CN102459392A - Reactive urethane compound, actinic-energy-ray-curable resin composition containing same, and use thereof - Google Patents

Reactive urethane compound, actinic-energy-ray-curable resin composition containing same, and use thereof Download PDF

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Publication number
CN102459392A
CN102459392A CN2010800243893A CN201080024389A CN102459392A CN 102459392 A CN102459392 A CN 102459392A CN 2010800243893 A CN2010800243893 A CN 2010800243893A CN 201080024389 A CN201080024389 A CN 201080024389A CN 102459392 A CN102459392 A CN 102459392A
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CN
China
Prior art keywords
compound
epoxy
curable resin
resin composition
active energy
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CN2010800243893A
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Chinese (zh)
Inventor
栗桥透
堀口尚文
小木聪
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • 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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Abstract

Provided are materials characterized by being capable of photopattering or by having flexibility required of flexible substrates, etc. and being less susceptible to alteration/discoloration even when exposed to high temperatures or light, while retaining heat resistance and long-lasting high insulating properties and retaining the intact basic properties of solder resists, color resists, or the like. One of the materials is a reactive polyurethane compound (A) obtained by reacting an epoxy carboxylate compound (a), a compound (b) having two hydroxy groups and one or more carboxy groups in the molecule, and a compound (c) containing no aromatic ring and having two isocyanate groups in the molecule, the compound (a) being obtained by reacting an epoxy resin (i) containing no aromatic ring and having two epoxy groups in the molecule with a compound (ii) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in the molecule. Others are a product of acid modification of the compound (A), an actinic-energy-ray-curable resin composition containing the compound (A) or the modification product, and a cured object formed from the composition.

Description

The reactive urethane compound thing, comprise active energy ray-curable resin composition of this compound and uses thereof
Technical field
The present invention relates to a kind of Yin Re of being difficult to or light and sex change/variable color and can access tough and softish solidify tunicle, can through development carry out the reactive polyurethane compound of photo-patterned (light パ タ one ニ Application グ) and contain this compound active energy ray-curable resin composition, its cured article, with and uses thereof.
Background technology
Miniaturization and with portable machine is a purpose with improving communication speed, requires tellite high precision, densification.Accompany therewith, the tunicle of lining circuit is formed with material, is the also raising day by day of requirement of so-called solder resist.Specifically; When making about tolerating the substrate that uses scolding tin etc. or the thermotolerance of the unit heat discharging during work, based on the safety of long term maintenance high-insulativity, can tolerate chemically treated performance such as plating etc.; With existing to compare requirement higher; The tunicle that people's demand has a more tough condensate performance forms uses material, but it is still undiscovered to satisfy the material of these various characteristicses.
In addition, in recent years, the purposes of softish tellites such as flexible base, board also enlarges.Under the situation of flexible base, board, the protection of circuit is carried out through the so-called covering layer film of lamination usually, but owing to reason such as wasting time and energy, the productivity aspect also leaves problem.Relative therewith, attempted using the tunicle of solder resist (the ソ Le ダ one レ ジ ス ト) type that can develop to form and used material, but this tunicle is more upright and more outspoken, do not find as yet a kind ofly can either follow bending, satisfy the material of other various necessary characteristics simultaneously.
In addition, also extensively attempted utilizing photodiode (so-called LED),,, on installation base plate, used the tunicle formation of white to use material usually in order more effectively to take out light for the tellite that this LED element is installed as light source.Form with material (being solder resist) for this tunicle, people are expecting to satisfy the desired various characteristics of above-mentioned solder resist, simultaneously the material that changes such as painted are not taking place at the element mounting process with between the secular usage period yet, but find as yet can practicality material.
In addition; Employed chromatic photoresist when manufacturing is used for the colour filter of so-called liquid crystal display or organic el panel; With tellite likewise, also have the thermal treatment when making or the problem of the heat when using or light sex change/variable color, color reprodubility variation.Therefore, need a kind ofly can to use sticker through the resist that alkaline development is carried out fine patterning and do not had a variable color.In addition, realize that flexible display screen needs flexible colour filter, so the flexibility that colour filter also need be same with flexible base, board.
But; If use epoxy acrylate used in existing solder resist or chromatic photoresist with aromatic nucleus; Then because the heat that thermal treatment such as the scolding tin processing of element when installing or LED element or backlight when using as the substrate of reality are produced or the influence of light; Resist resin meeting deterioration itself, variable color also leave problem in the practicality.
In order to solve above-mentioned variety of issue, patent documentation 1 and 2 etc. has been put down in writing following trial: with PEMULEN TR2 with have photoreactive compound as the compsn utilization; In order to give reactivity to PEMULEN TR2, the polymerisable ethylenic unsaturated group of grafting.But these materials are difficult to obtain in addition, do not have sufficient thermotolerance for the sufficient sensitivity of photo-patterned, so the safety of the thermotolerance in the thermal treatments such as scolding tin processing of element when installing etc., long term maintenance insulativity is insufficient.
In addition, the following trial that also had bibliographical information: use epoxy resin, derive reactive epoxy carbonate with ester ring type structure, and with its solder resist (referring to patent documentation 3) as white.But this material shortcoming flexibility is difficult to use in flexible base, board.
Put down in writing following trial in the patent documentation 4 and 5 etc.: will by have the compound of two hydroxyls and an above carboxyl concurrently in the two sense epoxy carbonates that contain aromatic nucleus, a part, the reactive polyurethane acryliccompound that diisocyanate cpd constitutes is used for solder resist.But record will not be used for solder resist etc. by the epoxy resin deutero-reactive urethane compound thing that does not contain aromatic nucleus fully.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-322546 communique
Patent documentation 2: TOHKEMY 2008-134621 communique
Patent documentation 3: TOHKEMY 2008-211036 communique
Patent documentation 4: japanese kokai publication hei 09-52925 communique
Patent documentation 5: TOHKEMY 2001-33960 communique
Summary of the invention
Invent problem to be solved
In view of foregoing; The present invention provides a kind of material that can be used for solder resist; It can carry out photo-patterned, have in the time of can tolerating the substrate that uses scolding tin etc. and make or the thermotolerance of the unit heat discharging during work, based on the safety of long term maintenance high-insulativity, for chemically treated tolerances such as plating; And provide a kind of and do not damage fundamental characteristics such as chromatic photoresist, have the flexibility that can be used for flexible base, board etc. and then have and also be difficult for Yin Gaowen or light and the material of the such performance of sex change/variable color.
Be used to solve the scheme of problem
The inventor furthers investigate in order to solve above-mentioned problem; The result has found to have accomplished the present invention thus through having the resulting reactive polyurethane compound of compound, its sour modified compound, the active energy ray-curable resin composition that contains this reactive polyurethane compound and/or its sour modified compound and the cured article thereof of two NCOs in the compound that has two hydroxyls and an above carboxyl in the epoxy carbonate that is obtained by the epoxy resin that does not contain aromatic nucleus, a part concurrently, a part.
Promptly; The present invention relates to a kind of reactive polyurethane compound (A); It makes the compound (b) that has two hydroxyls and an above carboxyl in epoxy carbonate (a), a part concurrently and does not contain compound (c) reaction that has two NCOs in aromatic nucleus and a part and obtains, and said epoxy carbonate (a) makes not contain and has more than one the compound of polymerisable ethylenic unsaturated group and an above carboxyl in the epoxy resin (i) that has two epoxy group(ing) in aromatic nucleus and a part and a part concurrently and (ii) react and obtain.
The present invention relates to a kind of sour modified-reaction based polyurethane compound (B) in addition, it makes multi-anhydride (d) obtain with above-mentioned reactive polyurethane compound (A) reaction.
The present invention relates to a kind of active energy ray-curable resin composition in addition, it comprises above-mentioned reactive polyurethane compound (A) and/or above-mentioned sour modified-reaction based polyurethane compound (B).
The present invention relates to above-mentioned active energy ray-curable resin composition in addition, it also comprises except that compound (A), reactive compounds (C) the compound (B).
The present invention relates to above-mentioned active energy ray-curable resin composition in addition, it comprises tinting pigment.
The present invention relates to above-mentioned active energy ray-curable resin composition in addition, it is the light transmission molding material.
The present invention relates to above-mentioned active energy ray-curable resin composition in addition, it uses material for painted tunicle forms.
The present invention relates to above-mentioned active energy ray-curable resin composition in addition, it uses material for the printing opacity tunicle forms.
The present invention relates to above-mentioned active energy ray-curable resin composition in addition, it uses material for resist.
The present invention relates to a kind of cured article of above-mentioned active energy ray-curable resin composition in addition.
The present invention relates to a kind of article in addition, it has carried out the outer article that cover for the cured article that uses above-mentioned active energy ray-curable resin composition.
The effect of invention
Reactive polyurethane compound of the present invention, its sour modified compound, the active energy ray-curable resin composition that contains this reactive polyurethane compound and/or its sour modified compound and cured article thereof are a kind of materials that can be used for solder resist; It can carry out photo-patterned, have in the time of can tolerating the substrate that uses scolding tin etc. and make or the thermotolerance of the unit heat discharging during work, based on chemically treated tolerances such as the safety of long term maintenance high-insulativity, anti-plating; And be a kind ofly not damage fundamental characteristics such as chromatic photoresist, have the flexibility that can be used for flexible base, board etc. and then have and also be difficult to Yin Gaowen or light and the material of the such performance of sex change/variable color.
Can be provided in the life-time service also non-staining white solder resist etc. thus, for instance, the solder resist of the LED installation base plate that can be suitable for using etc. as light source.In addition, effectively utilize the not characteristic of easy coloring, also be suitable as towards the resist layer sticker (レ ジ ス ト バ イ Application ダ one) or the optical waveguides formation material of the colour filter of liquid crystal display or organic el panel etc.In addition, material of the present invention therefore through being used for flexible base, board, can be brought into play effect of the present invention owing to also have flexibility concurrently to greatest extent.
Embodiment
Reactive polyurethane compound of the present invention (A) makes the compound (b) that has two hydroxyls and an above carboxyl in epoxy carbonate (a), a part concurrently, do not contain compound (c) reaction that has two NCOs in aromatic nucleus and a part obtains, and said epoxy carbonate (a) makes not contain and has more than one the compound of polymerisable ethylenic unsaturated group and an above carboxyl in the epoxy resin (i) that has two epoxy group(ing) in aromatic nucleus and a part and a part concurrently and (ii) react and obtain.That is, reactive polyurethane compound of the present invention (A) can obtain through following two reaction process: make epoxy resin (i) and compound (ii) react the epoxy carboxylic esterification operation that obtains epoxy carbonate (a); With make the compound (b) that has two hydroxyls and an above carboxyl in this epoxy carbonate (a), a part concurrently, do not contain the urethane operation of compound (c) reaction that has two NCOs in aromatic nucleus and a part.
Through epoxy resin (i) and compound are (ii) reacted, the epoxy carbonate (a) that obtains in the epoxy carboxylic esterification operation has two polymerisable ethylenic unsaturated groups and from two hydroxyls of epoxy resin (i) in a part.
In urethane operation subsequently; The compound (c) that utilization has NCO makes the hydroxyl that has the compound (b) of two hydroxyls and an above carboxyl in epoxy carbonate (a) and a part concurrently carry out urethane, thereby obtains reactive polyurethane compound (A).
The epoxy resin (i) that has two epoxy group(ing) in aromatic nucleus and a part that do not contain that uses in the epoxy carboxylic esterification operation is characteristic technical characterictic of the present invention.Since do not contain aromatic nucleus, thereby can be suppressed at the sex change/variable color under heat or the light, owing to have two epoxy group(ing), thereby can use the hydroxyl that generates behind the epoxy carboxylic esterification to carry out urethane.At this moment,, then can't adjust the molecular weight of resulting reactive polyurethane compound (A),, then be difficult to obtain suitable cured article rerum natura because of forming the higly branched chain structure if utilize the above epoxy compounds of trifunctional if utilize monofunctional epoxy compound.
As this epoxy resin (i), the compound of preferred formula (I) expression.
X-R-X (I)
(in the formula, X representes to have the functional group of epoxy group(ing), and R representes Direct Bonding or do not contain organic residue of aromatic nucleus.)
As the functional group in the general formula (I) with epoxy group(ing); For example; Can enumerate the aliphatics substituting group, 3 that glycidyl ether, Racemic glycidol ester group etc. have epoxy group(ing), 4-epoxycyclohexyl ether, 3,4-epoxycyclohexane carboxylate base etc. has the ester ring type substituting group of epoxy group(ing).
As the organic residue that does not contain aromatic nucleus in the general formula (I), only otherwise contain that aromatic nucleus is then not special to be limited.
When the compound of general formula (I) expression for example when making the compound that diol compound or dicarboxylic acid compound etc. and reactions such as epoxy chloropropane, Racemic glycidol, cyclohexene carboxylate, tetrahydrobenzene methyl alcohol obtain, R is the residue of this diol compound, dicarboxylic acid compound etc.
As the organic residue that does not contain aromatic nucleus, for example, can enumerate straight chain shape hydrocarbon residue, cyclic hydrocarbon residue, polyalkylene glycol residue, polyester glycol residue, cyclic ether diol residue etc.
As straight chain shape hydrocarbon residue; For example; Can enumerate glycol residue, Ucar 35 residue, butyleneglycol residue, pentanediol residue, pinakon residue, heptanediol residue, ethohexadiol residue, nonanediol residue, decanediol residue, hexanodioic acid residue, sebacic acid residue etc., preferred carbonatoms is 2～30, more preferably carbonatoms is organic residue of 6～18.When carbonatoms was less than this scope, the flexibility of resulting cured article was not enough, and obdurability is not enough under a lot of situation.
As the cyclic hydrocarbon residue; For example; Can enumerate cyclohexanediol residue, cyclohexanedimethanol residue, isobornyl diol residue, norbornylene diol residue, three ring decanediol residues, Hydrogenated Bisphenol A 99 residue, A Hydrogenated Bisphenol A F residue, hydrogenation xenol residue etc., preferred carbonatoms is 2～30, more preferably carbonatoms is organic residue of 6～18.When carbonatoms was less than this scope, the flexibility of resulting cured article was not enough, and obdurability is not enough under a lot of situation.As long as can replace, then substituent the position of substitution is not special to be limited.
As the polyalkylene glycol residue, for example, can enumerate polyoxyethylene glycol residue, W 166 residue, polytetramethylene glycol residue etc., the number-average molecular weight of polyalkylene glycol is preferably about 62～5000, more preferably about 500～2000.Number-average molecular weight is during less than this scope, and the flexibility of resulting cured article is not enough, and obdurability was not enough when number-average molecular weight was big.
As the polyester glycol residue; For example; Can enumerate polycaprolactone glycol residue, glycol adipate diol residue, straight chain hydrocarbon polycarbonate diol residue, cyclic hydrocarbon polycarbonate diol residue etc., the number-average molecular weight of polyalkylene glycol residue is preferably about 100～5000, more preferably about 500～2000.Number-average molecular weight is during less than this scope, and the flexibility of resulting cured article is not enough, and obdurability was not enough when number-average molecular weight was big.
As the cyclic ether diol residue, for example, can enumerate the spiroglycol residue with spirane structure, dioxane diol residue etc. with ethylidene ether ring structure.
Wherein, consider the compound that has ring texturees such as cyclohexane ring structure, spirane structure, ethylidene ether ring structure in the preferred molecule from the stable on heating aspect of cured article.That is, have among preferred organic residue R above-mentioned alicyclic structure, or the X of functional group with epoxy group(ing) contain the compound of ester ring type epoxy group(ing).
In addition, utilize epoxy chloropropane to make the fatty alcohol glycidyl ether and obtain under the situation of epoxy resin (i), be prone to residual from the chlorosity of epoxy chloropropane.When solder resist that is used for the long-term insulativity of requirement etc., this chlorine can cause disconnection, the short circuit of wiring because of ion migration.Therefore; Preferably utilize short-path distillation etc. to make with extra care; Perhaps use the epoxy resin do not utilize epoxy chloropropane and to make, perhaps use after utilizing epoxy chloropropane the what is called nuclear hydrogenated epoxy resin that aromatic nucleus is carried out selective hydration aromatic series phenol glycidyl ether.
About preferred chlorine content ranges, the chloride content that is contained in the epoxy resin (i) (utilize according to JIS K7243-3:2005 assay method) is 0 weight %～0.2 weight %, 0 weight %～0.1 weight % more preferably.
In addition, when R is Direct Bonding, for example, can enumerate 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters (manufacturing of Daicel chemistry, セ ロ キ サ イ De 2021) etc.
Compound (ii) is used for epoxy carboxylic esterification operation, and it has polymerisable ethylenic unsaturated group and an above carboxyl more than one concurrently in a part.Compound (ii) has following effect: utilize the reaction of epoxy carboxylicesters that above-mentioned epoxy resin (i) is imported in the diol compound, simultaneously the ethylenic unsaturated group is imported in the reactive polyurethane compound (A).
As this compound (ii); The preferred compound that does not have hydroxyl; For example, can enumerate (methyl) acrylic acid or the like, butenoic acid, alpha-cyano styracin, styracin, or saturated or unsaturated dibasic acid and contain reaction product between single glycidyl compound of unsaturated group etc.
As (methyl) acrylic acid or the like; For example,---reaction with same mole product of half ester class, saturated or unsaturated dibasic acid and (methyl) vinylformic acid list glycidyl ester derivatives class---the half ester class etc. of can enumerating the reaction with same mole product that has (methyl) acrylate derivative of 1 hydroxyl in the reaction product of (methyl) vinylformic acid, β-styrene acrylic, β-furfuryl group vinylformic acid, (methyl) acrylic acid dimer, (methyl) vinylformic acid and 6-caprolactone, saturated or unsaturated dicarboxylic acid anhydride and 1 molecule.
Wherein, the aspect of the sensitivity when processing active energy ray-curable resin composition is considered, the reaction product or the styracin of preferred (methyl) vinylformic acid, (methyl) vinylformic acid and 6-caprolactone.
In the epoxy carboxylic esterification operation, preferably with respect to 1 equivalent epoxy group(ing) of above-mentioned epoxy resin (i), the compound of use 90～120 equivalent % (ii).As long as in this scope, just can under more stable condition, make.Compound charging capacity (ii) is during more than above-mentioned scope, can remaining excessive carboxylic acid, thereby not preferred.In addition, unreacted epoxy groups is residual at least if cross, and the stability of the resin of manufacturing can have problems.
Epoxy carboxylic esterification operation can be reacted with solvent-free mode, also can be with reacting behind the solvent cut.As this solvent, the inert solvent is then not special to be limited so long as epoxy carboxylic esterification reaction is, in addition, the urethane operation of subsequent processing or use as required after state acid and increase in the operation, also preferably use the inert solvent.The consumption of this solvent should suitably be adjusted according to the viscosity and the purposes of resulting resin, with solid component meter be preferably about 30 weight %～100 weight %, more preferably about 50 weight %～90 weight % about.
As this solvent, varsol for example can be enumerated fragrant family hydrocarbon solvents such as toluene, YLENE, ethylbenzene, tetramethyl-benzene; Fatty family hydrocarbon solvent such as hexane, octane, decane, as their sherwood oil, white gasoline, solvent naphtha etc. of mixture.
In addition, as esters solvent, for example, can enumerate alkyl acetate classes such as ETHYLE ACETATE, propyl acetate, butylacetate; Cyclic ester classes such as gamma-butyrolactone; Single alkylene glycol monoalky lether monoacetate classes such as ethylene glycol monomethyl ether monoacetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Triethylene glycol ethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butyleneglycol monomethyl ether monoacetate or many alkylene glycols monoalky lether monoacetate class; Polycarboxylic acid alkyl esters such as pentanedioic acid dialkyl, dialkyl succinate, hexanodioic acid dialkyl etc.
In addition, as ether solvent, for example, can enumerate alkyl ethers such as diethyl ether, ethyl-butyl ether; Glycol ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dme, dipropylene glycol diethyl ether, triethylene glycol dme, triethylene glycol diethyl ether; Ring-type ethers such as THF etc.
In addition, as ketones solvent, for example, can enumerate acetone, methyl ethyl ketone, pimelinketone, isophorone etc.
In addition, can also with after the reactive compounds (C) stated etc. use separately or as mixed organic solvents.In this case, also can directly utilize with the form of active energy ray-curable resin composition.
In the epoxy carboxylic esterification operation; Preferably use catalyzer in order to promote reaction; With respect to reactant, promptly with respect to comprising above-mentioned epoxy resin (i), compound (ii) and the total amount of the reactant of the solvent that uses under some situation etc., this catalyst consumption is about 0.1 weight %～10 weight % about.Temperature of reaction is 60～150 ℃, and the reaction times is preferably 5～60 hours.
As this catalyzer; For example, can enumerate basic catalysts such as triethylamine, benzyldimethylamine, triethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, sad chromium, zirconium caprylate etc.
In addition, as hot stopper, preferably use hydroquinone monomethyl ether, 2-toluhydroquinone, quinhydrones, phenylbenzene bitter taste hydrazides, diphenylamine, 3,5-di-t-butyl-4-hydroxytoluene etc.
Epoxy carboxylic esterification operation is suitably sampled, simultaneously reach below the 5mgKOH/g, be preferably moment below the 2mgKOH/g as terminal point with the sample acid number.
The compound (b) that has two hydroxyls and an above carboxyl in a part that uses in the urethane operation concurrently is the material with following effect: through in reactive polyurethane compound (A), importing carboxyl, so that reactive polyurethane compound (A) is solvable in alkaline aqueous solution when photo-patterned.
As this compound (b), for example, can enumerate dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid etc.Wherein consider raw-material acquisition, preferred dimethylol propionic acid, dimethylolpropionic acid.
The compound (c) that not containing of using in the urethane operation has two NCOs in aromatic nucleus and a part carries out the urethane reaction, manufacturing reactive polyurethane compound (A) with the hydroxyl of epoxy carbonate (a) and compound (b) (compound (b) has two hydroxyls and an above carboxyl concurrently in a part).Thus, can form material with suitable flexibility.In addition, owing to do not contain aromatic nucleus, thus can suppress heat or the caused sex change/variable color of light.
As this compound (c); For example, can enumerate aliphatics ring-type vulcabond such as straight chain shape vulcabond such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, norbornylene vulcabond, hydrogenation of benzene dimethylene diisocyanate, hydrogenation methylene-bis phenylene diisocyanate etc.
In the urethane operation, preferably in the mixture of epoxy carbonate (a) and compound (b), mix compound (c) with NCO.
When making reactive polyurethane compound of the present invention (A), the value of the mole number of the compound (c) of (mole number of the mole number+compound (b) of epoxy carbonate (a))/have NCO, be that the ratio of hydroxyl and NCO in the reaction system is preferably 1.05～2 scope, is preferably 1.1～1.5 scope especially.This is because through making in the urethane reaction finally not residual isocyanate base, can improve the storage stability of reactive polyurethane compound (A).When the ratio of the hydroxyl in the reaction system and NCO is worth greater than this; The molecular weight of resulting reactive polyurethane compound (A) is too small; Be difficult to obtain tough cured article, in addition, when the ratio of the hydroxyl in the reaction system and NCO is worth less than this; The molecular weight of resulting resin is excessive, can manifest relatively poor detrimentally affects such as development property.
In addition, when making reactive polyurethane compound (A), the value of the mole number of the mole number/compound (b) of epoxy carbonate (a) is preferably 0.1～4 scope, is preferably 0.3～2 scope especially.This value was greater than 4 o'clock, and the carboxyl quantitative change in the reactive polyurethane resin (A) is few, is difficult to give desired development property.In addition, this was worth less than 0.1 o'clock, and the reactive group in the reactive polyurethane resin (A) tails off, and is difficult to the obdurability of giving sensitivity, filming.
The urethane operation can be reacted with solvent-free mode, also can be with reacting behind the solvent cut.As this solvent, so long as reaction is the then not special qualification of inert solvent to urethane.The consumption of this solvent should suitably be adjusted according to the viscosity and the purposes of resulting resin, with solid component meter be preferably 30 weight %～99 weight %, more preferably about 50 weight %～90 weight %.In addition, when in conduct, using solvent to make in the epoxy carboxylic esterification operation of an operation,, then can directly not supply in urethane operation as subsequent processing except that desolvating so long as two reactions are inertia yet.
As this solvent, can enumerate illustrative solvent in above-mentioned epoxy carboxylic esterification operation.In addition, as stated, also can with after the reactive compounds (C) stated etc. separately or mix as organic solvent, in this case, also can directly utilize as active energy ray-curable resin composition.
Hot stoppers etc. also can use and the same compound of above-mentioned epoxy carboxylic esterification operation.
The urethane operation also can be reacted with the mode of catalyst-free in fact, but in order to promote reaction also can use catalyzer.When using catalyzer; With respect to reactant, promptly with respect to comprising above-mentioned carbonate (a), compound (b), have the total amount of the reactant of solvent of using under compound (c) and some situation of NCO etc., this catalyst consumption is about 0.01 weight %～1 weight % about.Temperature of reaction is 40～150 ℃, and the reaction times is preferably 5～60 hours.
As this catalyzer, preferably use lewis-base catalyst such as known general basic catalyst, for example ethyl stannous caproate, stannous octoate.
In the urethane operation, with basically not the moment of residual isocyanate base as reaction end.In order to confirm this reaction end, can be to belonging to the 2250cm of NCO in the infrared absorption spectrometry -1Near the peak observe and carrying out, perhaps use based on the volumetry of JIS K 1556:1968 etc. and carry out.
About the preferred molecular weight range of the of the present invention reactive carbonate (A) that obtains like this, the polystyrene conversion weight-average molecular weight among the GPC (GPC) is 1000～30000 scope, 1500～20000 scope more preferably.
During less than this molecular weight, can't give full play to the obdurability of cured article, in addition, viscosity raises during greater than this molecular weight, is difficult to coating etc.
When reactive polyurethane compound of the present invention (A) is used as the resist of alkali-developable; Preferably feed intake with calculated amount, this calculated amount is to make the solids component acid number (based on JIS K5601-2-1:1999) of the reactive polyurethane compound (A) that finally obtains reach 30～120mgKOH/g, the value that calculates of 40～105mgKOH/g more preferably.The solids component acid number is when this scope, and active energy ray-curable resin composition of the present invention demonstrates good alkaline aqueous solution development property.That is, good pattern becomes second nature and to crossing also broad of the span of control of developing.
Also comprise the sour modified-reaction based polyurethane compound (B) that multi-anhydride (d) is obtained with reactive polyurethane compound (A) reaction among the present invention.Like this, compound not only capable of using (b) can also utilize other modes further to increase the needed acid number of alkaline development according to desired resin properties.Among the present invention, this reaction process is designated as acid increases operation (acid is paid and added engineering).
It is to make residual hydroxyl reaction in multi-anhydride (d) and the reactive polyurethane compound (A) that acid increases operation, imports the operation of carboxyl through ester bond.Therefore, can not carry out acid more than the equivalent with the residual hydroxyl in above-mentioned urethane operation end back increases.
As this multi-anhydride (d); Then all can use so long as have the compound of cyclic acid anhydride structure in a part; Consider from the aspect that excellent compound such as alkaline aqueous solution development property, thermotolerance, hydrolytic resistance is provided; For example, can enumerate aromatic anhydrides such as Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride; Alicyclic series acid anhydrides such as Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, 3-methyl-Tetra Hydro Phthalic Anhydride, 4-methyl-hexahydrophthalic anhydride; Aliphatic anhydride such as succinyl oxide, maleic anhydride, itaconic anhydride.Wherein, consider aliphatic acid anhydrides, alicyclic series acid anhydrides from the aspect of tint permanence.
Acid increases operation and carries out through in above-mentioned reactive polyurethane compound (A), adding multi-anhydride (d).The consumption of this multi-anhydride (d) can promptly suitably change from the acid number of compound (b), residual amount of hydroxyl groups, further needed acid number according to the set(ting)value of reactive polyurethane compound (A).
But; When using sour modified-reaction based polyurethane compound of the present invention (B) as the resist of alkali-developable; Feed intake with calculated amount, this calculated amount is to make its solids component acid number (based on JIS K 5601-2-1:1999) reach 30～120mgKOH/g, more preferably 40～105mgKOH/g and the amount that calculates.The solids component acid number is when this scope, and active energy ray-curable resin composition of the present invention demonstrates good alkaline aqueous solution development property.That is, good pattern is become second nature and also broad of the span of control of cross developing.
Acid increases in the operation; Preferably use catalyzer in order to promote reaction; With respect to reactant, promptly with respect to the total amount of the reactant that comprises solvent of using under above-mentioned reactive polyurethane compound (A), multi-anhydride (d) and some situation etc., this catalyst consumption is about 0.1 weight %～10 weight % about.Temperature of reaction is 60～150 ℃, and the reaction times is preferably 5～60 hours.
As this catalyzer, for example, can enumerate triethylamine, benzyldimethylamine, triethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, sad chromium, zirconium caprylate etc.
Acid increases operation can react with solvent-free mode, also can be with reacting behind the solvent cut.As this solvent,, acid is the then not special qualification of inert solvent so long as being increased reaction.In addition, when in conduct, using solvent to make in the urethane operation of an operation,, then also can directly not supply to increase in the operation in acid as subsequent processing except that desolvating so long as two reactions are inertia.
The consumption of this solvent should suitably be adjusted according to the viscosity and the purposes of resulting resin, with solid component meter be preferably about 30 weight %～90 weight %, more preferably about 50 weight %～80 weight % about.
As this solvent, for example, can use and above-mentioned epoxy carboxylic esterification operation or the same solvent of urethane operation.In addition, also can with after the reactive compounds (C) stated etc. separately or as mixed organic solvents, in this case, also can directly utilize as active energy ray-curable resin composition.
Hot stoppers etc. also can use and above-mentioned epoxy carboxylic esterification operation or the same compound of urethane operation.
Acid is increased operation suitably sample, utilize the acid number of aforesaid method assaying reaction thing simultaneously, the moment of positive and negative 10% scope of acid number that the acid number of being measured is reached setting is as terminal point.
As can contain in the active energy ray-curable resin composition of the present invention except that compound (A), reactive compounds (C) the compound (B); For example, can enumerate the so-called reactive oligomers classes such as vinyl compound class of (methyl) esters of acrylic acid of free radical reaction type, the epoxy compounds class of cationoid reaction type, not only suitable free radical reaction type but also suitable cationoid reaction type.
As the esters of acrylic acid of this free radical reaction type, can enumerate simple function (methyl) esters of acrylic acid, multifunctional (methyl) esters of acrylic acid, carbamate (methyl) propenoate, polyester (methyl) propenoate, other epoxies (methyl) propenoate etc.
As simple function (methyl) esters of acrylic acid; For example, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) lauryl acrylate, polyoxyethylene glycol (methyl) propenoate, polyoxyethylene glycol (methyl) propenoate monomethyl ether, (methyl) phenylethyl, (methyl) IBOA, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester etc.
As multifunctional (methyl) esters of acrylic acid, gather (methyl) propenoate, Dipentaerythritol of reaction product of two (methyl) propenoate, Dipentaerythritol and 6-caprolactone that can enumerate the 6-caprolactone affixture of butyleneglycol two (methyl) propenoate, pinakon two (methyl) propenoate, NSC 6366 two (methyl) propenoate, nonanediol two (methyl) propenoate, ethylene glycol bisthioglycolate (methyl) propenoate, Diethylene Glycol two (methyl) propenoate, polyoxyethylene glycol two (methyl) propenoate, three (methyl) acryloxy ethyl isocyanuric acid ester, W 166 two (methyl) propenoate, hexanodioic acid epoxy two (methyl) propenoate, ethoxylation bis-phenol two (methyl) propenoate, ethoxylation A Hydrogenated Bisphenol A (methyl) propenoate (water elementization PVC ス Off エ ノ one Le エ チ レ Application オ キ サ イ De (メ タ) ア Network リ レ one ト), bis-phenol two (methyl) propenoate, hydroxypivalic acid NSC 6366 gathers (methyl) propenoate, trimethylolpropane tris (methyl) propenoate, triethylol propane three (methyl) propenoate or its ethylene oxide adduct, tetramethylolmethane three (methyl) propenoate or its ethylene oxide adduct, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol six (methyl) propenoate or its ethylene oxide adduct etc.
In addition; Can enumerate same intramolecularly have concurrently can carbamate (methyl) propenoate of functional group and the amino-formate bond of reaction under the active energy beam effect, same intramolecularly have concurrently can polyester (methyl) propenoate of the functional group of the reaction active energy beam effect under and ester bond, derived from other epoxy resin and same intramolecularly have concurrently can the functional group of reacting under the active energy beam effect except that compound (A), epoxy (methyl) propenoate the compound (B), and can enumerate the two or more reactive oligomers that has in these compounds combinations etc.
Epoxy compounds class as this cationoid reaction type; The compound of epoxy group(ing) is then not special to be limited so long as have, and for example, can enumerate (methyl) glycidyl acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl base ether, dihydroxyphenyl propane diglycidyl ether, 3; 4-epoxycyclohexyl methyl-3 '; 4 '-epoxycyclohexane carboxylate (Union Carbide Corporation make, サ イ ラ キ ユ ア UVR-6110 etc.), 3,4-epoxycyclohexyl ethyl-3 ', 4 '-epoxycyclohexane carboxylate, VCH diepoxide () 、 limonene dioxide such as Union Carbide Corporation's manufacturing, ELR-4206 (manufacturing of Daicel chemical industry society, セ ロ キ サ イ De 3000 etc.), allyl group tetrahydrobenzene diepoxide, 3; 4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3; 4-epoxycyclohexyl-5,5-volution-3,4-epoxy) hexanaphthene-1; 3-dioxane, two (3; The 4-epoxycyclohexyl) adipic acid ester (Union Carbide Corporation's manufacturing, サ イ ラ キ ユ ア UVR-6128 etc.), two (3,4-epoxycyclohexyl methyl) adipic acid ester, two (3, the 4-epoxycyclohexyl) ether, two (3; 4-epoxycyclohexyl methyl) ether, two (3, the 4-epoxycyclohexyl) di-ethyl siloxane etc.
As this vinyl compound class, can enumerate vinyl ethers, styrenic, other vinyl compounds.
As vinyl ethers, for example, can enumerate ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol bisthioglycolate vinyl ether etc.
As styrenic, for example, can enumerate vinylbenzene, vinyl toluene, ethyl styrene etc.
As other vinyl compounds, for example, can enumerate cyanacrylate, tricarbimide methyl triallyl etc.
Wherein, as reactive compounds (C), (methyl) esters of acrylic acid of preferred especially free radical reaction type.When using the compound of cationoid reaction type, in order not make carboxylic acid and epoxy reaction, thereby need process two liquid mixed types.
With reactive polyurethane compound of the present invention (A) and/or sour modified-reaction based polyurethane compound (B) and mixing except that compound (A), reactive compounds (C) the compound (B) as required, can access active energy ray-curable resin composition of the present invention.At this moment, can also suitably add other compositions according to purposes.
About active energy ray-curable resin composition of the present invention, in said composition, comprise and be preferably 5 weight %～97 weight %, be preferably reactive polyurethane compound (A) and/or the sour modified-reaction based polyurethane compound (B) of 10 weight %～87 weight % especially; Be preferably 3 weight %～95 weight %, especially be preferably 3 weight %～90 weight % except that compound (A), reactive compounds (C) the compound (B).Can also comprise other compositions that are limited to about 70 weight % as required.
Active energy ray-curable resin composition of the present invention utilizes active energy beam to solidify easily, and cured article can be provided.At this,, can enumerate hertzian wave such as ultraviolet ray, visible rays, infrared rays, X ray, gamma-rays, laser rays as active energy beam; Beta lines such as alpha-ray, β ray, electron rays etc.Consider the purposes that the present invention is fit to, among these, preferred ultraviolet ray, laser rays, visible rays or electron rays.
The tinting pigment that can contain in the active energy ray-curable resin composition of the present invention is in order to be that coloured material uses with this active energy ray-curable resin composition.Even it is painted also few that material of the present invention is exposed under heat or the light, thereby be suitable for using in the purposes of coloured material.
As this tinting pigment, for example, can enumerate the pigment dyestuff of phthalocyanine system, azo system, quinacridone etc.; Mineral dye such as carbon black, titanium oxide.Wherein, be specially suitable particularly as being coloured to the purposes of material use of color (such as white, green, blueness etc.) that tonal variation receives the sensitivity influence of yellow variable color.
Molding material is meant the material that is used for following purposes among the present invention: uncured compsn is put into mold, perhaps press mold and after molding object, utilize active energy beam to make its curing and the purposes of moulding; Perhaps, make its curing and the purposes of moulding to uncured focused lights such as compsn irradiating laser etc.That is, can enumerate and be shaped to plane sheet material; The sealing material that is used for protecting component; To be impressed into through " template " of microfabrication and carry out fine moulding, so-called nano impression material on the uncured composition; And the purposes such as peripheral sealing material that particularly heat, light required harsh photodiode, photo-electric conversion element etc.
Tunicle forms and is utilized in order to be covered substrate surface with material among the present invention.Can enumerate ink materials such as photogravure ink, flexo printing ink, silk-screen ink, flexographic ink; Coating materials such as dura mater, finish paint, overprint varnish zhe, Clear paint; The various joint compounds that lamination is used etc. with, CD; Adhesivess such as tackiness agent; Solder resist, anticorrodent, micromotor are with purposes such as anticorrosive additive material such as resists.In addition, so-called dry film also is equivalent to tunicle and forms that use material, so-called dry film be to form like this: tunicle is formed with material temporarily coat on the separability base material and after carrying out film forming, fit on the target substrate formation tunicle originally.
Wherein, Reactive polyurethane compound (A) and/or sour modified-reaction property carbamate compounds (B) performance are the characteristic of solubility in alkaline aqueous solution, thereby the active energy ray-curable resin composition among also preferred the present invention is as liquid alkali developing type anticorrosive additive material compsn.
Resist is meant following material with material among the present invention: on base material, form said composition by rete; Thereafter; Irradiation ultraviolet radiation isoreactivity energy-ray partly is to utilize irradiating part, the material of the physical difference of the irradiating part active energy beam responsive type of drawing not.And be the material that uses with following purpose: utilize some method (for example utilize solvent etc. or basic soln etc. to make its dissolving, or the like) to remove irradiating part or irradiating part not, to draw.
Resist of the present invention is used material---and active energy ray-curable resin composition can be used in the various materials of patternable; For example particularly; Layer insulation material for solder resist material, lamination method (PVC Le De ア Star プ worker method) usefulness is useful; In addition, as optical waveguides, can also be used in printed substrate, optoelectronic substrate or photopolymer substrate such electric base material, electronic substrate and light base material etc.
As specially suitable purposes, give full play to can access soft and tough and then also be difficult to Yin Re or light and the characteristic of the cured article of sex change/variable color, preferably have the purposes of the chromatic photoresists such as permanent resist purposes, colour filter such as solder resist of painted purpose concurrently.
In addition, if need to be used to the flexible base, board purposes of flexibility, then can bring into play effect of the present invention to greatest extent.
As using active energy ray-curable resin composition of the present invention to form the method for tunicle; Not special restriction, can at random adopt planography ways such as porous printing mode, offset printing such as letterpress mode, silk screen printing such as intaglio printing mode, flexographic printing such as photogravure, various coating method (such as roller coating machine, cutter be coated with machine, mould is coated with machine, curtain coater, spin coater etc.).
The cured article that its curing is formed to active energy ray-curable resin composition irradiation active energy beam of the present invention is also contained among the present invention.
In addition, be fit for various uses, be limited to other compositions of 70 weight % on can also in this resin combination, adding in order to make active energy ray-curable resin composition of the present invention.As other compositions, the viscosity adjustment that can enumerate Photoepolymerizationinitiater initiater, various additive, paint material, is used to give coating flexibility etc. is with volatile solvent etc.
As this Photoepolymerizationinitiater initiater, can use free radical type Photoepolymerizationinitiater initiater, positively charged ion is Photoepolymerizationinitiater initiater etc.
As the free radical type Photoepolymerizationinitiater initiater, for example, can enumerate bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, bitter almond oil camphor propyl ether, bitter almond oil camphor ethyl isobutyl ether; Methyl phenyl ketone, 2; 2-diethoxy-2-phenyl methyl phenyl ketone, 2; 2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-acetophenones such as 1-ketone; Anthraquinone classes such as 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; 2, thioxanthene ketones such as 4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2-clopenthixal ketone; Ketal classes such as methyl phenyl ketone dimethyl ketal, benzoin dimethylether; UVNUL MS-40,4-benzoyl--4 '-methyldiphenyl thioether, 4,4 '-benzophenones such as two methylamino UVNUL MS-40; 2,4, the known general free radical type photoreaction initiator of phosphinoxidess such as 6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide etc.
As this positively charged ion is Photoepolymerizationinitiater initiater, can enumerate lewis acidic diazonium salt, lewis acidic salt compounded of iodine, lewis acidic sulfonium salt, Lewis acid De phosphonium salt, other halogenide, triazine series initiators, borate-based initiator, other light acid producing agent etc.
As lewis acidic diazonium salt; For example; Can enumerate p-methoxyphenyl diazonium hexafluorophosphate, N, N-diethylamino phenyl diazonium hexafluorophosphate (manufacturing of three new chemical industry societies, サ Application エ イ De SI-60L, サ Application エ イ De SI-80L, サ Application エ イ De SI-100L etc.) etc.
As lewis acidic salt compounded of iodine, for example, can enumerate diphenyl iodine hexafluorophosphate, phenylbenzene iodine hexafluoro antimonate etc.
As lewis acidic sulfonium salt, for example, can enumerate triphenylsulfonium hexafluorophosphate (Union Carbide Corporation's manufacturing, Cyracure UVI-6990 etc.), triphenylsulfonium hexafluoro antimonate (Union Carbide Corporation's manufacturing, Cyracure UVI-6974 etc.) etc.
As Lewis acid De phosphonium salt, for example, can enumerate triphenyl phosphorus hexafluoro antimonate etc.
As other halogenide; For example, can enumerate 2,2; 2-three chloro-[1-4 '-(dimethyl ethyl) phenyl] ethyl ketone (manufacturing of AKZO society, Trigonal PI etc.), 2; 2-two chloro-1-[4-(Phenoxyphenyl)] ethyl ketone (manufacturing of Sandoz society, Sandray 1000 etc.), α, α, α-trisbromomethyl phenyl sulfone (manufacturing of system iron chemistry society, BMPS etc.) etc.
As the triazine series initiators; For example; Can enumerate 2; 4; 6-three (trichloromethyl) triazine, 2-trichloromethyl-4-(4 '-p-methoxy-phenyl)-6-triazine (manufacturing of panchim society, Triazine A etc.), 2-trichloromethyl-4-(4 '-methoxyl-styrene)-6-triazine (manufacturing of panchim society, Triazine PMS etc.), 2-trichloromethyl-4-piperonyl-6-triazine (manufacturing of panchim society, Triazine PP etc.), 2-trichloromethyl-4-(4 '-methoxyl group naphthyl)-6-triazine (manufacturing of panchim society, Triazine B etc.), 2 [2 ' (5 "-methyl furan base) ethylidene]-4; two (the trichloromethyl)-s-triazine of 6-(three make with ケ ミ カ Le society), 2-(2 '-furyl ethylidene)-4, two (the trichloromethyl)-s-triazine of 6-(three make with ケ ミ カ Le society) etc.
As borate-based initiator, for example, can enumerate NK-3876 that Japanese photopigment makes and NK-3881 etc.
As other light acid producing agent etc., for example, can enumerate 9-phenylacridine, 2; 2 '-two (o-chloro-phenyl-)-4,4 ', 5; 5 '-tetraphenyl-1,2-bisglyoxaline (dark fund changes into the bisglyoxaline that society makes etc.), 2, two (2-aminopropane) dihydrochlorides of 2-azo (with the pure medicine of light society manufacturing, V50 etc.), 2; Two [2-(tetrahydroglyoxaline-2-yl) propane] dihydrochlorides of 2-azo (with the pure medicine of light society manufacturing, VA044 etc.), [eta-5-2-4-(cyclopentadecane base) (1,2,3; 4,5,6; Eta)-(methylethyl) benzene] iron (II) hexafluorophosphate (manufacturing of Ciba Geigy society, Irgacure 261 etc.), two (1-(2,4 difluorobenzene base)-3-pyrryl) two luxuriant titaniums (manufacturing of Ciba Geigy society, CGI-784 etc.) etc.
In addition, can also share temperature-sensitive peroxo-system free radical type initiators such as azo series initiators, Lucidol such as Diisopropyl azodicarboxylate etc.And also can share free base system and positively charged ion is these two kinds of Photoepolymerizationinitiater initiaters.
These Photoepolymerizationinitiater initiaters can use a kind of separately, also can suitably share two or more.
As these various additives, for example, can enumerate thermal curing catalysts such as trimeric cyanamide; Thixotropy imparting agents such as fumed silica; Silicone-based, fluorine are flow agent or skimmer; Stopper such as quinhydrones, hydroquinone monomethyl ether; Stablizer; Inhibitor etc.
As this paint material, can enumerate not to be colored as the pigment extender of purpose, for example talcum, permanent white, lime carbonate, magnesiumcarbonate, barium titanate, white lake, silicon-dioxide, clay etc.
In addition; Can also use active energy beam is not had reactive resene (so-called inert polymer), for example other epoxy resin, resol, carbamate resins, vibrin, ketone resin, cresol resin, xylene resin, diallyl phthalate resin, styron, guanamine resin, natural or viton, acrylics, polyolefin resin or their modifier.These resins preferably use with the scope below the 40 weight % in this resin combination.
Particularly, in the time will in the solder resist purposes, using the resin combination that comprises sour modified-reaction based polyurethane compound (B),, preferably use known general epoxy resin as active energy beam is not had reactive resene.After utilizing active energy beam to solidify; Also the carboxyl from compound (B) can residually be arranged; The water tolerance of its cured article or water-disintegrable tendency with deterioration; But active energy beam is not had reactive epoxy resin residual carboxyl is further reacted, form firm crosslinking structure, thereby can improve performance.
In this resin combination, can also be at 50 weight %, more preferably add this viscosity adjustment in the scope below the 35 weight % and use volatile solvent.
Embodiment
Below, the present invention will be described in more detail through embodiment, however the present invention is not limited to these embodiment.In addition, among the embodiment only otherwise special declaration, then part expression weight part.
Softening temperature, epoxy equivalent (weight) etc. utilize following condition to measure.
(1) epoxy equivalent (weight): utilize and measure based on the method for JIS K 7236:2001.
(2) chloride content: utilize and measure based on the method for JIS K 7243-3:2005.
(3) acid number: utilize and measure based on the method for JIS K 0070:1992.
(4) condition determination of GPC is following.
Type: TOSOH HLC-8220GPC
Post: TSKGEL Super HZM-N
Elutriant: THF (THF); 0.35ml/ minute, 40 ℃ of temperature
Detector: differential refractometer
Molecular weight standard: PS
Synthetic (the epoxy carboxylic esterification operation) of synthetic routine 1 epoxy carbonate (a)
To epoxy group(ing) is that the epoxy resin (i) of record in 1 mole the below table 1 is (with epoxy equivalent (weight) (WPE; G/eq) identical g number), as compound vinylformic acid (being called for short AA, molecular weight 72) (ii) 1 mole (72g), as the propylene glycol monomethyl ether monoacetate (being called for short PGMAc) that adds among the triphenylphosphine 3g of catalyzer as solvent; Making solids component is 80%; Under 100 ℃, make its reaction 24 hours, obtain epoxy carbonate (a) solution.Reaction end utilizes solids component acid number (AV; MgKOH/g) confirm.The solids component acid number is converted by the solution acid number of measuring in the reaction system.
Synthetic example 2: epoxy carbonate synthetic with aromatic nucleus
In addition the bisphenol A type epoxy resin that uses the amount of record in the table 1 likewise reacts with synthetic example 1 as epoxy resin.
[table 1]
The abbreviation of record in the table 1
WPE: epoxy equivalent (weight) (g/eq)
TCl: chloride content (%)
AV: the solution acid number in the reaction system; MgKOH/g
X: the kind of the epoxy group(ing) in the general formula (I) and its bonding form
GEth: glycidyl ether
CEst:3,4-epoxycyclohexane carboxylate base
CEth:3,4-epoxycyclohexyl ether
R: the diol residue in the general formula (I)
HD: pinakon residue (straight chain shape hydrocarbon residue)
PTMG650: polytetramethylene glycol residue (polyalkylene glycol residue; Molecular-weight average 650)
PCDL800: polycarbonate diol residue (polyester glycol residue; Molecular-weight average 800)
CHDM: cyclohexanedimethanol residue (cyclic hydrocarbon residue)
H-BisA: hydrogenation type dihydroxyphenyl propane residue (cyclic hydrocarbon residue)
TCD: tristane dimethanol residue (cyclic hydrocarbon residue)
DOG: dioxane diol residue (cyclic ether diol residue)
None: do not have the group (Direct Bonding) of binding
Bis-A: dihydroxyphenyl propane residue (dihydroxyphenyl propane residue) with aromatic nucleus
Embodiment 1: the manufacturing of reactive polyurethane compound (A) (urethane operation)
In reactive tank, add the dimethylol propionic acid by record amount in synthetic routine 1 synthetic epoxy carbonate (a) solution, the table 2 of record amount (solids component scaled value) in the table 2 as the compound (b) that has two hydroxyls and an above carboxyl in a part concurrently, as the propylene glycol methyl ether acetate (being called for short PGMAc) of solvent; Make reactive polyurethane compound (A) count 50% with solids component, and stirring and dissolving.In addition, add stannous octoate 1g, be heated to 100 ℃ as catalyzer.Next,, utilize tap funnel to add the vulcabond of putting down in writing in the table 2 of record amount, make its reaction as not containing the compound (c) that has two NCOs in aromatic nucleus and a part.Drip and finish continued reaction 2 hours, utilize infrared absorption spectrum to confirm not belong to the absorption peak of NCO, obtain reactive polyurethane compound (A).
Comparative example 1: manufacturing with reactive polyurethane compound of aromatic nucleus
Use by synthetic routine 2 synthetic epoxy carbonates among the comparative example 1-1, likewise make reactive polyurethane compound with aromatic nucleus with embodiment 1.Use compound among the comparative example 1-2, likewise make reactive polyurethane compound with aromatic nucleus with embodiment 1 with two NCOs with aromatic nucleus.
[table 2]
Figure BDA0000115413940000201
The abbreviation of record in the table 2
DMPA: dimethylol propionic acid
HMDI: hexamethylene diisocyanate
TMDI: trimethyl hexamethylene diisocyanate
IPDI: isophorone diisocyanate
TDI: tolylene diisocyanate (fragrant family)
(a+b)/and c: the value of the mole number of (mole number of the mole number+compound (b) of compound (a))/compound (c)
A/b: the value of the mole number of the mole number/compound (b) of compound (a)
AV: the acid number during reaction terminating (solids component scaled value); MgKOH/g
Embodiment 2: the manufacturing of sour modified-reaction based polyurethane compound (B) (acid increases operation)
Reactive polyurethane compound (A) solution that in reactive tank, adds record amount (solids component scaled value) in the table 3 by embodiment 1 manufacturing; The acid anhydrides that adds record in the table 3; Adding is as the propylene glycol methyl ether acetate (being called for short PGMAc) of solvent; Make sour modified-reaction based polyurethane compound (B) count 50% with solids component, and stirring and dissolving.Solution with 80 ℃ of heating 10 hours, is measured acid number, confirm to finish reaction behind the reaction terminating.
Comparative example 2: manufacturing (acid increases operation) with sour modified-reaction property carbamate compounds of aromatic nucleus
In reactive tank, use the reactive polyurethane compound of making by comparative example 1, likewise make sour modified-reaction property carbamate compounds with aromatic nucleus with embodiment 2.
[table 3]
Figure BDA0000115413940000211
The abbreviation of record in the table 3
THPA: Tetra Hydro Phthalic Anhydride
SA: succinyl oxide
AV (compound (A)): as acid number (solids component scaled value), the mgKOH/g of the compound (A) of raw material
AV (compound (B)): the acid number of the compound of manufacturing (B) (solids component scaled value), mgKOH/g
Embodiment 3: flexible base, board is with white solder resist preparation of compositions and evaluation
With sour modified-reaction property carbamate compounds (B) 54g that obtains among reactive polyurethane compound (A) that obtains among the embodiment 1 or the embodiment 2, as the HX-220 of reactive compounds (C) (trade(brand)name: Nippon Kayaku K. K makes, diacrylate monomer) 3.5g, as Lucirin TPO (BASF manufacturings) 5g of Photoepolymerizationinitiater initiater, as ester ring type diepoxide resin (the セ ロ キ サ イ De 2021P:Daicel chemistry is made) 15g of cure component, as the trimeric cyanamide 1g of thermal curing catalyst, as the methyl ethyl ketone 21g of concentration adjustment solvent with as titanium oxide (the TIPAQUE A-100: the former industry manufacturing of stone) 30g mixing of tinting pigment; After mixing, premix utilize three-roll grinder mixing; Make its homodisperse, obtain the resist resin combination.
Utilize silk screen print method that resulting resist resin combination is applied on the copper lamination polyimide film, make dried thickness be about 20 microns.Utilize electric furnace 80 ℃ of substrates of being coated with of heating 60 minutes, carry out solvent seasoning.
Next, use ultraviolet exposure apparatus according (オ of Co., Ltd. one Network is made institute, model HMW-680GW), see through the optics step-wedge No.2 that the mask that is painted with circuit pattern and the Kodak that is used to estimate sensitivity make, irradiation 500mJ/cm 2Ultraviolet ray., with 1% aqueous sodium carbonate carry out spray development, remove the not resin of irradiating part of ultraviolet ray thereafter.Behind the washing and drying, make printed base plate carry out the reaction that was heating and curing in 60 minutes, obtain cured film with 150 ℃ electric furnaces.
Sensitivity is estimated
Through investigating in the exposure portion that has seen through the optics step-wedge, the concentration part till which " level " of optics step-wedge is residual when developing, and judges sensitivity thus.Progression is more greatly then judged the high more (unit: level) of sensitivity.
The evaluation of development property
For development property, estimate development property (unit: second) with so-called time of developing (Block レ イ Network タ イ system) (this time is when the exposure portion that sees through pattern mask is developed, the time that is developed out fully until pattern form portion).Preferably can develop with the time about 20～50 seconds.Than this time in short-term, it is too fast to develop, the stability of development is easy to generate problem.In addition, during overlong time, the problem of productivity aspect can take place.
Solidified nature is estimated
For the solidified nature evaluation, estimate with the pencil hardness of the cured film after 150 ℃ of heating end.Evaluation method is according to JIS K 5600-5-4:1999.
Thermotolerance is estimated
For the thermotolerance evaluation, flux is handled the back and in 260 ℃ solder bath, was flooded 1 minute, takes out after washing, air-dry, carries out fitness test (JIS K 5600-2-6:1999), and estimates.
Zero: do not have and peel off
△: have slightly and peel off
*: peel off
Tint permanence is estimated
Utilize SUPER UV TESTER (the rugged electric manufacturing of rock) that resulting substrate is carried out 24 hours exposure, it is painted through visual valuation.
Zero: have basically no painted variation
△: variable color slightly
*: yellow variable color is serious, in fact can't use
Folding resistance is estimated
The polyimide printed base plate that will be formed with the cured film of resist on the cured film side being is converted into broken line mountain shape laterally, smooths kink fully with finger.Kink is restored, use the observation by light microscope etchant resist.For bending back sample out of question once, identical position is repeated to amount to five times bending, with the be full of cracks of the etchant resist of observation by light microscope kink.
◎: also do not have be full of cracks after repeating five times
Zero: once the bending back does not have be full of cracks
△: once observe be full of cracks slightly after the bending
*: peel off
[table 4]
Figure BDA0000115413940000241
More than, can find that by evaluation result the reactive polyurethane compound that contains aromatic nucleus is painted strongly with the degree that in fact can't use in the tint permanence evaluation with the sour modified-reaction based polyurethane compound that contains aromatic nucleus as white solder resist.On the other hand, do not contain the reactive polyurethane compound (A) of the application's invention of aromatic nucleus, sour modified-reaction based polyurethane (B) demonstrates excellence in each test performance.
In addition,, can adjust the balance of development property and other characteristics, can know that sour modification is a preferable methods through being modified as compound (B) by compound (A) acid.
Embodiment 4: white solder resist is with the long-term insulativity evaluation of compsn
Utilize silk screen print method to use compsn to be applied to the solder resist of making among the embodiment 3 and have on the BT resin that live width/line-spacing is 100 microns a comb type pattern (BT レ ジ Application) the seal carving brush substrate, making dried thickness is about 20 microns.Utilize the substrate after electric furnace will be coated with to heat 60 minutes down, carry out solvent seasoning at 80 ℃.Next, utilize ultraviolet exposure apparatus according irradiation 500mJ/cm 2Ultraviolet ray after, make printed base plate carry out the reaction that was heating and curing in 60 minutes with 150 ℃ electric furnaces, obtain cured film.Lead-in wire is connected on the resulting substrate, Yi Bian apply 100 volts voltage, Yi Bian under the environment of 85 ℃ of envrionment temperatures, relative humidity 85%, observe the variation of its resistance value.Measure to resistance value and be lower than the time till 10 megaohms.
◎: keep resistance value more than 2000 hours
Zero: the maintenance resistance value is more than 1000 hours and be lower than 2000 hours
△: the maintenance resistance value is more than 500 hours and be lower than 1000 hours
*: be below 10 megaohms less than 500 hours resistance values
[table 5]
Figure BDA0000115413940000251
The abbreviation of record in the table 5
TCl: chloride content (%)
AV: the solids component acid number (mgKOH/g) of compound (A) or compound (B)
R: the diol residue in the general formula (I)
HD: pinakon residue (straight chain shape hydrocarbon residue)
PTMG650: polytetramethylene glycol residue (polyalkylene glycol residue, molecular-weight average 650)
CHDM: cyclohexanedimethanol residue (cyclic hydrocarbon residue)
H-BisA: hydrogenation type dihydroxyphenyl propane residue (cyclic hydrocarbon residue)
TCD: tristane dimethanol residue (cyclic hydrocarbon residue)
None: do not have the group (Direct Bonding) of binding
Can know that by above result in the high embodiment of chloride content (embodiment 4-4), compare with the embodiment (embodiment 4-5) of the low chlorine with equal skeleton, secular insulating property demonstrate the tendency of reduction.In addition, the composition exhibiting that has the ester ring type skeleton in the skeleton goes out to have higher insulativity.
Can know by above-mentioned each test-results, reactive polyurethane compound of the present invention (A), or sour modified-reaction based polyurethane compound (B) have fundamental characteristics as solder resist, and variable color is few, has high flexibility flexibility and secular insulation characterisitic.
Industrial applicibility
Active energy ray-curable resin composition of the present invention as have solidified nature and flexibility concurrently and be difficult to the material of painted characteristic, in addition as the dura mater material, can alkaline development the painted anticorrosive additive material of needs flexibility be excellent.As the purposes that can effectively bring into play this characteristic; For example as the printing-ink of active energy ray curable, chromatic photoresist, particularly be difficult to variable color, be the excellent material of secular color reprodubility, can be particularly suitable for chromatic photoresist and lens material and flexible display screen etc. that LCD uses.

Claims (11)

1. a reactive polyurethane compound (A); It makes the compound (b) that has two hydroxyls and an above carboxyl in epoxy carbonate (a), a part concurrently and does not contain compound (c) reaction that has two NCOs in aromatic nucleus and a part and obtains; Said epoxy carbonate (a) (ii) reacts epoxy resin (i) and compound and obtains; Epoxy resin (i) does not contain and has two epoxy group(ing) in aromatic nucleus and a part, and compound (ii) has polymerisable ethylenic unsaturated group and an above carboxyl more than one concurrently in a part.
2. a sour modified-reaction based polyurethane compound (B), it makes multi-anhydride (d) with the described reactive polyurethane compound of claim 1 (A) reaction and obtain.
3. active energy ray-curable resin composition, it comprises reactive polyurethane compound (A) and/or sour modified-reaction based polyurethane compound (B).
4. active energy ray-curable resin composition as claimed in claim 3, it also comprises except that compound (A), reactive compounds (C) the compound (B).
5. like claim 3 or 4 described active energy ray-curable resin compositions, it comprises tinting pigment.
6. like each described active energy ray-curable resin composition of claim 3～5, it is the light transmission molding material.
7. like each described active energy ray-curable resin composition of claim 3～5, it uses material for painted tunicle forms.
8. like each described active energy ray-curable resin composition of claim 3～5, it uses material for the printing opacity tunicle forms.
9. like each described active energy ray-curable resin composition of claim 3～5, it uses material for resist.
10. the cured article of each described active energy ray-curable resin composition of claim 3～5.
11. article, it has carried out the outer article that cover for the cured article that uses the described active energy ray-curable resin composition of claim 10.
CN2010800243893A 2009-06-04 2010-05-27 Reactive urethane compound, actinic-energy-ray-curable resin composition containing same, and use thereof Pending CN102459392A (en)

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CN109776756A (en) * 2019-01-21 2019-05-21 深圳市道尔顿电子材料有限公司 A kind of dual modified epoxy acrylate and its photoresist

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