする場合があり、充分な塗膜物性を得にくい等の問題等があった。
例えば、多官能性オリゴマーとして多官能性ウレタンアクリレート系化合物を用い、多官能性反応性界面活性剤として親水性基と疎水性基とを有するウレタンアクリレート系化合物を用い、多官能性オリゴマーが、多官能性反応性界面活性剤の存在下に、水性媒体中で分散されてなる活性エネルギー線硬化型エマルジョン組成物(例えば、特許文献1参照。)が提案されている。また、硬化塗膜の耐温水性を向上させたり、温水浸漬後における塗膜外観の白化を改善するために、比較的極性の高いポリオールを構造中に導入したウレタン(メタ)アクリレート系化合物を含有する活性エネルギー線硬化型エマルジョン組成物(例えば、特許文献2参照。)も提案されている。
また、汎用性のあるプラスチック基材としては、ABS基材の他に、より耐熱性を有するポリカーボネート基材があるが、そのいずれに対しても実用上必要とされる塗膜密着性を有する活性エネルギー線硬化型樹脂組成物が求められる。
なお、本発明において、(メタ)アクリルとはアクリルあるいはメタクリルを、(メタ)アクリロイルとはアクリロイルあるいはメタクリロイルを、(メタ)アクリレートとはアクリレートあるいはメタクリレートをそれぞれ意味するものである。
本発明の活性エネルギー線硬化型樹脂組成物は、ウレタン(メタ)アクリレート系化合物(A)及びエチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート(B)を含有してなるものである。
なお、本発明で用いられるウレタン(メタ)アクリレート系化合物(A)は、親水性を有する一般式(1)で示されるオキシアルキレン基含有化合物(a3)由来の親水性の構造部位を有し、かつ水酸基含有(メタ)アクリレート系化合物(a2)の疎水性残基を有することから界面活性剤としての役割を果たすものである。
これら多価イソシアネート系化合物(a1)は1種を単独で、又は2種以上を組み合わせて使用することができる。
単官能の水酸基含有(メタ)アクリレート系化合物としては、例えば、2-ヒドロキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、5-ヒドロキシペンチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、8-ヒドロキシオクチル(メタ)アクリレート、10-ヒドロキシデシル(メタ)アクリレート、(4-ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキルエステル等の1級水酸基含有(メタ)アクリレート;2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート等の2級水酸基含有(メタ)アクリレート;2,2-ジメチル-2-ヒドロキシエチル(メタ)アクリレート等の3級水酸基含有(メタ)アクリレート等が挙げられる。
2官能の水酸基含有(メタ)アクリレート系化合物としては、例えば、イソシアヌル酸エチレンオキサイド変性ジ(メタ)アクリレート、グリセロールエピクロロヒドリン変性1,6-ヘキサンジオールジ(メタ)アクリレート等が挙げられる。
3官能以上の水酸基含有(メタ)アクリレート系化合物としては、例えば、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、カプロラクトン変性ジペンタエリスリトールペンタ(メタ)アクリレート、カプロラクトン変性ペンタエリスリトールトリ(メタ)アクリレート、エチレンオキサイド変性ジペンタエリスリトールペンタ(メタ)アクリレート、エチレンオキサイド変性ペンタエリスリトールトリ(メタ)アクリレート等が挙げられる。
その他の水酸基含有(メタ)アクリレート系化合物としては、例えば、2-ヒドロキシエチルアクリロイルホスフェート、2-(メタ)アクリロイロキシエチル-2-ヒドロキシプロピルフタレート、2-ヒドロキシ-3-(メタ)アクリロイロキシプロピル(メタ)アクリレート、カプロラクトン変性2-ヒドロキシエチル(メタ)アクリレート等が挙げられる。
これら水酸基含有(メタ)アクリレート系化合物(a2)は1種又は2種以上組み合わせて使用することができる。
上記、アルキル基としては、通常、炭素数1~20、好ましくは1~10のものが用いられる。これらの中でも、特にメチル基、エチル基であることが好ましい。
上記アシル基としては、例えば、アセチル基、アセトイミドイル基、チオアセチル基、ベンゼンスルホニル基、ホスホノニトリドイル基、ホスホノイル基等が挙げられるが、これらの中でもアセチル基が好ましい。
エチレンオキサイド付加モル数nが小さすぎると安定した乳化分散液が得難い傾向があり、大きすぎると硬化塗膜とした際の硬度や耐温水性が低下する傾向がある。更には、硬化性への影響の点で、Yが水素原子、アルキル基、(メタ)アクリロイル基であることが好ましく、特に好ましくは水素原子である。
なお、粘度はE型粘度計により測定される。
なお、ウレタン(メタ)アクリレート系化合物(D)は、1種のみを用いてもよいし、2種以上を併用してもよい。
通常、上記ウレタン(メタ)アクリレート系化合物(D1)の場合は、多価イソシアネート系化合物(d1)及び水酸基含有(メタ)アクリレート系化合物(d2)を反応器に一括または別々に仕込み公知の反応手段によりウレタン化反応させて製造することができる。
また、上記ウレタン(メタ)アクリレート系化合物(D2)の場合は、多価イソシアネート系化合物(d1)及び水酸基含有(メタ)アクリレート系化合物(d2)の他に、更にポリオール系化合物(d3)を反応器に一括または別々に仕込み公知の反応手段によりウレタン化反応させて製造することができるが、この場合には、ポリオール系化合物(d3)と多価イソシアネート系化合物(d1)とを予め反応させて得られる反応生成物に、水酸基含有(メタ)アクリレート系化合物(d2)を反応させて製造する方法が、ウレタン化反応の安定性や副生成物の低減等の点で有用である。
かかるエチレン性不飽和基数が多すぎると硬化後の架橋密度が高くなりすぎて、硬化収縮が大きくなるため密着性が低下する傾向があり、少なすぎると充分な架橋密度が得られず、硬化塗膜における硬度の向上が見込めない傾向がある。
特に、ウレタン(メタ)アクリレート系化合物(D)として、ウレタン(メタ)アクリレート系化合物(D1)を用いる場合、重量平均分子量としては、好ましくは500~10,000、特に好ましくは800~8,000、更に好ましくは1,000~5,000、殊に好ましくは1,200~3,500である。
かかる重量平均分子量が高すぎると組成物の粘度が高くなり、水分散し難くなる傾向があり、かかる重量平均分子量が低すぎると相対的な架橋密度が高くなるものの、硬化塗膜の硬度向上が見込めない傾向がある。
なお、粘度はE型粘度計により測定される。
単官能モノマーとしては、例えば、スチレン、ビニルトルエン、クロロスチレン、α-メチルスチレン、メチル(メタ)アクリレート、エチル(メタ)アクリレート、(メタ)アクリロニトリル、酢酸ビニル、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、2-フェノキシ-2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、3-クロロ-2-ヒドロキシプロピル(メタ)アクリレート、グリセリンモノ(メタ)アクリレート、グリシジル(メタ)アクリレート、ラウリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、n-ブチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ドデシル(メタ)アクリレート、n-ステアリル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノールエチレンオキサイド変性(メタ)アクリレート、ノニルフェノールプロピレンオキサイド変性(メタ)アクリレート、2-(メタ)アクリロイルオキシ-2-ヒドロキシプロピルフタレート等のフタル酸誘導体のハーフエステル(メタ)アクリレート、フルフリル(メタ)アクリレート、カルビトール(メタ)アクリレート、ベンジル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、アリル(メタ)アクリレート、(メタ)アクリロイルモルフォリン、2-ヒドロキシエチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-ビニルピロリドン、2-ビニルピリジン、2-(メタ)アクリロイルオキシエチルアシッドホスフェートモノエステル等が挙げられる。
上記のウレタン(メタ)アクリレート系化合物(A)及びエチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート(B)を含有する活性エネルギー線硬化型樹脂組成物を水性媒体中で分散させることにより、本発明の活性エネルギー線硬化型エマルジョン組成物が得られ、本発明のコーティング剤組成物として用いることができる。
(1)ウレタン(メタ)アクリレート系化合物(A)、エチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート(B)及び水性媒体、必要に応じて、更に、光重合開始剤(C)やウレタン(メタ)アクリレート系化合物(D)、エチレン性不飽和モノマー(E)を一括で仕込み、通常30~70℃、好ましくは50~65℃で撹拌する方法、
(2)ウレタン(メタ)アクリレート系化合物(A)及びエチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート(B)、必要に応じて、更に、光重合開始剤(C)やウレタン(メタ)アクリレート系化合物(D)、エチレン性不飽和モノマー(E)を通常40~65℃、好ましくは55~60℃で混合し、撹拌しながら水性媒体を滴下する方法、
(3)エチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート(B)、必要に応じて、更に、光重合開始剤(C)やウレタン(メタ)アクリレート系化合物(D)、エチレン性不飽和モノマー(E)を通常40~43℃、好ましくは55~65℃に加温して、界面活性剤として作用し、水に分散させたウレタン(メタ)アクリレート系化合物(A)を滴下して、撹拌する方法、
(4)水に分散させたウレタン(メタ)アクリレート系化合物(A)中に、エチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート(B)を室温で滴下して、通常、室温~40℃で撹拌する方法。
本発明の活性エネルギー線硬化型エマルジョン組成物の製造方法は、これらの方法に限定されるものではない。また、いずれの方法においても、光重合開始剤(C)を用いる場合には、遮光下もしくは、光重合開始剤(C)の開裂が起こらない光源下で混合作業を行うことが好ましい。
なお、平均粒子径は以下の方法より求められるものである。
500gの水にエマルジョン組成物を0.1g滴下し、撹拌分散して評価用サンプルを作成し、Particle Sizing Systems社製「NICOMP380」を用い、23℃における平均粒子径をVolume-Wt NICOMP DISTRIBUTIONモードによって求める。
なお、粘度はB型粘度計により測定される。
かくして本発明で用いる活性エネルギー線硬化型エマルジョン組成物が得られるのであり、当該エマルジョン組成物は各種基材上に塗膜を形成するための硬化性樹脂組成物(コーティング剤組成物)として、例えば、各種基材へのトップコート剤やアンカーコート剤などとして有効に用いられるものである。例えば、活性エネルギー線硬化型エマルジョン組成物を基材に塗工し、乾燥させた後、活性エネルギー線を照射することにより塗膜が硬化されて、基材上に硬化塗膜を形成することができる。
塗工方法としては、特に限定されるものではなく、例えば、スプレー、シャワー、ディッピング、ロール、スピン、スクリーン印刷等のようなウェットコーティング法が挙げられる。
なお、電子線照射を行う場合は、光重合開始剤(C)を用いなくても硬化し得る。
紫外線照射後は、必要に応じて加熱を行って硬化の完全を図ることもできる。
なお、例中「部」、「%」とあるのは、断りのない限り重量基準を意味する。
温度計、撹拌機及び水冷コンデンサーを備えた4つ口フラスコに、イソホロンジイソシアネート(a1)(イソシアネート基含有量37.8%)94.1g(0.42モル)と2,6-ジ-tert-ブチルクレゾール2.0g、ジブチルスズジラウリレート0.02gを仕込み、60℃以下でジペンタエリスリトールペンタアクリレート(a2)(0.51モル)(ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物(水酸基価50.0mgKOH/g)569.8gとして仕込む)を約2時間で滴下し、60℃で2時間反応させた。残存イソシアネート基が2.1%となった時点で更にポリエチレングリコール(a3)(重量平均分子量993.1、エチレンオキサイド付加モル数22、水酸基価113mgKOH/g)336.2g(0.34モル)を55℃にて添加し、60℃で4時間反応させて、残存イソシアネート基が0.3%となった時点で反応を終了し、ウレタンアクリレート(A-1)を含有する樹脂組成物を得た(樹脂分濃度100%)。
上記の調製で得られた組成物は、ウレタンアクリレート(A-1)が69.4%含有され、エチレン性不飽和モノマー(E-1)(ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物)が30.6%含有されたものであり、また、重量平均分子量は2,500であった。
・(B-1)エトキシ化トリメチロールプロパントリアクリレート(BASFジャパン(株)製、「ラロマーLR-8863」)
・(C-1)1-ヒドロキシ-シクロヘキシル-フェニル-ケトンとベンゾフェノンの混合物(BASF社製、「イルガキュア500」)
上記で得られたウレタンアクリレート(A-1)を含有する樹脂組成物144.1部(ウレタンアクリレート(A-1)100部、エチレン性不飽和化合物(E-1)44.1部)、エトキシ化トリメチロールプロパントリアクリレート(B-1)1296.8部を含有する活性エネルギー線硬化型樹脂組成物を調製した。
上記で調製した活性エネルギー線硬化型樹脂組成物を60℃で撹拌混合して均一とした樹脂溶液に、60℃に保ち撹拌を続けながら、イオン交換水1440.9部を滴下して乳化分散液を得た。得られた乳化分散液を室温に戻し、光重合開始剤(C-1)57.6部、レベリング剤(共栄社化学(株)製、「ポリフローKL260」)4.32部を添加した後、均一に混合して、活性エネルギー線硬化型エマルジョン組成物(不揮発分濃度50%)を得た。
各成分の配合量を表1のとおりとした以外は実施例1と同様にして、活性エネルギー線硬化型樹脂組成物を調製し、更に活性エネルギー線硬化型エマルジョン組成物(不揮発分濃度50%)を得た。
エトキシ化トリメチロールプロパントリアクリレート(B-1)を含有させず、各成分の配合量を表1のとおりとした以外は実施例1と同様にして、活性エネルギー線硬化型樹脂組成物を調製し、更に活性エネルギー線硬化型エマルジョン組成物(不揮発分濃度50%)を得た。
エトキシ化トリメチロールプロパントリアクリレート(B-1)を含有させず、下記の親水性モノマー(E-2)~(E-4)をさらに含有させた以外は実施例4と同様にして、活性エネルギー線硬化型樹脂組成物を調製し、活性エネルギー線硬化型エマルジョン組成物(不揮発分濃度50%)を得た。
・(E-2)アクリロイルモルフォリン(KJケミカルズ(株)製、「ACMO」)
・(E-3)エトキシ化グリセリントリアクリレート(新中村化学工業(株)製、「A-GLY-20E」)
・(E-4)エトキシ化ペンタエリスリトールテトラアクリレート(新中村化学工業(株)製、「ATM-35E」)
実施例及び比較例の評価結果を表2に示す。
上記で得られた実施例1~5および比較例1~4の活性エネルギー線硬化型エマルジョン組成物(活性エネルギー線硬化型樹脂組成物の乳化分散液)を常温下で静置し、24時間後の外観を目視で確認した。
(評価基準)
○・・・分散液の分離は確認されなかった。
×・・・分散液の分離が発生していた。
上記で得られた活性エネルギー線硬化型エマルジョン組成物を、ポリカーボネート基板(日本テストパネル(株)製、標準試験板)上にアプリケーターを用いて、乾燥後の膜厚が25μmとなるように塗工し、60℃で10分間乾燥した後、高圧水銀灯ランプ80W、1灯を用いて、18cmの高さから3.4m/minのコンベア速度で2パスの紫外線照射(積算照射量800mJ/cm2)を行い、硬化塗膜を形成した。得られた硬化塗膜について、基材への塗膜密着性を、JIS K 5400(1990年版)に準じて碁盤目テープ法により評価した。
また、得られた硬化塗膜の塗膜外観を目視にて観察した。
(評価基準)
○・・・100/100(試験後も、塗膜が全て基材に密着)であり、
かつ目視観察において塗膜外観が透明であった。
△・・・100/100(試験後も、塗膜が全て基材に密着)であったが、
目視観察において塗膜外観に曇りがあった。
×・・・99/100~0/100(試験後に、塗膜が基材から一部剥離~全て剥離)
上記で得られた硬化塗膜について、JIS K 5600-5-4に準じて鉛筆硬度を測定した。
(評価基準)
○・・・HB以上
×・・・HB未満
〔塗膜密着性〕
上記平時での塗膜密着性評価において、100/100となったものについて、80℃に保持した精製水に1時間浸漬した後、基材への塗膜密着性を、JIS K 5400(1990年版)に準じて碁盤目テープ法により評価した。
なお、温水浸漬後の塗膜密着性の評価は、温水から硬化塗膜を取り出した直後および1時間後において実施した。
また、温水浸漬後の塗膜外観を目視にて観察した。
(評価基準)
○・・・100/100(試験後も、塗膜が全て基材に密着)であり、
かつ目視観察において塗膜外観が透明であった。
△・・・100/100(試験後も、塗膜が全て基材に密着)であったが、
目視観察において塗膜外観に曇りがあった。
×:99/100~0/100(試験後に、塗膜が基材から一部剥離~全て剥離)
一方、特定構造を有するエチレン性不飽和化合物であるエチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート(B)を含有しない比較例1の活性エネルギー線硬化型樹脂組成物からなる活性エネルギー線硬化型エマルジョン組成物は、硬化塗膜を形成した際に平時においてさえも、基材への塗膜密着性が得られなかった。
また、エチレンオキサイド変性トリメチロールプロパントリアクリレート(B)の代わりに、親水性のモノマーであるアクリロイルモルフォリン、親水骨格を有するグリセリントリアクリレートのエチレンオキサイド付加体、ペンタエリスリトールのエチレンオキサイド付加体を含有してなる比較例2~4の活性エネルギー線硬化型樹脂組成物からなる活性エネルギー線硬化型エマルジョン組成物は、溶液安定性、硬化塗膜を形成した際の平時の塗膜密着性、塗膜硬度、耐温水性のいずれかに劣り、全てを満足することはできないものであった。
Claims (4)
- エチレンオキサイド変性トリメチロールプロパントリ(メタ)アクリレート(B)の含有量が、ウレタン(メタ)アクリレート系化合物(A)100重量部に対して、40~1,500重量部であることを特徴とする請求項1記載の活性エネルギー線硬化型樹脂組成物。
- 請求項1または2記載の活性エネルギー線硬化型樹脂組成物が水性媒体に分散してなることを特徴とする活性エネルギー線硬化型エマルジョン組成物。
- 請求項1または2記載の活性エネルギー線硬化型樹脂組成物が水性媒体に分散してなることを特徴とするコーティング剤組成物。
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TW202210542A (zh) * | 2020-09-02 | 2022-03-16 | 日商荒川化學工業股份有限公司 | 活性能量射線硬化性樹脂組成物、硬化膜及薄膜 |
KR20220044113A (ko) * | 2020-09-30 | 2022-04-06 | 아라까와 가가꾸 고교 가부시끼가이샤 | 활성 에너지선 경화형 수지조성물 및 적층체 |
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