CN105829464B - Smears and layered product - Google Patents

Smears and layered product Download PDF

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Publication number
CN105829464B
CN105829464B CN201480068831.0A CN201480068831A CN105829464B CN 105829464 B CN105829464 B CN 105829464B CN 201480068831 A CN201480068831 A CN 201480068831A CN 105829464 B CN105829464 B CN 105829464B
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Prior art keywords
polyalcohol
resin
methyl
smears
acrylate
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CN201480068831.0A
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CN105829464A (en
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小柳达史
北田满
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • 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
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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    • 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
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    • 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
    • C08G18/6633—Compounds of group C08G18/42
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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Abstract

The present invention provides a kind of smears containing aqueous resin composition (D) and Carbodiimides crosslinking agent (E), wherein, the aqueous resin composition (D) is by vinyl ester resin (A) and obtained from the carbamate resins (B) with aromatic rings are scattered in aqueous medium (C)；The vinyl ester resin (A) is to make obtained from epoxy resin (a1) and compound (a2) react, wherein, the epoxy resin (a1) is that, selected from one or more of group being made up of novolac type epoxy resin and bisphenol-type epoxy resin, the compound (a2) has acidic group and polymerism unsaturated group；The carbamate resins (B) are to make obtained from the polyalcohol (b1) containing polyalcohol (b1 1) and polyalcohol (b1 2) and polyisocyanates (b2) react, wherein, the polyalcohol (b1 1) has aromatic rings, and the polyalcohol (b1 2) has hydrophily base.The smears of the present invention can make the adaptation of base material and the cured coating film of active energy ray-curable composition improve and form chemical-resistant and the excellent priming coat of humidity resistance.

Description

Smears and layered product
Technical field
, can be with the present invention relates to a kind of in the cured coating film of substrate surface formation Actinic-radiation curable composition As the smears and layered product for improving base material and the silane coupling agent (primer) of the cured coating film adaptation.
Background technology
In recent years, it have studied answering in the film or piece towards optical applications for aqueous urethane resin compositions With.As the optical applications, it can specifically enumerate：Liquid crystal display, touch panel etc..The display dress such as described liquid crystal display Put generally for display clearly image, and multiple optical films with various functions are laminated and constituted, as the optical film, It can enumerate：Antireflection film, phase retardation film, prismatic lens piece etc..
Because optical characteristics, mechanical strength, excellent in te pins of durability, polyester film is used as the base material of these optical films, especially It is polyethylene terephthalate (PET) film.In addition, in optical applications, on the surface of polyester film or by being coated with and admittedly Change Actinic-radiation curable composition and form hard conating, or set Actinic-radiation curable composition injection molding The layer obtained, using polyester film as prismatic lens, and but exist because the crystallinity height of polyester film causes to consolidate with active energy beam The problem of adaptation of the cured coating film of the property changed composition is low.
As the method for the adaptation for the cured coating film for improving polyester film and Actinic-radiation curable composition, propose Acrylic compounds are being included as setting between the polyester film of base material and the cured coating film of Actinic-radiation curable composition The priming coat of resin (referring for example to patent document 1).But, even if setting the priming coat for including acrylic resin, polyester film Also it is insufficient to the adaptation of the cured coating film of Actinic-radiation curable composition.
In addition, having used the layers of carbamate resins as priming coat, there are the following problems：Although being penetrated with active-energy The adaptation of the cured coating film of line solidification compound is enough, but for the adaptation and chemical-resistant after hot resistance test not Enough performances can be shown.
Accordingly it is desirable to which the adaptation for having the cured coating film for making polyester film and Actinic-radiation curable composition reaches foot It is enough, and the smears that can be used in the priming coat with excellent chemical-resistant and humidity resistance.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-215843 publications
The content of the invention
The invention problem to be solved
Problem to be solved by this invention is to provide a kind of solidification for base material or active energy ray-curable composition Film is respectively provided with excellent adaptation and can form the smears of chemical-resistant and the excellent priming coat of humidity resistance.
The means to solve the problem
As a result the present inventor etc. have found for the in-depth study repeatedly that solved the above problems and carried out：Make specific ring Oxygen tree fat, with vinyl ester resin obtained from the compound reaction with acidic group and polymerism unsaturated group and with aromatic rings Carbamate resins be scattered in aqueous medium and obtain aqueous resin composition, by using the water-base resin combine The silane coupling agent of crosslinking agent is combined in thing, even being difficult to the base material being bonded as polyester film, the base material can also be improved With the adaptation of the cured coating film of Actinic-radiation curable composition, and greatly improve priming coat chemical-resistant and Humidity resistance, so as to complete the present invention.
I.e. the present invention relates to a kind of smears and layered product, it is characterised in that contains aqueous resin composition in the smears (D) and Carbodiimides crosslinking agent (E), wherein, the aqueous resin composition (D) is by vinyl ester resin (A) and tool The carbamate resins (B) for having aromatic rings are scattered in obtained from aqueous medium (C)；
The vinyl ester resin (A) is made obtained from epoxy resin (a1) and compound (a2) react, wherein, it is described Epoxy resin (a1) is selected from one or more of group being made up of novolac type epoxy resin and bisphenol-type epoxy resin, institute Compound (a2) is stated with acidic group and polymerism unsaturated group；
The carbamate resins (B) be make the polyalcohol (b1) containing polyalcohol (b1-1) and polyalcohol (b1-2) with Obtained from polyisocyanates (b2) reaction, wherein, the polyalcohol (b1-1) has aromatic rings, polyalcohol (b1-2) tool There is hydrophily base.
Invention effect
Even being difficult to the base material being bonded as polyester film, smears of the invention is also used as that the base can be improved The adaptation and chemical-resistant and humidity resistance of material and the cured coating film of Actinic-radiation curable composition are excellent Silane coupling agent, is thus suitable for using polyester film as base material, and is formed with Actinic-radiation curable composition on its surface The layered product of cured coating film.As such layered product, for example, it can enumerate：The light such as antireflection film, phase retardation film, prismatic lens piece Learn film.In addition, these optical films can be applied to the image display device using liquid crystal display as representative.
Embodiment
The smears of the present invention contains aqueous resin composition (D) and Carbodiimides crosslinking agent (E), wherein, it is described Aqueous resin composition (D) be by vinyl ester resin (A) and the carbamate resins (B) with aromatic rings be scattered in it is aqueous Obtained in medium (C).
The vinyl ester resin (A) is made obtained from epoxy resin (a1) and compound (a2) react, wherein, epoxy Resin (a1) is selected from one or more of group being made up of novolac type epoxy resin and bisphenol-type epoxy resin, compound (a2) there is acidic group and polymerism unsaturated group.
The polymerism unsaturated group that the compound (a2) has is not involved in it in the reaction with the epoxy resin Reaction, result hereof is that, the vinyl ester resin (A) has the polymerism for coming from the compound (a2) unsaturated Base.In polymerism unsaturated group and Actinic-radiation curable composition described later that the vinyl ester resin (A) has Polymerisation occurs for the polymerism unsaturated group that contained resin, monomer have, and is consequently formed covalent bond, make with comprising this hair The closely sealed of the priming coat of bright smears becomes firm.
The equivalent for the polymerism unsaturated group that the vinyl ester resin (A) has is preferably 250~2,000g/eq. Scope.
The epoxy resin (a1) is in the group being made up of novolac type epoxy resin and bisphenol-type epoxy resin More than one epoxy resin, following epoxy resin specifically can be used.
As the novolac type epoxy resin, for example, it can enumerate：Cresol novalac type epoxy resin, phenol are linear Phenol aldehyde type epoxy resin etc..In addition, as the bisphenol-type epoxy resin, can enumerate：Bisphenol A type epoxy resin, bisphenol-f type ring Oxygen tree fat, bisphenol-s epoxy resin, tetrabromobisphenol A type epoxy resin etc..These epoxy resin (a1) can be used alone, Can be simultaneously using two or more.
In the epoxy resin (a1), preferably use with multiple acid-base reactions that can have with the compound (a2) Epoxy radicals novolac type epoxy resin.
In addition, the epoxide equivalent of the epoxy resin (a1) is preferably 150~2,000g/eq. scope, more preferably 160~1,000g/eq. scope.
Also, it is preferred that make 80~100 moles of % in the total amount for the epoxy radicals that the epoxy resin (a1) has and institute Compound (a2) acid-base reaction is stated, more preferably makes the acid-base reaction all with the compound (a2) of the epoxy radicals.
The compound (a2) is the compound with acidic group and polymerism unsaturated group.By making the compound (a2) The acidic group being had, the epoxy reaction having with the epoxy resin (a1), so as to which polymerism unsaturated group is led Enter in the vinyl ester resin (A).
As the compound (a2), for example, it can enumerate：Acrylic acid, methacrylic acid, itaconic acid, 2- acryloxy second Base succinate, 2- methacryloyloxyethyl.uccinates, 2,2,2 ,-three acryloyloxymethyl ethyl phthalic acids Ester etc.., preferably can be by easy resin, monomer with Actinic-radiation curable composition described later in these compounds The propylene that the acryloyl group of polymerisation is imported in the vinyl ester resin (A) occurs for the polymerism unsaturated group being had Acid.In addition, these compounds (a2) can be used alone, can also be simultaneously using two or more, in the compound (a2) Acrylic acid more than 50 mass % is preferably used in total amount.
The reaction temperature of the epoxy resin (a1) and the compound (a2) is preferably 60~150 DEG C of scope, more excellent Elect 80~120 DEG C of scope as.
In addition, when making the epoxy resin (a1) be reacted with the compound (a2), in order to prevent the compound (a2) thermal polymerization occurs for the polymerism unsaturated group having, and preferably uses polymerization inhibitor.Relative to the epoxy resin (a1) and The gross mass of the compound (a2), the addition of polymerization inhibitor is preferably 500~5,000ppm scope.
As the polymerization inhibitor, for example, it can enumerate：2,6- double (tert-butyl group) -4- methylphenols, hydroquinones, methyl are to benzene Diphenol, hydroquinone monomethyl ether's (p methoxy phenol), p-tert-butyl catechol, nitrobenzene, nitrobenzoic acid, adjacent dinitro Benzene, m-dinitrobenzene, paradinitrobenzene, 2,4-DNP, trinitrobenzen etc..These polymerization inhibitors can be used alone, Can be simultaneously using two or more.
Also, when making the epoxy resin (a1) be reacted with the compound (a2), catalysts can be used.Relatively In the mass parts of the epoxy resin (a1) 100, the consumption of the catalysts is preferably the scope of 0.1~5 mass parts.
As the catalysts, for example, it can enumerate：Amine catalyst, imidazole catalyst, phosphorus catalyst, B catalyst, Phosphorus-B catalyst etc..It can specifically enumerate：The alkyl substituted guanidines such as ethyl guanidine, trimethyl guanidine, guanidines, diphenylguanidine；3- (3, 4- dichlorophenyls) 3- such as -1,1- dimethyl ureas, 3- phenyl -1,1- dimethyl urea, 3- (4- chlorphenyls) -1,1- dimethyl ureas takes For phenyl -1,1- dimethyl urea；2-methylimidazole quinoline, 2- benzylimidazolines, 2- undecyl imidazoles quinoline, 2- heptadecyl imidazoles The imidazolines such as quinoline；The monoamine yl pyridines such as PA；N, N- dimethyl-N-(2- hydroxyl -3- allyloxys propyl group) amine-N ' - The amine acid imide such as lactamide；It is ethyl phosphine, propyl group phosphine, butyl phosphine, Phenylphosphine, trimethyl-phosphine, triethyl phosphine, tributylphosphine, three pungent Base phosphine, triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine-triphenylborane complex compound, tetraphenylphosphoniphenolate tetraphenyl borate salts etc. are organic The diazas such as phosphorus catalyst, the carbon -7- alkene of 1,8- diazabicyclos [5.4.0] 11, Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane are double Ring hendecene catalyst etc..These catalysts can be used alone, can also be simultaneously using two or more.
Because the dispersion stabilization of resin particle is improved, therefore it is used as the vinyl ester resin (A) obtained with methods described Weight average molecular weight be preferably 500~10,000 scope, more preferably 1,000~6,000 scope.
Carbamate resins (B) with aromatic rings be make it is polynary containing polyalcohol (b1-1) and polyalcohol (b1-2) Obtained from alcohol (b1) reacts with polyisocyanates (b2), wherein, the polyalcohol (b1-1) has aromatic rings, the polyalcohol (b1-2) there is hydrophily base.
The polyalcohol (b1-1) is used as to the raw material of the carbamate resins (B), thus the carbamate Resin (B) turns into the resin with aromatic rings.In addition, the aromatic rings concentration in the polyalcohol (b1-1) be preferably 1.5~ The scope of 8mol/kg scope, more preferably 1.6~5mol/kg.
As the polyalcohol (b1-1), for example, it can enumerate：Aromatic polyester polyol, aromatic copolycarbonate are polynary Alcohol, aromatic polyether polyalcohol, alkylene oxide addition product of bis-phenol etc..These be can be used alone, and two kinds can also be used simultaneously More than.
In addition, being preferably aromatic polyester because base material adaptation and resistance to blocking are excellent, in the polyalcohol (b1-1) Polyalcohol, as bis-phenol alkylene oxide addition product a kind of bisphenol-A alkylene oxide addition product.Thus, as the polyalcohol (b1-1) polyalcohol of at least one of the alkylene oxide addition product comprising aromatic polyester polyol and bisphenol-A, is preferably used.
The aromatic polyester polyol is made obtained from polybasic carboxylic acid and polyalcohol carry out esterification, using described There is the aromatic polyester polyol of aromatic rings at least one of polybasic carboxylic acid and polyalcohol.
In the polybasic carboxylic acid, as the polybasic carboxylic acid with aromatic rings, for example, it can enumerate：Phthalic acid, isophthalic two The aromatic binary carboxylic acids such as formic acid, terephthalic acid (TPA), naphthalenedicarboxylic acid or its carboxylate.In addition, as many without aromatic rings First carboxylic acid, for example, can enumerate：Succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, the last of the ten Heavenly stems Diacid, chlorendic acid, 1, the aliphatic two such as 2,4- butane tricarboxylic acids, decane dicarboxylic, cyclohexane cyclohexanedimethanodibasic, dimeric dibasic acid, fumaric acid Carboxylic acid or its carboxylate.These polybasic carboxylic acids or its carboxylate can be used alone, can also be simultaneously using two or more.
In the polyalcohol, as the polyalcohol with aromatic rings, for example, it can enumerate：Benzene dimethanol, toluene dimethanol, two The aromatic diols such as toluene dimethanol.In addition, as the polyalcohol without aromatic rings, such as can enumerate：Ethylene glycol, the third two Alcohol, 1,3-PD, BDO, 1,6- hexylene glycols, 1,8- ethohexadiols, diethylene glycol, triethylene glycol, Isosorbide-5-Nitrae-hexamethylene two The aliphatic polyols such as alcohol, 1,4-CHDM, neopentyl glycol ethylene glycol.These polyalcohols can be used alone, and also may be used With simultaneously using two or more.
The polyalcohol (b1-2) is the polyalcohol with hydrophily base.As the hydrophily base, it can enumerate：Anion Property base, cationic base, nonionic base, preferably anionic property base, be preferably carboxyl, sulfonic group in anionic property base.
As with the polyalcohol using carboxyl as hydrophily base, for example, it can enumerate：2,2- dihydromethyl propionic acids, 2,2- dihydroxies Methylbutanoic acid, 2,2- dihydroxymethyl valeric acids etc..Among them, preferably 2,2- dihydromethyl propionic acids.In addition it is also possible to using making The polyalcohol with carboxyl is stated with having the PEPA of carboxyl obtained by polybasic carboxylic acid reaction.
As with the polyalcohol using sulfonic group as hydrophily base, can for example enumerate：Make 5- sulfoisophthalic acids, sulfo group Dicarboxylic acids or their salt and the second such as terephthalic acid (TPA), 4- sulfosalicylic phthalates, 5- (4- sulfophenoxies) M-phthalic acid Gather obtained by the reaction of the low molecular polylols such as glycol, propane diols, BDO, 1,6- hexylene glycols, diethylene glycol, neopentyl glycol Ester polyol etc..
Because can the carbamate resins (B) be assigned with good water dispersible, therefore preferably by the anion Part or all of property base is neutralized with alkali compounds.
As the alkali compounds, for example, it can enumerate：Ammonia；Triethylamine, morpholine, MEA, diethyl ethylene diamine etc. Organic amine；Metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide etc..Because the aqueous of the present invention can be improved more The dispersion stability of resin combination, the consumption of the alkali compounds is with the mol ratio of alkali compounds and anionic property base [alkali compounds/anionic property base] is counted, preferably 0.5~3 scope, more preferably 0.7~1.5 scope.
In esterification when manufacturing the aromatic polyester polyol, in order to promote esterification, ester is preferably used Change catalyst.As the esterification catalyst, for example, it can enumerate：The metals such as titanium, tin, zinc, aluminium, zirconium, magnesium, hafnium, germanium；Four isopropanols Titanium, four butanol titaniums, acetylacetone,2,4-pentanedione oxygen titanium, Dibutyltin oxide, dibutyltin diacetate, dibutyl tin laurate, tin octoate, 2 ethyl hexanoic acid tin, zinc acetylacetonate, zirconium chloride, zirconium chloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrochysene Metallic compounds such as furans complex compound, germanium oxide, tetraethoxy germanium etc..
The alkylene oxide addition product of the bisphenol-A is addition alkylene oxide in the phenolic hydroxyl group having in bisphenol-A.Make For the alkylene oxide, it can enumerate：Oxirane, expoxy propane etc..In addition, the bisphenol-A relative to 1 mole, alkylene oxide is averaged Addition molal quantity is preferably 1~8 scope, more preferably 1~4 scope.
In the present invention, polyalcohol (b1) as must composition and contain the polyalcohol (b1-1) and the polyalcohol (b1- 2) polyalcohol (b1-3) in addition to them can also, be contained.As the polyalcohol (b1-3), for example, it can enumerate：Aliphatic PEPA, aliphatic polycarbonate polybasic alcohol, aliphatic poly ethoxylated polyhydric alcohol, alkylene oxide addition product of A Hydrogenated Bisphenol A etc..This Outside, as the polyalcohol (b1-3), it can also use described in being enumerated as the raw material of the aromatic polyester polyol Polyalcohol.These polyalcohols (b1-3) can be used alone, can also be simultaneously using two or more.
In addition, because more improving the polyalcohol with aromatic rings contained in the adaptation to base material, polyalcohol (b1) (b1-1) ratio is preferably the scope of 40~98 mass % scope, more preferably 60~98 mass %.
As the polyisocyanates (b2) of the raw material as the carbamate resins (B), for example, it can enumerate：4,4 '- Methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate, the isocyanide of Carbodiimide-Modified diphenyl methane two The fragrance such as acid esters, rough methyl diphenylene diisocyanate, phenylene diisocyanate, toluene di-isocyanate(TDI), naphthalene diisocyanate Race's polyisocyanates；Hexamethylene diisocyanate, lysine diisocyanate, XDI, tetramethyl The aliphatic polyisocyantes such as XDI；Cyclohexane diisocyanate, the isocyanic acid of double-hexyl methane two Ester, IPDI etc..These polyisocyanates (b2) can be used alone, can also simultaneously using two kinds with On.
Because more improving the adaptation to base material, aromatic series polyisocyanic acid is preferably comprised in the polyisocyanates (b2) Ester.The content of the aromatic polyisocyanate in the polyisocyanates (b2) now is preferably 15~35 mass % model Enclose.
The carbamate resins (B) can mix described many for example in the presence of solvent-free lower or organic solvent First alcohol (b1) and the polyisocyanates (b2), are allowed to react at a temperature of 40~120 DEG C and are manufactured for 3~20 hours.This Outside, when manufacturing carbamate resins (B), as needed, chain extender can also be used.
The polyalcohol (b1) and the reaction hydroxyl that preferably polyalcohol (b1) has of the polyisocyanates (b2) The equivalent proportion [NCO/hydroxyl] for the NCO that base has with the polyisocyanates (b2) is 0.5~3.5 In the range of carry out, more preferably in the range of 0.9~2.5 carry out.
As the organic solvent that can be used when manufacturing carbamate resins (B), for example, it can enumerate：Acetone, first The ketone solvents such as ethyl ketone；The ether solvents such as tetrahydrofuran, dioxanes；The acetate solvents such as ethyl acetate, butyl acetate；The nitriles such as acetonitrile are molten Agent；Amide solvents such as dimethylformamide, 1-METHYLPYRROLIDONE etc..These organic solvents can be used alone, can also be same When using two or more.
Because more improving the adaptation of the cured coating film of base material and Actinic-radiation curable composition, as with above-mentioned The obtained weight average molecular weight of the carbamate resins (B) of method be preferably 3,000~200,000 scope, it is more excellent Elect as 3,000~100,000 scope.
As aqueous medium (C), it can enumerate：Water, the organic solvent and their mixture mixed with water.As with The organic solvent that water is mixed, for example, can enumerate：The alcoholic solvents such as methanol, ethanol, normal propyl alcohol, isopropanol；The ketone such as acetone, MEK are molten Agent；The PAGs such as ethylene glycol, diethylene glycol, propane diols；The alkyl ether solvents of PAG；N- methyl -2- pyrroles Lactam solvents such as pyrrolidone etc..Organic solvents that these and water are mixed can be used alone, can also simultaneously using two kinds with On.
In addition, if it is considered that security and mitigation environmental pressure, then be preferably only as the aqueous medium (C) The mixture of water or water and the organic solvent mixed with water, more preferably only water.
The ratio of the aqueous medium (C) is preferably 10~90 mass % scope, more preferably 30~70 mass %'s Scope.
Aqueous resin composition (D) is to be scattered in the vinyl ester resin (A) and the carbamate resins (B) Obtained by the aqueous medium (C).Now, the vinyl ester resin (A) can also with the carbamate resins (B) It is present in as respective resin particle in the aqueous medium (C), preferably uses and form the vinyl ester resin (A) Part or all is built in the article of the resin particle (F) in the carbamate resins (B) particle.More specifically, excellent Elect the vinyl ester resin (A) formation core, the resin of the core/shell mould in the carbamate resins (B) formation shell portion as Particle (F).
The resin particle (F) can manufacture by the following method：The previously fabricated vinyl ester resin (A) and described Carbamate resins (B), it is then described to the carbamate resins (B) the mixing vinyl ester resin (A), neutralization The alkali compounds and the aqueous medium (C) for the anionic property base that carbamate resins (B) have.
In the case of containing organic solvent in the aqueous resin composition (D) obtained with methods described, in order to realize peace Full property and mitigation carrying capacity of environment, can also remove the organic solvent using way of distillation etc..Thus, it is possible to obtain the resin Particle (F) is scattered in the aqueous resin composition (D) in aqueous medium (C).
Because more improving the adaptation with the cured coating film of Actinic-radiation curable composition, the vinyl esters tree The mass ratio [(A)/(B)] of fat (A) and the carbamate resins (B) is preferably 60/40~10/90 scope, more excellent Elect as 55/45~20/80 scope.It is explained, the scope is by the vinyl ester resin (A) and the carbamate Resin (B) is as also identical in the case of the resin particle (F).
In addition, the vinyl ester resin (A) and the carbamate in aqueous resin composition (D) total amount The ratio of the total amount of resin (B) is preferably the scope of 10~90 mass % scope, more preferably 30~70 mass %.
As needed, it can coordinate in the aqueous resin composition (D)：It is coalescents, curing agent, plasticizer, antistatic Agent, wax, light stabilizer, flowing regulator, dyestuff, levelling agent, rheology control agent, ultra-violet absorber, antioxidant, photocatalysis The additives such as property compound, inorganic pigment, organic pigment, extender pigment；Polyester resin, carbamate resins, acrylic compounds Others resin such as resin etc..
The smears of the present invention is required composition with Carbodiimides crosslinking agent (E).What the crosslinking agent (E) had The hydrophily bases such as the carboxyl that carbodiimide-based has with the carbamate resins (B) react the crosslinking structure to form three-dimensional Make, thus improve the adaptation of base material and the cured coating film of Actinic-radiation curable composition, in addition, by the present invention's In the case that smears is used as silane coupling agent, the high adhesion after hot resistance test can be assigned to the priming coat of formation and excellent Chemical-resistant.
It is used as the crosslinking agent (E), it is however preferred to have the crosslinking agent of two or more carbodiimide-based, is handed over as such Join agent, for example, can enumerate：Poly- (4,4 '-diphenyl methane carbodiimides), poly- (to phenylene carbodiimides), a poly- (Asia Phenyl carbodiimides), poly- (diisopropyl phenyl carbodiimides), the aromatic series such as poly- (triisopropyl phenyl carbodiimides) Polycarbodiimide；Alicyclic polycarbodiimides such as poly- (double-hexyl methane carbodiimides), poly- (diisopropyl carbonization two Imines) etc. aliphatic polycarbodiimide etc..
In addition, as the crosslinking agent (E), because the smears of the present invention is by the vinyl ester resin (A) and institute State carbamate resins (B) to be scattered in obtained by aqueous medium (C), therefore be preferably with water-soluble or water dispersible The crosslinking agent of (emulsion-type).
As the commercially available product that can be used as the crosslinking agent (E), it can enumerate：The manufacture of Nisshinbo KCC “CARBODILITE SV-02”、“CARBODILITE V-02”、“CARBODILITE V-02-L2”、“CARBODILITE V- 04 ", " CARBODILITE E-01 ", " CARBODILITE E-02 " etc..
Because the enough cross-linking properties of performance, the consumption of the crosslinking agent (E) is preferably can be with hydrophily base 80~100 The amount of mole % reaction, the more preferably amount with 100 moles of % reactions, wherein, the hydrophily base is can be with carbodiimides The hydrophily base that the carbamate resins (B) of base reaction have.
In addition, because adaptation, the storage stability with the aqueous resin composition (D) are improved, relative to the water Property resin combination (D), the crosslinking agent (E) is added preferably in the range of 3~5 mass %.
The layered product of the present invention is that have the priming coat for the smears formation of the invention for using described above and described The surface of priming coat has the layered product of the cured coating film using Actinic-radiation curable composition formation.
As the Actinic-radiation curable composition, resin and tool with polymerism unsaturated group are preferably comprised There is the monomer of polymerism unsaturated group, these have the resin of polymerism unsaturated group and the monomer with polymerism unsaturated group Characteristic of the species preferably according to required by the cured coating film of the Actinic-radiation curable composition properly select.
As the resin with polymerism unsaturated group, it can enumerate：Carbamate (methyl) acrylate, Unsaturated polyester resin, epoxy (methyl) acrylate, polyester (methyl) acrylate, acryloyl group (methyl) third Alkene acid ester resin, resin with dimaleoyl imino etc..There is the resin of polymerism unsaturated group can be used alone for these, Can also be simultaneously using two or more.
In the present invention, " (methyl) acrylate " refers to one of acrylate and methacrylate or both, " (first Base) acryloyl group " refer to one of acryloyl group and methylacryloyl or both.
As the carbamate (methyl) acrylate, for example, it can enumerate：Make aliphatic polyisocyante or Aromatic polyisocyanate occurs have ammonia obtained from urethane reaction with (methyl) acrylate with hydroxyl Resin of carbamate key and (methyl) acryloyl group etc..
As the aliphatic polyisocyante, for example, it can enumerate：Tetramethylene diisocyanate, the isocyanide of pentamethylene two Acid esters, hexamethylene diisocyanate, heptamethylene diisocyanate, eight methylene diisocyanates, the isocyanide of decamethylene two Acid esters, 2- methyl isophthalic acids, 5- pentane diisocyanates, 3- methyl isophthalic acids, 5- pentane diisocyanates, the isocyanic acid of ten dimethylene two Ester, 2- methyl pentamethylene diisocyanate, 2,2,4- trimethyl hexamethylene diisocyanates, the methylene of 2,4,4- trimethyl six Group diisocyanate, IPDI, norbornene alkyl diisocyanate, hydrogenated diphenyl methane diisocyanate, Hydrogenated toluene diisocyanate, hydrogenation XDI, hydrogenation tetramethylxylylene diisocyanate, ring Hexyl diisocyanate etc..In addition, as the aromatic polyisocyanate, can enumerate：Toluene di-isocyanate(TDI), 4,4 '-two Methylenebis phenyl isocyanate, XDI, 1,5- naphthalene diisocyanates, tolidine diisocyanate, PPDI etc..
As described (methyl) acrylate with hydroxyl, for example, it can enumerate：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls, 1,5- penta 2 Alcohol list (methyl) acrylate, 1,6- hexylene glycols list (methyl) acrylate, neopentyl glycol single (methyl) acrylate, hydroxyl are special List (methyl) acrylate of the dihydric alcohols such as valeric acid neopentyl glycol single (methyl) acrylate；Trimethylolpropane two (methyl) third Olefin(e) acid ester, ethoxylated trimethylolpropane (methyl) acrylate, propoxylation trimethylolpropane two (methyl) acrylic acid The trihydroxylic alcohols such as ester, glycerine two (methyl) acrylate, double (2- (methyl) acryloyl-oxyethyl) hydroxyethyl isocyanuric acid esters List or two (methyl) acrylate or the list with the hydroxyl for being modified a part for these alcohol hydroxyl groups with 6-caprolactone With two (methyl) acrylate；Pentaerythrite three (methyl) acrylate, double trimethylolpropane three (methyl) acrylate, two Pentaerythrite five (methyl) acrylate etc. has the chemical combination of (methyl) acryloyl group more than hydroxyl and trifunctional of simple function Thing, or multifunctional (methyl) acrylate with the hydroxyl for being further modified the compound with 6-caprolactone；Dipropyl two Alcohol list (methyl) acrylate, diethylene glycol list (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyethylene glycol Single (methyl) acrylate etc. has (methyl) acrylate compounds of oxyalkylene chain；Polyethylene glycol propane diols list (first Base) acrylate, polybutylene-polyoxypropylene list (methyl) acrylate etc. have block structure oxyalkylene chain (methyl) Acrylate compounds；Poly- (ethylene glycol-BDO) single (methyl) acrylate, poly- (propane diols-BDO) are single (methyl) acrylate etc. has (methyl) acrylate compounds of oxyalkylene chain of disordered structure etc..
The unsaturated polyester resin be by α, β-unsaturated dibasic acid or its acid anhydrides, aromatic series monounsaturated dicarboxylic acid or its Curable resin obtained from the polycondensation of acid anhydrides and glycol.As the α, β-unsaturated dibasic acid or its acid anhydrides for example may be used Enumerate：Maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlorine maleic acid and their ester etc..It is used as the virtue Fragrant race's monounsaturated dicarboxylic acid or its acid anhydrides, can be enumerated：Phthalic acid, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA), Nitrophthalic acid, tetrabydrophthalic anhydride, Nadic anhydride, halophthalic acid acid anhydride and it Ester etc..As aliphatic or alicyclic monounsaturated dicarboxylic acid, it can enumerate：Ethanedioic acid, malonic acid, succinic acid, adipic acid, the last of the ten Heavenly stems Diacid, azelaic acid, glutaric acid, hexahydrophthalic anhydride and their ester etc..As the glycol, it can enumerate：Ethylene glycol, third Glycol, diethylene glycol, DPG, 1,3-BDO, BDO, 2- methylpropanes -1,3- glycol, neopentyl glycol, three Ethylene glycol, tetraethylene glycol, 1,5-PD, 1,6- hexylene glycols, bisphenol-A, hydrogenated bisphenol A, the ethylene carbonate, (4- of 2,2- bis- Hydroxy propyloxy group diphenyl) propane etc., in addition, it also can similarly use the oxides such as oxirane, expoxy propane.
As the epoxy (methyl) acrylate, it can enumerate：Make (methyl) acrylic acid and bisphenol type epoxy tree The epoxy resin such as fat, bisphenol f type epoxy resin, phenol novolac type epoxy resin, cresol novalac type epoxy resin Resin obtained from epoxy reaction.
As the polyester (methyl) acrylate, for example, it can enumerate：Make (methyl) acrylic acid and PEPA Hydroxyl reaction obtained from resin.
As the acryloyl group (methyl) acrylate, for example, it can enumerate the resin obtained by reacting as follows： Make GMA and (methyl) acrylate monomer such as (methyl) alkyl acrylate gathers as needed Close, obtain after the acrylic resin with epoxy radicals, make (methyl) acrylic acid and the epoxy reaction.
As the resin with dimaleoyl imino, it can enumerate：By N- hydroxyethyls maleimide and different Fo Er Bifunctional maleimides' carbamate compounds obtained from ketone diisocyanate carries out urethane, by Malaysia acyl Bifunctional maleimides' ester compounds obtained from imines acetic acid and BDO are esterified, by maleimidohexanoic acid Tetrafunctional maleimide ester compounds obtained from being esterified with the tetraoxane addition product of pentaerythrite, by Malaysia acyl Multifunctional maleimide ester compounds etc. obtained from imines acetic acid is esterified with polyol compound.
As the monomer with polymerism unsaturated group, for example, it can enumerate：Ethylene glycol two (methyl) acrylate, two Ethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, number-average molecular weight are in the range of 150~1000 Polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, DPG two (methyl) acrylate, three Polypropylene glycol two (methyl) acrylic acid of propane diols two (methyl) acrylate, number-average molecular weight in the range of 150~1000 Ester, neopentyl glycol two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, BDO two (methyl) propylene Acid esters, 1,6- hexylene glycols two (methyl) acrylate, 3-hydroxypivalic acid ester neopentyl glycol two (methyl) acrylate, bisphenol-A two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane two (methyl) acrylate, season penta Tetrol four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two seasons Penta tetrol five (methyl) acrylate, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) methyl acrylate, (methyl) acrylic acid third Ester, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) propylene are misery Ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, Different stearyl ester of (methyl) acrylic acid etc. aliphatic alkyl (methyl) acrylate, (methyl) glycerol acrylate, (methyl) propylene Sour 2- hydroxy methacrylates, (methyl) acrylic acid 3- chlorine-2-hydroxyls propyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid Allyl ester, (methyl) acrylic acid 2- butoxyethyls, (methyl) acrylic acid 2- (diethylamino) ethyl ester, (methyl) acrylic acid 2- (dimethylamino) ethyl ester, γ-(methyl) acryloxypropyl trimethoxy silane, (methyl) acrylic acid 2- methoxyl group second Ester, methoxyl group diethylene glycol (methyl) acrylate, methoxyl group DPG (methyl) acrylate, the poly- second two of Nonylphenoxy Alcohol (methyl) acrylate, Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) acrylate, benzene oxygen Base DPG (methyl) acrylate, phenoxy group polypropylene glycol (methyl) acrylate, polybutadiene (methyl) acrylate, Polyethylene glycol propane diols (methyl) acrylate, polyethylene glycol butanediol (methyl) acrylate, polystyrene-based second Base (methyl) acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, the bicyclic pentyl ester of (methyl) acrylic acid, (first Base) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) isobornyl acrylate, methoxylation ring last of the ten Heavenly stems triolefin (methyl) acrylate, (first Base) phenyl acrylate；Maleimide, N- methylmaleimidos, NEM, N- propylmaleimides, N- butyl maleimides, N- hexyls maleimide, N- octyl groups maleimide, N- dodecyls maleimide, N- are hard Aliphatic radical maleimide, N-phenylmaleimide, N- N-cyclohexylmaleimides, 2- Mailed Ethyls-ethyl carbonate Ester, 2- Mailed Ethyls-propyl carbonate, N- ethyls-(2- Mailed Ethyls) carbamate, N, the methylenes of N- six Base BMI, polypropylene glycol-bis- (3- maleimides propyl group) ether, double (2- Mailed Ethyls) carbonic esters, 1, Maleimide compounds such as 4- BMI hexamethylenes etc..These have the monomer of polymerism unsaturated group can be independent It is two or more using can also use simultaneously.
The Actinic-radiation curable composition can be coated on after base material etc., by irradiating active energy beam and It is used as cured coating film.As the active energy beam, it can enumerate：Ultraviolet, electron beam, alpha ray, β rays, gamma-rays etc. are ionized Radioactive ray.The irradiation ultraviolet radiation as active energy beam, is applied the Actinic-radiation curable composition as solidification In the case of film, add Photoepolymerizationinitiater initiater preferably into the Actinic-radiation curable composition and improve curability. In addition, if it is desired, further can also add sensitising agent and improve curability.On the other hand, as active energy beam Irradiating electron beam, alpha ray, β rays or gamma-rays, using the Actinic-radiation curable composition as cured coating film feelings Under condition, also can rapidly it solidify even if without using Photoepolymerizationinitiater initiater or sensitising agent, therefore Photoepolymerizationinitiater initiater need not be added Or sensitising agent.
As the Photoepolymerizationinitiater initiater, for example, it can enumerate：1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyl -1- benzene Base propane -1- ketone, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxy-methyl -1- propane -1- ketone, 2- methyl isophthalic acids-[4- (first Sulfenyl) phenyl] -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, it is double (2, 6- Dimethoxybenzoyls) -2,4,4- trimethylpentylphosphine oxides, the oxidation of double (2,4,6- trimethylbenzoyl)-phenyl Phosphine etc..
As the sensitising agent, for example, it can enumerate：The amines such as aliphatic amine, aromatic amine, o-tolyl thiocarbamide etc. Sulphur compounds such as carbamide compound, diethyldithioposphoric acid sodium, s- benzylisothioureas-tosilate etc..
As the base material of the layered product for the present invention, for example, it can enumerate：Metal base, plastic basis material, glass baseplate, paper Base material, wood substrates, fiber base material etc..In these base materials, in order to improve consolidating for the Actinic-radiation curable composition Change the adaptation of film and base material, be suitably plastics in the case where the aqueous resin composition of the present invention is used as into silane coupling agent Base material
As the material of the plastic basis material, it can enumerate：Polyester, acrylic resin (polymethyl methacrylate etc.), Makrolon, acrylonitrile-butadiene-styrene copolymer (ABS resin), compound resin, the polyphenyl of ABS resin and makrolon Ethene, polyurethane, epoxy resin, polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycyclic alkene (COP) etc.), three Acetylcellulose (TAC) etc..
In above-mentioned plastic basis material, smears of the invention is highly useful as the silane coupling agent of polyester base material.As described The concrete example of polyester, can be enumerated：Polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT) etc..
As the plastic basis material, for example, it can enumerate：Mobile phone, household appliances, automobile interior exterior package material, OA equipment etc. Formed products.In addition, can also enumerate using plastics as raw material film base material.It is regarding film base material as layered product of the invention Base material in the case of, may be used at the optical films such as antireflection film, phase retardation film, prismatic lens piece；The food bag such as aluminium-vapour deposition film In the high functional membrane of dress etc..
In addition, using the present invention layered product as the optical films such as antireflection film, phase retardation film, prismatic lens piece situation Under, it can be used as the various pictures such as liquid crystal display (LCD), organic el display (OLED), plasma scope (PDP) and show The part of device.
The smears of the present invention can be for example coated with by directly on the surface of the base material, then be allowed to dry and solidify, So as to form film on the surface of base material.Can be normal as the method for making the smears of the present invention dry and be solidified The method of the lower maintenance 1~10 day or so of temperature, in order to can promptly be solidified, is preferably heated at a temperature of 100 DEG C~150 DEG C The method of 1~600 second or so.In addition, in the case where using the plastic basis material for easily deforming or changing colour at relatively high temperatures, it is excellent It is selected under 70 DEG C~100 DEG C or so of lower temperature and heats.
In the method on the surface of the base material, for example, it can enumerate as by the coating agent of the present invention and use following painting Cloth method：Gravure coater, roll coater, comma type coating machine, knife type coater, Kohler coater, curtain coater, lick painting machine, pouring Painting machine, flow coater, spin coater, dipping, silk-screen printing, spraying, hairbrush coating, applicator, bar coater etc..
Can suitably it be adjusted according to use using the thickness of the film of the smears formation of the present invention, it is usually preferred to For 0.01~20 μm of scope.
The layered product of the present invention can be obtained in the following way：In the painting as the smears of the invention obtained as described above Film is the surface of priming coat, is further coated with the Actinic-radiation curable composition and irradiates active energy beam, by This forms the cured coating film of the Actinic-radiation curable composition.It is explained, the active energy ray-curable The coating method identical method with above-mentioned smears of the invention can be used in the coating method of composition.
Embodiment
Below, the present invention is specifically described by embodiment and comparative example.
(synthesis example 1：The synthesis of aromatic polyester polyol (1))
While nitrogen is imported in the reaction vessel for possessing thermometer, nitrogen ingress pipe, mixer, while adding isophthalic two The mass parts of formic acid 27.6, the mass parts of terephthalic acid (TPA) 27.6, the mass parts of diethylene glycol 19.9 and the mass of Dibutyltin oxide 0.03 Part, at 230 DEG C carry out polycondensation reaction in 24 hours until at 180~230 DEG C acid number be less than 1, obtain aromatic polyester many First alcohol (1) (acid number 0.6, hydroxyl value 50.0, aromatic rings concentration 4.77mol/Kg).
(Production Example 1：The synthesis of vinyl ester resin (1))
Cresol novalac type epoxy resin (Dainippon Ink Chemicals's system " EPICLON N-673- are added into reaction vessel 80M ", solid constituent epoxide equivalent：209g/eq., involatile constituent：80 mass %, solvent：MEK) 46.7 mass parts, The mass parts of acrylic acid 13.3, the mass parts of p methoxy phenol 0.08, the mass parts of MEK 13.3, stirring are allowed to equably mix. Then the mass parts of triphenylphosphine 0.37 are added, it is less than 1.5 to be reacted at 80 DEG C of reaction temperature to acid number, obtains vinyl The involatile constituent of ester resin (1) is 75 mass % solution.
The raw material of the vinyl ester resin (1) synthesized in Production Example 1 is as shown in table 1.
[table 1]
(Production Example 2：The synthesis of carbamate resins (1) with aromatic rings)
In reaction vessel by the mass parts of aromatic polyester polyol (1) 100.0 obtained in synthesis example 1 under reduced pressure It is dehydrated, is then cooled to after 80 DEG C at 100 DEG C, add the mass parts of MEK 66.6, is stirred and equably mix.Then, 2 are added, the mass parts of 2 '-dihydromethyl propionic acid 6.1 are subsequently added into the mass parts of IPDI 23.1, at 80 DEG C Reaction 12 hours, implements urethane process.It is less than 0.1% to confirm isocyanate value, adds the mass of n-butanol 3 Part, further reaction 2 hours after, be cooled to 50 DEG C, obtain the carbamate resins (1) with aromatic rings it is non-volatile into It is divided into 65 mass % solution.
(preparation example 1：The preparation of aqueous resin composition (1))
The involatile constituent of the carbamate resins (1) with aromatic rings obtained into Production Example 2 is 65 matter Add and obtained in Production Example 1 in the mass parts of solution 147.7 (being 96 mass parts as the carbamate resins (1)) for measuring % The mass % of involatile constituent 75 mass parts of solution 128.0 of vinyl ester resin (1) (be used as the vinyl ester resin (1) be 96 mass parts), the mass parts of triethylamine 5.5, be slowly added the mass parts of ion exchange water 938.5 implement water-solubleization.Then Under reduced pressure, MEK is removed at 30~50 DEG C, obtains the aqueous resin composition that involatile constituent is 40 mass % (1)。
The composition of the aqueous resin composition (1) obtained in embodiment 1~9 is as shown in table 2.It is explained, the group in table Into expression involatile constituent amount (being only the amount of resin).
[table 2]
(preparation example 2：The preparation of ultra-violet solidified composition (UV-1))
Mixed amino formic acid esters acrylate (Dainippon Ink Chemicals's system " UNIDIC V-4260 ") 50 mass parts, 3 third The mass parts of omega-diol diacrylate 50 and Photoepolymerizationinitiater initiater (BASF Amada Co., Ltd. system " IRGACURE 184 ", 1- hydroxyls Butylcyclohexyl phenyl ketone) 3 mass parts, thus obtain ultra-violet solidified composition (UV-1).
(preparation example 3：The preparation of ultra-violet solidified composition (UV-2))
Hybrid epoxidized acrylate (Dainippon Ink Chemicals's system " UNIDIC V-5500 ") 50 mass parts, tripropylene glycol two The mass parts of acrylate 50 and Photoepolymerizationinitiater initiater (BASF Amada Co., Ltd. system " IRGACURE 184 ") 3 mass parts, by This obtains ultra-violet solidified composition (UV-2).
(embodiment 1：The making of silane coupling agent (1))
It is mixed with the mass parts of aqueous resin composition (1) 100, the carbodiimide cross-linker (Nisshinbo obtained in example 1 KCC's system " CARBODILITE E-02 ") 2.8 mass parts and the mass parts of ion exchange water 593, thus obtain primary coat Agent (P-1).
(embodiment 2：The making of silane coupling agent (2))
It is mixed with the mass parts of aqueous resin composition (1) 100, the carbodiimide cross-linker (Nisshinbo obtained in example 1 KCC's system " CARBODILITE V-02 ") 2.8 mass parts and the mass parts of ion exchange water 589, thus obtain primary coat Agent (P-2).
(embodiment 3：The making of silane coupling agent (3))
It is mixed with the mass parts of aqueous resin composition (1) 100, the carbodiimide cross-linker (Nisshinbo obtained in example 1 KCC's system " CARBODILITE SV-02 ") 2.8 mass parts and the mass parts of ion exchange water 593, thus obtain primary coat Agent (P-3).
(embodiment 4：The making of layered product (1))
On the surface of polyethylene terephthalate (hereinafter abbreviated as " PET ") membrane material (125 μm of thickness) with Dried thickness is about the silane coupling agent (P-1) obtained in 1 μm of mode coating Examples 1, is heated 5 minutes at 150 DEG C, by This forms priming coat on the surface of the base material.Then, with 15 μm of coating thickness, it is coated with and prepares on the surface of the priming coat The ultra-violet solidified composition (UV-1) obtained in example 2, using high-pressure sodium lamp as light source, with exposure intensity 0.5J/cm2To this Coated face irradiation ultraviolet radiation, thus obtains having priming coat on the surface of the base material and has purple on the surface of the priming coat The layered product (1) of the cured coating film (hereinafter abbreviated as " UV films ") of outside line solidification compound.
(embodiment 5：The making of layered product (2))
The ultraviolet for replacing using in embodiment 4 using the ultra-violet solidified composition (UV-2) obtained in preparation example 3 Solidification compound (UV-1), in addition, is made similarly to Example 4, obtains layered product (2).
(embodiment 6：The making of layered product (3))
The primary coat obtained on the surface of PET film base material in the way of dried thickness is about 1 μm in coating Examples 2 Agent (P-2), heats 5 minutes at 150 DEG C, thus forms priming coat on the surface of the base material.Then, it is thick with 15 μm of coating Degree, the ultra-violet solidified composition (UV-2) obtained in the surface coating preparation example 3 of the priming coat, is made with high-pressure sodium lamp For light source, with exposure intensity 0.5J/cm2To the coated face irradiation ultraviolet radiation, thus obtain that there is bottom on the surface of the base material Coating and the layered product (3) on the surface of the priming coat with UV films.
(embodiment 7：The making of layered product (4))
The silane coupling agent (P-2) for replacing using in embodiment 6 using the silane coupling agent (P-3) that obtains in embodiment 3, except this with Outside, made similarly to Example 6, obtain layered product (4).
Using the smears and layered product obtained in the above embodiments and comparative example, following adaptations is commented Valency.
[evaluation method of the adaptation (initial stage) of base material and priming coat]
So that thickness when drying reaches about 1 μm, in 125 μm of the base for including polyethylene terephthalate of thickness The surface coating silane coupling agent of material, is heated 5 minutes at 150 DEG C, is thus produced on the surface of the base material comprising being laminated with primary coat The breadboard of the part of layer.
On the surface of the priming coat of the breadboard made of methods described, the 24mm of NICHIBAN Co., Ltd. manufacture is pasted Wide adhesive tape.
Then, by the adhesive tape along the vertical direction stretching relative to the priming coat, according to following evaluation criterions, Visual assessment by the adhesive tape from the sur-face peeling of priming coat when the priming coat surface state：
◎：Priming coat is not peeled off from the substrate surface for constituting breadboard completely.
○：Very at least part of priming coat is peeled off from the substrate surface for constituting breadboard, relative to the skin for constituting breadboard The gross area of film, the scope of the stripping is less than 10%.
△：Relative to constitute breadboard priming coat area for 10% less than 50% scope priming coat from The substrate surface for constituting breadboard is peeled off.
×：The gross area relative to the priming coat for constituting breadboard is tested for the priming coat of more than 50% scope from composition The substrate surface of plate is peeled off.
[priming coat and the evaluation method of the adaptation (initial stage) of UV films]
The surface of the UV films of the layered product obtained in embodiment and comparative example is constituted, pastes NICHIBAN Co., Ltd. The adhesive tape wide 24mm of manufacture.
Then, by the adhesive tape along the vertical direction stretching relative to the UV films, according to following evaluation criterions, Visual assessment by the adhesive tape from the sur-face peeling of UV films when the UV films surface state：
◎：UV films are not peeled off from the substrate surface for constituting layered product completely.
○：Very at least part of UV films are peeled off from the substrate surface for constituting layered product, relative to the UV for constituting layered product The gross area of film, the scope of the stripping is less than 10%.
△：Relative to constitute layered product UV films area for 10% less than 50% scope UV films from The substrate surface for constituting layered product is peeled off.
×：The gross area relative to the UV films for constituting layered product is laminated for the UV films of more than 50% scope from composition The substrate surface of body is peeled off.
[adaptation (after hot resistance test) of priming coat and UV films]
By 50 hours in the obtained layered product input temperature 60 C, the high temperature humidistat of relative humidity 90%.Afterwards, Take out the layered product, according to the adaptation (initial stage) of UV films [priming coat with] same method evaluate priming coat with The adaptation of UV films.
[adaptation (after chemical-resistant experiment) of priming coat and UV films]
By 30 minutes in obtained 25 DEG C of the temperature of layered product input, 5% sodium hydrate aqueous solution.Afterwards, institute is taken out Layered product is stated, after washing/drying, according to same with [evaluation method of the adaptation (initial stage) of priming coat and UV films] Method evaluates the adaptation of priming coat and UV films.
[evaluation method of film forming]
So that thickness when drying reaches about 1 μm, in 125 μm of the base for including polyethylene terephthalate of thickness The surface of material is coated with the silane coupling agent, is heated under 150 DEG C of In 5 minutes, thus forms priming coat on the surface of the base material.
○：To be transparent during the surface of visual observations priming coat.
△：It is transparent during the surface of visual observations priming coat, but can confirms there is crackle.
×：During the surface of visual observations priming coat, find there is the crackle of albefaction degree, a part for priming coat is easily from poly- Ethylene glycol terephthalate base material is peeled off.
The base material that is used in layered product (1)~(4) obtained in embodiment 10~20, silane coupling agent and ultra-violet solidified group Compound, evaluation result are as shown in table 3.
[table 3]
(comparative example 1：The making of silane coupling agent (P ' -1))
The mass parts of aqueous resin composition (1) 100 and the mass parts of ion exchange water 577 are mixed, silane coupling agent is thus obtained (P’-1)。
(comparative example 2：The making of silane coupling agent (P ' -2))
Mix the mass parts of aqueous resin composition (1) 100, melamine crosslinkers (Dainippon Ink Chemicals system " BECKAMINE M-3 ") 3 mass parts and the mass parts of ion exchange water 613, thus obtain silane coupling agent (P ' -2).
(comparative example 3：The making of silane coupling agent (P ' -3))
Mix the mass parts of aqueous resin composition (1) 100, oxazoline crosslinking agent (Nippon Shokubai Co., Ltd's system " EPOCROS WS-700 ") 9.2 mass parts and the mass parts of ion exchange water 606, thus obtain silane coupling agent (P ' -3).
(comparative example 4：The making of silane coupling agent (P ' -4))
Mix the mass parts of aqueous resin composition (1) 100, epoxy crosslinking agent (Dainippon Ink Chemicals's system " CR-5L ") 3 matter Part and the mass parts of ion exchange water 648 are measured, silane coupling agent (P ' -4) is thus obtained.
(comparative example 5：The making of layered product (R1))
On the surface of PET film base material the primary coat obtained in comparative example 2 is coated with the way of dried thickness is about 1 μm Agent (P ' -1), heats 5 minutes at 150 DEG C and heats, thus form priming coat on the surface of the base material.Then, with 15 μm Coating thickness, the ultra-violet solidified composition (UV-2) obtained in the surface coating preparation example 3 of the priming coat, with high pressure Mercury lamp is as light source, with exposure intensity 0.5J/cm2To the coated face irradiation ultraviolet radiation, thus obtain on the surface of the base material There is the layered product (R1) of UV films with priming coat and on the surface of the priming coat.
(comparative example 6~8：Layered product (R2)~(R4) making)
The primary coat used in comparative example 5 is replaced using silane coupling agent (P ' -2)~(P ' -4) obtained in comparative example 2~4 respectively Agent (P ' -1), in addition, is made in the same manner as comparative example 5, obtains layered product (R2)~(R4).
The layered product (R1) obtained in comparative example 4~7 and the base material used in (R2), silane coupling agent and ultra-violet solidified group Compound, evaluation result are as shown in table 4.
[table 4]
By the evaluation result shown in table 3, the priming coat and base material using the smears formation of the present invention are confirmed Excellent adhesion, the adaptation with the cured coating film of Actinic-radiation curable composition is also excellent.
In addition, the priming coat of the smears formation using the present invention, high closely sealed after confirming with hot resistance test Property and excellent chemical-resistant.
On the other hand, comparative example 5 is the example using the smears for not containing crosslinking agent.Confirm with using the present invention Smears formation priming coat compare, the adaptation after its hot resistance test is insufficient to, in addition, chemical-resistant is also not enough It is enough.
Comparative example 6 is the example using melamine crosslinkers.Confirm with using the present invention's sub- containing carbonization two The priming coat of the smears formation of amine crosslinker is compared, and its chemical-resistant is insufficient to.
Comparative example 7 is the example of Shi Yong oxazoline crosslinking agents.Confirm with containing carbodiimides using the present invention The priming coat of the smears formation of crosslinking agent is compared, and the adaptation after its hot resistance test is insufficient to, in addition, chemical-resistant It is insufficient to.
Comparative example 8 is the example using epoxy crosslinking agent.Confirm with being handed over using the present invention containing carbodiimides The priming coat of the smears formation of connection agent is compared, and its chemical-resistant is insufficient to.

Claims (11)

1. a kind of smears, it is characterised in that the smears contains aqueous resin composition D and Carbodiimides crosslinking agent E, Wherein, the aqueous resin composition D is by vinyl ester resin A and the carbamate resins B with aromatic rings is scattered in Obtained from aqueous medium C；
The vinyl ester resin A is made obtained from epoxy resin a1 and compound a 2 react, wherein, the epoxy resin a1 For selected from one or more of group being made up of novolac type epoxy resin and bisphenol-type epoxy resin, the compound a 2 has There are acidic group and polymerism unsaturated group；
The carbamate resins B is to make the polyalcohol b1 containing polyalcohol b1-1 and polyalcohol b1-2 and polyisocyanates b2 Obtained from reaction, wherein, the polyalcohol b1-1 has aromatic rings, and the polyalcohol b1-2 has hydrophily base.
2. smears according to claim 1, wherein, the consumption of the crosslinking agent E is rubbed with the 80~100 of hydrophily base The amount of your % reactions, the hydrophily base is had by the carbamate resins B that can be reacted with carbodiimide-based Hydrophily base.
3. smears according to claim 1, wherein, the aromatic rings concentration in the polyalcohol b1-1 is 1.5~8mol/ Kg scope.
4. smears according to claim 1, wherein, the polyalcohol b1-1 with aromatic rings is containing fragrant adoption At least one of the alkylene oxide addition product b1-b of ester polyol b1-a and bisphenol-A polyalcohol.
5. smears according to claim 1, wherein, the contained polyalcohol with aromatic rings in the polyalcohol b1 B1-1 ratio is 40~98 mass % scope.
6. smears according to claim 1, wherein, the polyisocyanates b2 contains aromatic polyisocyanate.
7. smears according to claim 1, wherein, the compound a 2 is acrylic or methacrylic acid.
8. smears according to claim 1, wherein, part or all of the vinyl ester resin A is built in institute State in carbamate resins beta particle and form resin particle F.
9. smears according to claim 1, wherein, the vinyl ester resin A and carbamate resins B's Mass ratio is the scope that A/B is 60/40~10/90.
10. a kind of layered product, it is characterised in that have on the surface of base material in coating claim 1~9 described in any one Smears and by priming coat formed by drying, and have on the surface of the priming coat and use active energy ray-curable Property cured coating film formed by composition.
11. layered product according to claim 10, wherein, the Actinic-radiation curable composition contains with poly- The resin of conjunction property unsaturated group and the monomer with polymerism unsaturated group.
CN201480068831.0A 2013-12-20 2014-12-04 Smears and layered product Active CN105829464B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
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