CN103224609B - Reactive epoxy carboxylic acids's ester cpds, reactive polycarboxylic compounds, active energy ray-curable resin composition and article - Google Patents

Reactive epoxy carboxylic acids's ester cpds, reactive polycarboxylic compounds, active energy ray-curable resin composition and article Download PDF

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CN103224609B
CN103224609B CN201310088076.XA CN201310088076A CN103224609B CN 103224609 B CN103224609 B CN 103224609B CN 201310088076 A CN201310088076 A CN 201310088076A CN 103224609 B CN103224609 B CN 103224609B
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reactive
carboxylic acids
epoxy
active energy
ester cpds
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CN103224609A (en
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山本和义
栗桥透
堀口尚文
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Nippon Kayaku Co Ltd
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Priority claimed from JP2007214733A external-priority patent/JP5279214B2/en
Priority claimed from JP2007274912A external-priority patent/JP5473208B2/en
Priority claimed from JP2008129547A external-priority patent/JP2009275167A/en
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    • 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
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C08F290/08—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 side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • C08G59/186—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 using pre-adducts of epoxy compounds with curing agents with acids
    • 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
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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

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Abstract

The present invention relates to reactive epoxy carboxylic acids's ester cpds, reactive polycarboxylic compounds, active energy ray-curable resin composition and article.Described resin combination utilizes ultraviolet isoreactivity energy-ray etc. and solidifies, and can obtain tough tunicle or formed material.Described reactive epoxy carboxylic acids's ester cpds makes compound (b) reaction having more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl in the epoxy resin (a) shown in general formula (1) and a part concurrently obtain, in general formula (1), R 1mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; R 2represent carbonatoms be 7 ~ 16 divalent multi-ring alkyl or carbonatoms be 7 ~ 18 sub-aralkyl; M represents the integer of 1 ~ 4; N represents the positive number of 1 ~ 10 in mean value.By the curable resin composition using this reactive compounds, tough cured article can be obtained.This reactive compounds has given play to good pigment-dispersing.

Description

Reactive epoxy carboxylic acids's ester cpds, reactive polycarboxylic compounds, active energy ray-curable resin composition and article
The application is divisional application, the China national application number of its original application is 200880103586.7, the applying date is on August 8th, 2008, and denomination of invention is " reactive carbonate, the active energy ray-curable resin composition using this reactive carbonate and uses thereof ".
Technical field
The present invention relates to reactive epoxy carboxylic acids's ester cpds (A) and the reactive polycarboxylic compounds (B) as its sour modifier, this reactive epoxy carboxylic acids's ester cpds (A) makes to have concurrently in the representative compound (b) having more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl in the molecule concurrently such as vinylformic acid and molecule the phenol-type epoxy resin (a) comprising ad hoc structure in the compound (c) of more than one hydroxyl and more than one carboxyl and molecule and reacts and obtain.These reactive epoxy carboxylic acids's ester cpds (A) and reactive polycarboxylic compounds (B) have good affinity with pigment, and can obtain tough cured article by the resin combination comprising these compounds.
Background technology
Rise to object with the miniaturization of portable machines and communication speed, printed circuit board (PCB) is just being required high precision, densification.Accompany therewith, the requirement of the solder resist of coating this circuit itself is also improved day by day, compared with existing requirement, also require that it is while keeping thermotolerance, thermostability, there is substrate adaptation, high-insulativity, the performance of electroless plating gold can be tolerated.People's demand has the tunicle formation material of more tough solidification physical property.
In order to adapt to, to the high performance requirement of solder resist, to have developed the epoxy resin comprising ad hoc structure in the molecule, comprise the resin of these epoxy resin or the cured article of its sour modified epoxy carboxylicesters resin is well-known.
With such as phenol aralkyl-type epoxy resin (such as, the NC-3000 series that Japan's chemical drug manufactures, NC-2000 are serial etc.) be recorded in patent documentation 1 or patent documentation 2 for the sour modified epoxy acrylic ester of basic framework, and it is generally known as the material demonstrating high-strong toughness after solidification.Further, also the purposes as the solder resist using this material is studied.
Patent documentation 3 describes to have the sour modified epoxy acrylic ester compound and cured article thereof that the epoxy resin of multi-ring alkyl is basic framework, and describes it and have higher obdurability after hardening.Further, the solder resist using this material is also described.But though this solder resist has higher reliability, insufficient have the performance that can meet higher reliability, higher reliability is with required by the electronization of conveying machine in recent years etc.
In addition, as the purposes of the sour modified epoxy acrylic ester generated by these epoxy resin, also attempt the black matrix layer resist (Block ラ ッ Network マ ト リ Network ス レ ジ ス ト) being applied to the uses such as display panels by tinting pigments such as disperse black carbons.
The tinting pigment such as disperse black carbon in the above-mentioned sour modified epoxy acrylic ester being basic framework with phenol aralkyl-type epoxy resin and obtain black matrix layer resist, the application examples towards described black matrix layer resist is recorded in patent documentation 4, patent documentation 5.
In addition, the tinting pigment such as disperse black carbon in the sour modified epoxy acrylic ester compound being basic framework with the epoxy resin with multi-ring alkyl and be applied to black matrix layer resist, this trial is also well-known.(patent documentation 6)
But, in the black matrix layer resist purposes that display panels etc. uses, when by compounding for the tinting pigments such as carbon black one-tenth high density, because pigment and resin is affine and disperse well, even if thus pigment exists with high density, also demonstrate good developability, the development without pigment residue becomes possibility.In this case, the developability under more high pigment levels is needed, that is, higher pigment-dispersing.Though existing sour modified epoxy acrylic ester class demonstrates better pigment-dispersing, there is dispersible pigment dispersion pseudo agglutination, the bad such difficult problem of stability.
On the other hand, the carbonate that the carboxylic acid cpd making vinylformic acid and have a hydroxyl react with general epoxy resin simultaneously and obtains is low but the material with the developability of excellence is known as acid number, and patent documentation 7 also describes this compound and has resistance to ink adaptive.
Patent documentation 1: Japanese Unexamined Patent Publication 11-140144 publication
Patent documentation 2: Japanese Unexamined Patent Publication 5-194708 publication
Patent documentation 3: Japanese Unexamined Patent Publication 5-214048 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-55814 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2003-183354 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2004-295084 publication
Patent documentation 7: Japanese Unexamined Patent Publication 6-324490 publication
Summary of the invention
Though use the above-mentioned curable resin composition comprising the epoxy resin of ad hoc structure in the molecule can obtain more tough cured article, but as the material of the purposes towards the high reliability of requirement of carrying machine such, need more tough solidification physical property, such as, needs can also tolerate the bending of substrate, etc.
In addition, in the purposes of the anticorrosive additive material as colour system, when making its composition, need a kind of sour modified epoxy acrylic ester, this sour modified epoxy acrylic ester is better to the dispersion of tinting pigment (particularly carbon black etc.), even if thus pigment concentration is higher also has good developing property.For this situation, need there is higher molecular weight and there is the material of right development.And the resin combination being dispersed with tinting pigment needing not observe cohesion in dispersible pigment dispersion and demonstrate long-term storing stability.
In order to solve above-mentioned problem, the present inventor finds, the reactive epoxy carboxylic acids's ester cpds obtained as follows and reactive polycarboxylic compounds have resin characteristics excellent especially and the resin characteristics as its cured article, this reactive epoxy carboxylic acids's ester cpds is the compound (b) making to have concurrently in molecule more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl, the compound (c) having more than one hydroxyl and more than one carboxyl in a part concurrently reacts with the epoxy resin comprising ad hoc structure in the molecule and obtains, this reactive polycarboxylic compounds makes multi-anhydride (d) and this reactive epoxy carboxylic acids's ester cpds react and obtain again.
Find in addition, this resin combination particularly has good affinity with tinting pigment, and finds, even if it can become the anticorrosive additive material that pigment concentration height also has good developability.
Namely, the present invention relates to a kind of reactive epoxy carboxylic acids's ester cpds (A), it makes to have concurrently in the epoxy resin (a) shown in following general formula (1), a part compound (c) reaction having more than one hydroxyl and more than one carboxyl in the compound (b) of more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl and a part concurrently and obtains.
[changing 1]
(in formula (1), R 1mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; R 2represent carbonatoms be 7 ~ 16 divalent multi-ring alkyl or carbonatoms be 7 ~ 18 sub-aralkyl; M represents the integer of 1 ~ 4; And n represents the positive number of 1 ~ 10 in mean value.)
The invention still further relates to a kind of reactive epoxy carboxylic acids's ester cpds (A), wherein, epoxy resin (a) is as shown in general formula (2).
[changing 2]
(in formula (2), R 3mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; O represents the integer of 1 ~ 4; And p represents the positive number of 1 ~ 10 in mean value.)
The invention still further relates to a kind of reactive epoxy carboxylic acids's ester cpds (A), wherein, epoxy resin (a) is as shown in general formula (3).
[changing 3]
(in formula (3), R 4mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; Q represents the integer of 1 ~ 4; And r represents the positive number of 1 ~ 10 in mean value.)
The invention still further relates to a kind of reactive epoxy carboxylic acids's ester cpds (A), wherein, epoxy resin (a) is as shown in general formula (4).
[changing 4]
(in formula (4), R 5mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; S represents the integer of 1 ~ 4; And t represents the positive number of 1 ~ 10 in mean value.)
The invention still further relates to a kind of reactive polycarboxylic compounds (B), it makes multi-anhydride (d) and reactive carbonate (A) obtained above react and obtain.
The invention still further relates to a kind of active energy ray-curable resin composition, it is characterized in that, described composition comprises above-mentioned reactive carbonate (A) and/or reactive polycarboxylic compounds (B).
The present invention relates to a kind of active energy ray-curable resin composition, it is characterized in that, described composition also comprises the reactive compounds (C) except (A), (B).
The present invention relates to a kind of active energy ray-curable resin composition, it is characterized in that, described composition is also containing tinting pigment.
The present invention relates to a kind of active energy ray-curable resin composition, it is characterized in that, described composition also comprises Photoepolymerizationinitiater initiater.
The invention still further relates to above-mentioned active energy ray-curable resin composition, wherein, described composition is molding material.
The invention still further relates to above-mentioned active energy ray-curable resin composition, wherein, described composition is tunicle formation material.
The invention still further relates to above-mentioned active energy ray-curable resin composition, wherein, described composition is anticorrosive additive material composition.
The invention still further relates to a kind of cured article, it is the cured article of above-mentioned active energy ray-curable resin composition.
The invention still further relates to a kind of article, it is the article using above-mentioned active energy ray-curable resin composition to cover surface.
The active energy ray-curable resin composition comprising the epoxy resin in the molecule with ad hoc structure of the present invention not only provides tough cured article, even and if be in only make solvent seasoning state under also there is excellent resin characteristics.The cured article obtained by active energy ray-curable resin composition of the present invention compatibly can use material for requiring the tunicle of thermotolerance and mechanical obdurability to be formed.As particularly preferred purposes, Solder-Resist Inks for Printed Circuit Board, multilayer printed circuit board interlayer dielectic, flexible printed circuit board solder resist, resist plating, photosensitivity optical waveguides etc. can be enumerated, can be used in the purposes requiring extra high characteristic.
In addition, the tinting pigments such as the active energy ray-curable resin composition obtained and carbon black have high-affinity, even if therefore when pigment concentration is higher, also demonstrate good pigment-dispersing, thus can play high developability.Further, can the colo(u)rant dispersion state of its tinting pigment dispersion liquid of long term maintenance, the resin combination of the storage stability can guaranteeing high dispersion state can be provided.Thus, as particularly preferred purposes, can compatibly for the anticorrosive additive material of chromatic photoresist, colour filter, particularly black matrix layer material etc.
Embodiment
Reactive epoxy carboxylic acids's ester cpds (A) of the present invention is used in the reactive compound (b) of imparting and compound (c) reacts with phenol-type epoxy resin (a) and obtains, wherein, described phenol-type epoxy resin (a) is the phenol-type epoxy resin as shown in the formula the feature skeleton shown in (1) being connected with phenolic epoxy group(ing) with the alkyl of ad hoc structure, described compound (b) is the compound having more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl in molecule concurrently, described compound (c) is the compound having more than one hydroxyl and more than one carboxyl in a part concurrently.That is, in molecular chain, import ethylenic unsaturated group and hydroxyl by epoxy carboxylic acids's esterification simultaneously, make feature of the present invention be played thus.
[changing 5]
The feature of the epoxy resin (a) represented with general formula (1) used in the present invention is, it is that this repetition skeleton is phenolic epoxy group(ing) and R by the phenol-type epoxy resin repeating skeleton and form 2represent, carbonatoms be 7 ~ 16 divalent multi-ring alkyl or carbonatoms be the repetition skeleton of the alkyl as sub-aralkyl of 7 ~ 18.
In above-mentioned formula, R 1mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4.Fluorine atom, chlorine atom, bromine atoms, atomic iodine is represented at this halogen atom.And the alkyl that carbonatoms is 1 ~ 4 represents saturated hydrocarbyl and the unsaturated alkyls such as methyl, ethyl, vinyl, n-propyl, sec.-propyl, propenyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, butenyl.
R 2represent carbonatoms be 7 ~ 16 divalent multi-ring alkyl or carbonatoms be 7 ~ 18 sub-aralkyl.As the divalent multi-ring alkyl that carbonatoms is 7 ~ 16, dicyclo [2,2,1] heptane two base, dicyclo [2 can be enumerated, 2,2] octane two base, octahydro pentalene two base, naphthane two base, tetrahydro-dicyclopentadiene two base, tetrahydrochysene dicyclo hexadiene two base.Among these, preferably use tetrahydro-dicyclopentadiene two base.
And, as the sub-aralkyl that carbonatoms is 7 ~ 18, phenylene dimethylene, phenylene acetylene, biphenylene dimethylene, biphenylene acetylene, naphthylidene dimethylene, anthracene dimethylene, luxuriant and rich with fragrance dimethylene, pyrene dimethylene etc. can be enumerated.Among these, preferably use phenylene dimethylene, biphenylene dimethylene.
In addition, in general formula (1), m represents the integer of 1 ~ 4, represents the functional group number imported.N does not represent the positive number of 1 ~ 10 with mean value score, is preferably 1 ~ 6.When the value of n be less than 10, be preferably less than 6 time, epoxy resin (a) is in suitable range of viscosities.It should be noted that, the mean value of n refers to averaged repeating numbers, can be calculated by the measured value utilizing gel permeation chromatography (GPC) to obtain.
As the epoxy resin (a) used in the present invention, the epoxy resin with feature biphenyl backbone shown in following general formula (2) preferably can be used.
[changing 6]
In above-mentioned formula, R 3mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4.Halogen atom represents fluorine atom, chlorine atom, bromine atoms, atomic iodine.In addition, o represents the integer of 1 ~ 4, and p does not represent the positive number of 1 ~ 10 with mean value score, is preferably 1 ~ 6.When the value of p be less than 10, be preferably less than 6 time, epoxy resin (a) is in suitable range of viscosities.
Among epoxy resin (a) shown in general formula (2), R 3be all that the epoxy resin (a) of hydrogen atom can obtain at low cost, thus preferably.Generally can obtain NC-3000 series commercially available product by Japanese chemical drug.About NC-3000 series, in above-mentioned formula, R 3be all hydrogen atom, and p does not represent the positive number of 1 ~ 10 with mean value score.In the present invention, the product of suitable grade can be selected aptly in series.
Further, as the epoxy resin (a) used in the present invention, the phenol aralkyl-type epoxy resin shown in general formula (3) can preferably be used.
[changing 7]
In above-mentioned formula, R 4mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4.In addition, q, for replacing number, represents the integer of 1 ~ 4; And r represents the positive number of 1 ~ 10 in mean value.
Among epoxy resin shown in general formula (3), preferred R 4be all the epoxy resin of hydrogen atom or methyl.Epoxy resin shown in general formula (3) generally can be obtained as NC-2000 series by Japanese chemical drug.About NC-2000 series, in above-mentioned formula, R 4be all hydrogen atom, and r count the positive number of 1 ~ 10 with mean value.In the present invention, the product of suitable grade can be selected aptly in series.
Further, as the epoxy resin (a) used in the present invention, the epoxy resin with multi-ring alkyl shown in general formula (4) can preferably be used.
[changing 8]
In above-mentioned formula, R 5mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; S, for replacing number, represents the integer of 1 ~ 4; And t represents the positive number of 1 ~ 10 in mean value.
Wherein, R 5be all compound or the R of hydrogen atom 5for the compound of methyl can obtain at low cost, thus preferably.R 5all be hydrogen atom and t represent using mean value the positive number of 1 ~ 10 compound can from Japanese chemical drug (strain) as XD-1000 series obtain.In the present invention, the compound of suitable grade can be selected aptly in series.
The compound (b) having more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl in a part used in the present invention concurrently makes it react to give to the reactivity of active energy beam.Monocarboxylic acid compound, polycarboxylic compounds can be enumerated in these compounds.
As the monocarboxylic acid compound comprising a carboxyl in a part, can enumerate, such as (methyl) acrylic acid or the like, butenoic acid, alpha-cyano styracin, styracin or saturated or unsaturated dibasic acid and the single glycidyl compound containing unsaturated group reaction product.In above-claimed cpd, as acrylic acid or the like, can enumerate such as (methyl) vinylformic acid, β-styrene acrylic, β-furfuryl acrylic acid, (methyl) acrylic acid dimer, as having the half ester class of the reaction with same mole product of (methyl) acrylate derivative of 1 hydroxyl, the half ester class etc. as the reaction with same mole product of saturated or unsaturated dibasic acid and (methyl) vinylformic acid list glycidyl ester derivatives class in saturated or unsaturated dicarboxylic acid anhydride and 1 molecule.
In addition, for the polycarboxylic compounds in a part with more than 2 carboxyls, can enumerate, as the half ester class of the reaction with same mole product of (methyl) acrylate derivative and dibasic acid anhydride in a part with more than 2 hydroxyls, as saturated or unsaturated dibasic acid and the half ester class etc. of reaction with same mole product of (methyl) glycidyl acrylate derivatives class with more than 2 epoxy group(ing).
Among those, most preferably, from the viewpoint of making the sensitivity after active energy ray-curable resin composition, resultant of reaction or the styracin of (methyl) vinylformic acid, (methyl) vinylformic acid and 6-caprolactone can be enumerated.
As the compound (b) having more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl in a part concurrently, not there is in preferred compound the compound of hydroxyl.
The compound (c) having more than one hydroxyl and more than one carboxyl in a part used in the present invention concurrently makes it react to import hydroxyl in carbonate.These compounds comprise in a part the compound having more than one hydroxyl and more than two carboxyls in the compound having a hydroxyl and a carboxyl concurrently, the compound having two or more hydroxyl and a carboxyl in a part concurrently, a part concurrently.
As the compound having a hydroxyl and a carboxyl in a part concurrently, such as hydroxy-propionic acid, hydroxybutyric acid, oxystearic acid etc. can be enumerated.
Further, as the compound having two or more hydroxyl and a carboxyl in a part concurrently, dihydroxymethyl acetic acid, dimethylol propionic acid, dimethylolpropionic acid etc. can be enumerated.
As the compound having more than one hydroxyl and more than two carboxyls in a part concurrently, hydroxyl phthalic etc. can be enumerated.
Among these, consider effect of the present invention, in preferred a part, comprise the compound of more than two hydroxyls.In addition, consider the stability that carboxylic esterification reacts, the carboxyl in preferred a part is the compound of.Most preferably there is in a part the compound of two hydroxyls and a carboxyl.Consider raw-material acquisition, dimethylol propionic acid and dimethylolpropionic acid are specially suitable.
As the compound (c) having more than one hydroxyl and more than one carboxyl in a part concurrently, preferably not there is in compound the compound (c) of the ethylenic unsaturated group that can be polymerized.
Among these, if consider above-mentioned epoxy resin (a) and the stability of two kinds of carboxylic acid cpds (b) with the reaction of (c), then preferably (b) and (c) is monocarboxylic acid, even if when share monocarboxylic acid and polycarboxylic acid, also the preferred value represented with the total molar weight of the total of monocarboxylic acid molar weight/polycarboxylic acid is for more than 15.
Epoxy resin (a) in this reaction should change according to purposes is suitable with the ingredient proportion of carboxylic acid cpd (b) with the total of the carboxylic acid of (c).That is, when by whole epoxy group(ing) carboxylic esterifications, because unreacted epoxy group(ing) is without remaining, the storage stability thus as reactive carbonate is higher.In this case, the reactivity only utilizing the double bond imported to provide.
On the other hand, deliberately make unreacted remaining epoxy group(ing) remaining by reducing the charging capacity of carboxylic acid cpd (b) and (c), also can the reaction that causes of the reactivity that provides of the unsaturated link(age) that imports of complicated utilization and remaining epoxy group(ing), such as, by polyreaction or the heat polymerization of the catalysis of light cationic catalyst.But, in this case, should be noted that the preservation of reactive carbonate and the research of manufacturing condition.
When manufacturing reactive epoxy carboxylic acids's ester cpds (A) of not remaining reactive epoxy group(ing), preferably relative to 1 equivalent epoxy group(ing) of above-mentioned epoxy resin (a), carboxylic acid cpd (b) adds up to 90 ~ 120 equivalent % with (c's).As long as within the scope of this, just can manufacture under more stable condition.When the charging capacity of carboxylic acid cpd is more than above-mentioned scope, the carboxylic acid cpd (b) of the remaining surplus of meeting, therefore not preferred.
Further, when deliberately making epoxy group(ing) remain, preferably relative to the above-mentioned epoxy resin (a) of 1 equivalent, carboxylic acid cpd (b) adds up to 20 ~ 90 equivalent % with (c's).When outside this scope, the decreased effectiveness of composite curing.Certainly, in this case, the ageing stability of the gelation in reaction, carbonate (A) is needed to give one's full attention to.
About the compound (b) having more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl concurrently and the usage ratio of compound (c) having more than one hydroxyl and more than one carboxyl concurrently, with the molar ratio computing of carboxyl, (b): (c) is preferably 9:1 ~ 1:9, is more preferably the scope of 4:6 ~ 8:2.As long as within the scope of this, sensitivity decrease when (b) just can be prevented very few, and the effect of (c) when (c) can be prevented very few reduces.
The reaction of this carboxylic esterification also can be reacted in solvent-free mode, or also can react with after solvent cut.As can solvent as used herein, as long as to the solvent of carboxylic esterification reaction in inertia, be just not particularly limited.
Preferred solvent load should carry out suitable adjustment according to the viscosity of obtained resin and purposes, but uses solvent, makes solids component preferably reach 90 ~ 30 quality %, more preferably reach 80 ~ 50 quality %.
If exemplify the concrete example that can be used as above-mentioned solvent, then can enumerate, the fragrant family hydrocarbon solvents such as such as toluene, dimethylbenzene, ethylbenzene, tetramethyl-benzene; The fatty family hydrocarbon solvent such as hexane, octane, decane and sherwood oil, white gasoline, solvent naphtha etc. as their mixture.
Further, as ester series solvent, can enumerate, the alkyl acetate classes such as ethyl acetate, propyl acetate, butylacetate; The cyclic ester classes such as gamma-butyrolactone; Single alkylene glycol monoalky lether monoacetate class or many alkylene glycols monoalky lether monoacetate classes such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Triethylene glycol ethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol methyl ether acetate, butyleneglycol methyl ether acetate; The polycarboxylic acid alkyl esters etc. such as dialkyl glutarate, dialkyl succinate, hexanedioic acid dialkyl ester.
Further, as ether series solvent, can enumerate, the alkyl ethers such as diethyl ether, ethyl-butyl ether; The glycol ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl ether, dipropylene glycol diethyl ether, TRIGLYME, triethylene glycol diethyl ether; The ring-type ethers etc. such as tetrahydrofuran (THF).
Further, as ketone series solvent, acetone, methyl ethyl ketone, pimelinketone, isophorone etc. can be enumerated.
In addition, reaction can also be carried out separately or in mixed organic solvents at the reactive compounds (C) except (A) described later, (B) etc.In this case, when using with the form of curing composition, owing to can directly be used in the form of compositions, be therefore preferred.
In order to promote that reaction preferably uses catalyzer during reaction, relative to reactant, namely, relative to the total amount comprising above-mentioned epoxy compounds (a), compound (b), compound (c) and the reactant of the solvent that uses etc. in some cases, the consumption of this catalyzer is 0.1 ~ 10 quality %.Temperature of reaction is now 60 ~ 150 DEG C, and the reaction times is preferably 5 ~ 60 hours.As the concrete example of spendable catalyzer, can enumerate, the general basic catalyst etc. that such as triethylamine, benzyldimethylamine, triethylamine hydrochloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, sad chromium, zirconium caprylate etc. are known.
Further, as hot stopper, hydroquinone monomethyl ether, 2-toluhydroquinone, quinhydrones, phenylbenzene bitter taste hydrazides, diphenylamine, BHT etc. are preferably used.
Suitably sample to this reaction, reach below 5mgKOH/g with sample acid number, the moment preferably reaching below 2mgKOH/g is the terminal of this reaction simultaneously.
As the preferred molecular weight range of the reactive carbonate (A) obtained like this, the scope of the polystyrene conversion weight-average molecular weight obtained by GPC is 1,000 ~ 30,000, be more preferably 1,500 ~ 20,000.
When being less than this molecular weight, the obdurability of cured article cannot be given full play to; And when being greater than this molecular weight, viscosity raises, and is difficult to coating etc.
Next, the of the present invention reactive polycarboxylic compounds (B) obtained by sour addition operation is described.The object of carrying out sour addition operation is, is imported by carboxyl in the reactive carbonate (A) obtained in front operation as required, to obtain reactive polycarboxylic compounds (B).The importing of carboxyl is for following object: such as needing to be formed in the purposes of Resist patterns etc., give the solubility to buck to active energy beam non-irradiated portion, and gives the adaptation with metal, inorganics etc., etc.
Specifically, make multi-anhydride (d) and the hydroxyl generation addition reaction generated by epoxy carboxylic acids's esterification, by ester bond, carboxyl is imported thus.
As the concrete example of multi-anhydride (d), such as, all multi-anhydrides can be used, as long as it is the compound in a part with acid anhydride structure, but succinyl oxide, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic acid 1,2-anhydride or maleic anhydride that particularly preferably alkali aqueous solution developability, thermotolerance, hydrolytic resistance etc. are excellent.
The reaction of addition multi-anhydride (d) can by adding multi-anhydride (d) to carry out in above-mentioned carboxylic esterification reaction solution.Addition should change according to purposes is suitable.
But, when the resist that polycarboxylic compounds of the present invention (B) will be used as alkali-developable, the charging capacity of preferred multi-anhydride (d) is that the solids component acid number (based on JISK5601-2-1:1999) of the reactive polycarboxylic compounds (B) making finally to obtain reaches 30 ~ 120mgKOH/g, more preferably reaches the value that 40 ~ 105mgKOH/g calculates.When solids component acid number is now this scope, the alkali aqueous solution developability of active energy ray-curable resin composition of the present invention demonstrates good developability.That is, patternability is good and also wider to the span of control crossing development, and also can not remain superfluous acid anhydrides.
In order to promote that reaction preferably uses catalyzer during reaction, relative to reactant, namely, relative to the total amount of reactant comprising the carbonate (A) that obtained by above-mentioned epoxy compounds (a), carboxylic acid cpd (b) and (c) and multi-anhydride (d), the solvent that uses in some cases etc., the consumption of this catalyzer is 0.1 ~ 10 quality %.Temperature of reaction is now 60 ~ 150 DEG C, and the reaction times is preferably 5 ~ 60 hours.As the concrete example of spendable catalyzer, such as triethylamine, benzyldimethylamine, triethylamine hydrochloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, sad chromium, zirconium caprylate etc. can be enumerated.
This sour addition reaction also can be reacted in solvent-free mode, or also can react with after solvent cut.As can solvent as used herein, as long as be the solvent of inertia to sour addition reaction, be just not particularly limited.Specifically, can use react with the carboxylic esterification in front operation in illustrative solvent phase with solvent.When using solvent to carry out manufacturing in the carboxylic esterification reaction of front operation, react in inertia for condition with solvent to described two, also can not except desolventizing directly for the sour addition reaction as subsequent processing.
Preferred solvent load should carry out suitable adjustment according to the viscosity of obtained resin and purposes, but uses solvent, makes solids component preferably reach 90 ~ 30 quality %, more preferably reach 80 ~ 50 quality %.
In addition, this sour addition reaction can also be carried out separately or in mixed organic solvents at reactive compounds described later (C) etc.In this case, when using with the form of curing composition, owing to can directly be used in the form of compositions, therefore preferably.
Further, the preferred hot stopper using the illustration in reacting with above-mentioned carboxylic esterification same such as hot stopper.
This reaction is sampled aptly, simultaneously with the acid number of reaction product reach set acid number positive and negative 10% the point of scope as the terminal of this reaction.
Active energy ray-curable resin composition of the present invention comprises epoxy carboxylic acids's ester cpds (A) and/or polycarboxylic compounds (B).Epoxy carboxylic acids's ester cpds (A) and/or polycarboxylic compounds (B) can use flexibly according to its purposes is suitable.Such as, in the purposes of solder resist and so on, when not developing and utilize print process to form pattern or when utilizing solvent etc. to make the diffluence of unreacted position (so-called solvent developable), use epoxy carboxylic acids's ester cpds (A); When utilizing buck to make it develop, use polycarboxylic compounds (B).Generally considering from easily producing fine pattern such aspect liquid alkali developing type, in this purposes, using polycarboxylic compounds (B) more.Certainly, epoxy carboxylic acids's ester cpds (A) and polycarboxylic compounds (B) is share also without any problem.
Active energy ray-curable resin composition of the present invention also can comprise the reactive compounds (C) except epoxy carboxylic acids's ester cpds (A) and polycarboxylic compounds (B) further.
As the concrete example of reactive compounds (C) spendable in the present invention, the epoxy compounds class of the esters of acrylic acid of free radical reaction type, cationoid reaction type and alloytype thereof can be enumerated, be not only applicable to free radical reaction type but also be applicable to the vinyl compound class etc. of cationoid reaction type, so-called reactive oligomers class.
As spendable esters of acrylic acid, simple function (methyl) esters of acrylic acid, multifunctional (methyl) acrylate can be enumerated, also have epoxy acrylate, polyester acrylate, urethane acrylate etc.
As simple function (methyl) esters of acrylic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) lauryl acrylate, polyoxyethylene glycol (methyl) acrylate, polyoxyethylene glycol (methyl) acrylate monomethyl ether, (methyl) phenylethyl ethyl ester, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester etc. can be enumerated.
As multifunctional (methyl) esters of acrylic acid, butyleneglycol two (methyl) acrylate can be enumerated, hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, nonanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, three (methyl) acryloyl-oxyethyl isocyanuric acid ester, polypropylene glycol two (methyl) acrylate, hexanodioic acid epoxy two (methyl) acrylate, Ethoxylated bisphenol two (methyl) acrylate, ethoxylated hydrogenated bis-phenol (methyl) acrylate, bis-phenol two (methyl) acrylate, two (methyl) acrylate of the 6-caprolactone affixture of hydroxypivalic acid neopentyl glycol, poly-(methyl) acrylate of the reaction product of Dipentaerythritol and 6-caprolactone, Dipentaerythritol gathers (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, triethylol propane three (methyl) acrylate and ethylene oxide adduct thereof, tetramethylolmethane three (methyl) acrylate and ethylene oxide adduct thereof, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate and ethylene oxide adduct etc. thereof.
As spendable vinyl compound class, vinyl ethers, styrenic, other vinyl compounds can be enumerated.As vinyl ethers, ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether etc. can be enumerated.As styrenic, vinylbenzene, vinyl toluene, ethyl styrene etc. can be enumerated.As other vinyl compounds, triallyl isocyanurate, front three can be enumerated for allyl iso cyanurate etc.
In addition, as so-called reactive oligomers class, can enumerate the urethane acrylate having functional group and the amino-formate bond that can react under active energy beam effect in same a part concurrently, the polyester acrylate having functional group and the ester bond that can react under active energy beam effect equally in same a part concurrently, derived from other epoxy resin and have concurrently in same a part can react under active energy beam effect the epoxy acrylate of functional group, the combination of these acrylate is by the reactive oligomers etc. of compound use.
In addition, as cationoid reaction type monomer, as long as generally have the compound of epoxy group(ing), be just not particularly limited.Can enumerate such as, (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 (" サ イ ラ キ ュ ア UVR-6110 " that ユ ニ オ ン カ ー バ イ De society manufactures etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexane carboxylate, vinyl cyclohexene diepoxide (" ELR-4206 " that ユ ニ オ ン カ ー バ イ De society manufactures etc.), limonene dioxide (" セ ロ キ サ イ De 3000 " that Daicel chemical industry society manufactures 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 (3,4-epoxycyclohexyl) adipic acid ester (" サ イ ラ キ ュ ア UVR-6128 " that ユ ニ オ ン カ ー バ イ De society manufactures etc.), two (3,4-epoxycyclohexyl-methyl) adipic acid ester, two (3,4-epoxycyclohexyl) ether, two (3,4-epoxycyclohexyl-methyl) ether, two (3,4-epoxycyclohexyl) di-ethyl siloxane etc.
Among these, as reactive compounds (C), the most preferably esters of acrylic acid of radical-curable.When cationic, because carboxylic acid and epoxy group(ing) can react, thus need to make two liquid mixed types.
By carbonate of the present invention (A) and/or reactive polycarboxylic compounds (B) and the mixing of the reactive compounds (C) except (A), (B) added if desired, active energy ray-curable resin composition of the present invention can be obtained.Now, other compositions can also be added aptly according to purposes.
For active energy ray-curable resin composition of the present invention, in the composition containing 97 ~ 5 quality %, the carbonate (A) being preferably 87 ~ 10 quality % and/or reactive polycarboxylic compounds (B), the reactive compounds (C) except (A), (B) containing 3 ~ 95 quality %, more preferably 3 ~ 90 quality %.As required, other compositions that the upper limit be about 70 quality % can also be contained.
In the present invention, spendable tinting pigment is in order to use for coloured material with active energy ray-curable resin composition of the present invention.The balance of the hydroxyl of the carbonate (A) used in the present invention, reactive polycarboxylic compounds (B) is in specified range, therefore can know by inference, can play the affinity to pigment excellent especially, that is, dispersed.This mechanism is still not clear, however due to good dispersion carry out, therefore its result can improve pigment concentration; And due in the composition needing development, dispersion is in more suitably state, therefore can play good pattern Formation and characteristics; And because the development residue in developer dissolves portion is also less, therefore active energy ray-curable resin composition of the present invention is suitable.
As tinting pigment, the pigment dyestuffs such as phthalocyanine system, azo system, quinacridone can be enumerated; The mineral dye such as carbon black etc., titanium dioxide.Among these, the high and most preferably carbon black of carbon black dispersion.
In active energy ray-curable resin composition of the present invention, in order to carry out effectively and solidify fully, Photoepolymerizationinitiater initiater can be added.As Photoepolymerizationinitiater initiater, free radical type Photoepolymerizationinitiater initiater, positively charged ion system Photoepolymerizationinitiater initiater, other polymerization starters can be enumerated.
As free radical type Photoepolymerizationinitiater initiater, the benzoin ketones such as such as bitter almond oil camphor, bitter almond oil camphor methyl ether, bitter almond oil camphor ether, bitter almond oil camphor propyl ether, bitter almond oil camphor ethyl isobutyl ether can be enumerated; Methyl phenyl ketone, 2,2-diethoxy-2-phenyl acetophenone, 2, the acetophenones such as 2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone; The Anthraquinones such as 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; The thioxanthene ketones such as 2,4-diethyl thioxanthone, ITX, CTX; The ketal classes such as methyl phenyl ketone dimethyl ketal, benzyl dimethyl ketal; Benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4, the benzophenones such as 4 '-bis-methylamino benzophenone; The known general free radical type photoreaction initiator such as phosphine oxide class such as 2,4,6-trimethylbenzoyldiphenyl oxide compound, two (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
And, as positively charged ion system Photoepolymerizationinitiater initiater, lewis acidic diazonium salt, lewis acidic salt compounded of iodine, lewis acidic sulfonium salt, Lewis acid phosphonium salt, other halogenide, triazine series initiators, borate-based initiator and other Photoacid generator etc. can be enumerated.
As lewis acidic diazonium salt, p-methoxyphenyl diazonium fluoride phosphoric acid salt, N, N-diethylamino phenyldiazonium hexafluorophosphate (the サ Application エ イ De SI-60L/SI-80L/SI-100L etc. that three new chemical industry societies manufacture) etc. can be enumerated; As lewis acidic salt compounded of iodine, diphenyl iodine hexafluorophosphate, phenylbenzene iodine hexafluoro antimonate etc. can be enumerated; As lewis acidic sulfonium salt, triphenylsulfonium hexafluorophosphate (CyracureUVI-6990 etc. that UnionCarbide society manufactures), triphenylsulfonium hexafluoro antimonate (CyracureUVI-6974 etc. that UnionCarbide society manufactures) etc. can be enumerated; As Lewis acid phosphonium salt, triphenyl phosphorus hexafluoro antimonate etc. can be enumerated.
As other halogenide, can 2 be enumerated, 2,2-tri-chloro-[1-4 '-(dimethyl ethyl) phenyl] ethyl ketone (TrigonalPI etc. that AKZO society manufactures), 2, the chloro-1-4-of 2-bis-(Phenoxyphenyl) ethyl ketone (Sandray1000 etc. that Sandoz society manufactures), α, α, α-trisbromomethyl phenyl sulfone (BMPS etc. that iron chemistry society processed manufactures) etc.As triazine series initiators, can 2 be enumerated, 4, 6-tri-(trichloromethyl)-s-triazine, 2, 4-trichloromethyl-(4 '-p-methoxy-phenyl)-6-triazine (TriazineA etc. that Panchim society manufactures), 2, 4-trichloromethyl-(4 '-methoxyl-styrene)-6-triazine (TriazinePMS etc. that Panchim society manufactures), 2, 4-trichloromethyl-(piperonyl)-6-triazine (TriazinePP etc. that Panchim society manufactures), 2, 4-trichloromethyl-(4 '-methoxyl group naphthyl)-6-triazine (TriazineB etc. that Panchim society manufactures), 2-[2 '-(5 ' '-methyl furan base) ethylidene]-4, two (the trichloromethyl)-s-triazine of 6-(three and ケ ミ カ Le society manufacture), 2-(2 '-furylethylidene)-4, two (the trichloromethyl)-s-triazine of 6-(three and ケ ミ カ Le society manufacture) etc.
As borate-based initiator, NK-3876 and NK-3881 etc. that Japanese photopigment manufactures can be enumerated, as other Photoacid generators etc., 9-phenylacridine can be enumerated, 2, 2 '-bis-(Chloro-O-Phenyl)-4, 4 ', 5, 5 '-tetraphenyl-1, 2-bisglyoxaline (dark fund changes into the bisglyoxaline etc. that society manufactures), 2, two (2-aminopropane) dihydrochloride of 2-azo (with the V50 etc. that Guang Chun medicine society manufactures), 2, two [2-(tetrahydroglyoxaline-2-base) propane] dihydrochloride of 2-azo (with the VA044 etc. that Guang Chun medicine society manufactures), [η-5-2-4-(cyclopentadecane base) (1, 2, 3, 4, 5, 6-η)-(methylethyl) benzene] iron (II) hexafluorophosphate (Irgacure261 etc. that CibaGeigy society manufactures), two (η 5-cyclopentadienyl) two [2, the fluoro-3-of 6-bis-(1H-pyrroles-1-base) phenyl] titanium (CGI-784 etc. that CibaGeigy society manufactures) etc.
In addition, azo series initiators, the benzoyl peroxides etc. such as Diisopropyl azodicarboxylate can also be share to heat sensitive peroxidation system free radical type initiator etc.Further, free base system and these two kinds of initiators of positively charged ion system can also be share.Initiator can also be used alone one, can also share two or more.
In addition, in order to make active energy ray-curable resin composition of the present invention be fit for various uses, other compositions that the upper limit is 70 quality % can also be added in resin combination.As other compositions, can enumerate other additives, paint material, coloured material and volatile solvent etc., volatile solvent adds to give coating adaptive etc. to adjust viscosity.Other compositions spendable illustrate as follows.
As other additives, the thermal curing catalysts such as such as trimeric cyanamide can be used; The thixotropy conferring agents such as fumed silica; Silicone-based, fluorine system flow agent or defoamer; The stopper such as quinhydrones, hydroquinone monomethyl ether; Stablizer; Antioxidant etc.
Further, as other paint materials, can also use such as, not to be colored as the so-called pigment extender of object.Can enumerate such as, talcum, barium sulfate, calcium carbonate, magnesiumcarbonate, barium titanate, aluminium hydroxide, silicon-dioxide, clay etc.
In addition, to active energy beam do not show reactive resene (so-called inert polymer) can use such as other epoxy resin, resol, carbamate resins, vibrin, ketone resin, cresol resin, xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin and their modifier.Preferably these resins use in the scope of below 40 quality %.
Particularly, when reactive polycarboxylic compounds (B) will be used in solder resist purposes, do not show reactive resene as to active energy beam, preferably use known general epoxy resin.This is because, after reaction under active energy beam effect, solidification, also can remain the carboxyl from (B), the water tolerance of its cured article of result or water-disintegrable deterioration.Therefore, by using epoxy resin, making the further carboxylic esterification of carboxyl remained, forming more strong crosslinking structure.
And according to application target, in order to adjust viscosity, can also at below 50 quality % in resin combination, preferably the scope of below 35 quality % is interior further adds volatile solvent.
The present invention relates to the active energy ray-curable resin composition as molding material, tunicle formation material or anticorrosive additive material composition.
Molding material in the present invention refers to the material for following purposes: uncured composition is put into mold, or presses mold and after shaping effluent body, utilize active energy beam to make it curing reaction occur and shaping purposes; Or to focused lights etc. such as uncured composition irradiating lasers, make it curing reaction occur and shaping purposes.
As concrete purposes, can enumerate and be shaped to plane sheet material; For the protection of the sealing material of element; " mold " through microfabrication is impressed in uncured composition and carries out fine shaping, so-called Nano-imprinting materials; And particularly heat management requires the peripheral sealing material etc. of harsh photodiode, photo-electric conversion element etc., these are applicable purposes.
Tunicle formation material in the present invention is utilized in order to coating substrate surface.As concrete purposes, the ink materials such as photogravure ink, flexo ink, silk-screen ink, flexographic ink; The coating materials such as dura mater, finish paint, overprint varnish zhe, Clear coating; The various joint compounds such as lamination use, CD use; The adhesivess such as (pressure-sensitive) tackiness agent; The anticorrosive additive materials etc. such as solder resist, anticorrosion layer, micromotor resist are equivalent to tunicle formation material.In addition, so-called dry film is also equivalent to tunicle formation material, and so-called dry film is formed like this: temporarily to be coated by tunicle formation material on separability base material and after carrying out film forming, to fit in target substrate originally, form tunicle.
Among these purposes, by importing the carboxyl of reactive polycarboxylic compounds (B), be improved with the adaptation of base material, the tunicle formation material therefore in the present invention preferably uses in the purposes for coating plastic basis material or metal base.
In addition, it is the feature of solubility that unreacted reactive polycarboxylic compounds (B) gives full play in alkali aqueous solution, thus the active energy ray-curable resin composition also preferably in the present invention is used as liquid alkali developing type anticorrosive additive material composition.
Anticorrosive additive material composition in the present invention refers to following composition: formed on base material said composition by rete, thereafter, irradiation ultraviolet radiation isoreactivity energy-ray partly, to utilize irradiation portion, the composition of active energy beam responsive type that the physical difference of non-irradiation unit is drawn.Specifically, be the composition used with following object: utilize some method (such as utilize solvent etc. or basic solution etc. to make it dissolve, etc.) to remove irradiation portion or non-irradiation unit, to draw.
Active energy ray-curable resin composition of the present invention utilizes active energy beam easily to solidify.At this, as the concrete example of active energy beam, the hertzian wave such as ultraviolet, visible rays, infrared rays, X-ray, gamma-rays, laser rays can be enumerated; The beta lines etc. such as alpha-ray, β ray, electron rays.Consider the purposes that the present invention is applicable to, among these, preferred ultraviolet, laser rays, visible rays or electron rays.
Active energy ray-curable resin composition of the present invention can be suitable for the various materials of patternable, such as particularly, layer insulation material for solder resist material, lamination method (PVC Le De ア ッ プ engineering method) is useful, in addition, as optical waveguides, the such electric base material of printed circuit board (PCB), optoelectronic substrate or photopolymer substrate, electronic substrate and light base material etc. can also be used in.
As specially suitable purposes, give full play to the characteristic that can obtain tough cured article, the permanent resist purposes such as preferred solder resist; Give full play to the characteristic that pigment-dispersing is well such, the purposes of chromatic photoresist, particularly the black matrix layer resists such as preferred printing-ink, colour filter.
In addition, be particularly suitable for dry film purposes, dry film purposes has physical strength before requiring the curing reaction under active energy beam effect.That is, the hydroxyl of above-mentioned epoxy resin (a) used in the present invention, the balance of epoxy group(ing) are in specified range, although therefore reactive carbonate of the present invention has higher molecular weight, can give play to good developability also.
As the method forming tunicle, be not particularly limited, but at random can adopt the planography ways such as porous printing mode, offset printing such as letterpress mode, the silk screen printings such as intaglio printing mode, the flexographic printings such as photogravure, various coating method (such as roller coating machine, knife, mould are coated with machine, curtain coater, spin coater etc.).
The cured article of active energy ray-curable resin composition of the present invention refers to, in order to for such use, irradiates active energy beam, the cured article obtained after making it solidify to active energy ray-curable resin composition of the present invention.
The article covering surface with active energy ray-curable resin composition of the present invention refer to, suitable base material is formed active energy ray-curable resin composition of the present invention by rete, irradiation ultraviolet radiation isoreactivity energy-ray partly, makes the article that the tunicle cured layer on base material is formed.Now, can be the article cured article of this resin combination being defined entirely tunicle cured layer on base material, also can be define through the article of Resist patterns with the tunicle cured layer drawn, be not particularly limited.
Embodiment
Below, by embodiment, the present invention will be described in more detail, but the present invention is not limited to these embodiments.Further, in embodiment only otherwise special declaration, " part " expression " mass parts ".
Softening temperature, epoxy equivalent (weight) etc. utilize following condition to measure.
1) epoxy equivalent (weight): utilize the method based on JISK7236:2001 to measure.
2) softening temperature: utilize the method based on JISK7234:1986 to measure.
3) acid number: utilize the method based on JISK0070:1992 to measure.
4) condition determination of GPC is as follows.
Type: TOSOHHLC-8220GPC
Post: TSKGELSuperHZM-N
Elutriant: THF (tetrahydrofuran (THF)); Per minute 0.35ml, 40 DEG C
Detector: Differential refractometer
Molecular weight standard: polystyrene
Reference example 1: utilize the epoxy resin shown in general formula (2) to prepare carbonate (A)
Add the 288gNC-3000H (R provided in Japanese chemical drug manufacture, softening temperature 70 DEG C, epoxy equivalent (weight) 288g/eq, general formula (2) 3being all hydrogen atom, p count 3 using mean value) dimethylol propionic acid (abbreviation DMPA, Mw=134) of record amount that has concurrently in molecule in the compound (b) of more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl, table 1 as the vinylformic acid (being called for short AA, Mw=72) of the record amount in epoxy resin (a), table 1 has the compound (c) of more than one hydroxyl and more than one carboxyl concurrently in molecule.Describe with mol ratio and to feed intake equivalence ratio relative to each AA, DMPA of epoxy group(ing).
Add 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % as solvent, in 100 DEG C reaction 24 hours, obtain carbonate of the present invention (A) solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine, measured value is recorded in table 1.For determination of acid value, reaction soln is utilized to carry out measuring and the acid number be converted into solid component meter.
Reference example 2: utilize the epoxy resin shown in general formula (3) to prepare carbonate (A)
Add 230gNC-2000 (Japanese chemical drug manufacture, the R provided in softening temperature 60 DEG C, epoxy equivalent (weight) 230g/eq, general formula (3) 4being all hydrogen atom, r count 5 using mean value) dimethylol propionic acid of record amount as the vinylformic acid of the record amount in epoxy resin (a), table 1 as compound (b) and in table 1 is as compound (c).Describe with mol ratio and to feed intake equivalence ratio relative to each AA, DMPA of epoxy group(ing).
Add 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % of reaction solution as solvent, in 100 DEG C reaction 24 hours, obtain carbonate (A) solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine, measured value is recorded in table 1.For determination of acid value, reaction soln is utilized to carry out measuring and the acid number be converted into solid component meter.
Reference example 3: utilize the epoxy resin shown in general formula (4) to manufacture epoxy carboxylic acids's ester cpds (A)
Add 250gXD-1000 (Japanese chemical drug manufacture, the R provided in softening temperature 70 DEG C, epoxy equivalent (weight) 250g/eq, general formula (4) 5being all hydrogen atom, t count 3 using mean value) dimethylol propionic acid of record amount as the vinylformic acid of the record amount in epoxy resin (a), table 1 as compound (b) and in table 1 is as compound (c).Describe with mol ratio and to feed intake equivalence ratio relative to each AA, DMPA of epoxy group(ing).
Use 3g triphenylphosphine as catalyzer, add and make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % as solvent, in 100 DEG C of reactions 24 hours, obtain epoxy carboxylic acids's ester cpds (A) solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine, measured value is recorded in table 1.For determination of acid value, reaction soln is utilized to carry out measuring and the acid number be converted into solid component meter.
Embodiment 1: compare the preparation with carbonate
Add 288gNC-3000H, 72g (mol ratio: 1.0) vinylformic acid as compound (b), 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % as solvent, in 100 DEG C of reactions 24 hours, obtain carbonate solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine, measured value is recorded in table 1.For determination of acid value, reaction soln is utilized to carry out measuring and the acid number be converted into solid component meter.
Embodiment 2: compare the preparation with carbonate
Add 230gNC-2000,72g (mol ratio: 1.0) vinylformic acid as compound (b), 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % of reaction solution as solvent, in 100 DEG C of reactions 24 hours, obtain carbonate solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine, measured value is recorded in table 1.For determination of acid value, reaction soln is utilized to carry out measuring and the acid number be converted into solid component meter.
Embodiment 3: compare the preparation with epoxy carboxylic acids's ester cpds
Add 250gXD-1000,72g (mol ratio: 1.0) vinylformic acid as compound (b), 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % as solvent, in 100 DEG C of reactions 24 hours, obtain epoxy carboxylic acids's ester cpds solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine, measured value is recorded in table 1.For determination of acid value, reaction soln is utilized to carry out measuring and the acid number be converted into solid component meter.
Comparative example 4-1: compare the preparation with carbonate
Add 200g cresol novolac type epoxy resin EOCN-103S (Japanese chemical drug manufacture, softening temperature 80 DEG C, epoxy equivalent (weight) 200g/eq), 36g (mol ratio: 0.5) vinylformic acid is as the compound (b), the 67g (mol ratio that have more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl in molecule concurrently; 0.5) dimethylol propionic acid is as the compound (c) having more than one hydroxyl and more than one carboxyl in molecule concurrently.
Add 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % as solvent, in 100 DEG C reaction 24 hours, obtain comparing and use carbonate solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine, measured value is recorded in table 1.For determination of acid value, reaction soln is utilized to carry out measuring and the acid number be converted into solid component meter.
Comparative example 4-2: compare the preparation with carbonate
Add 200g cresol novolac type epoxy resin jER-1002 (manufacture of ジ ャ パ Application エ Port キ シ レ ジ Application society, epoxy equivalent (weight) 400g/eq), 18g (mol ratio: 0.5) vinylformic acid is as compound (b), 34g (mol ratio: 0.5) dimethylol propionic acid is as compound (c).
Add 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % of reaction solution as solvent, in 100 DEG C reaction 24 hours, obtain comparing and use carbonate solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine, measured value is recorded in table 1.For determination of acid value, reaction soln is utilized to carry out measuring and the acid number be converted into solid component meter.
Table 1
Table 1 reference example 1,2,3 and embodiment 1,2,3, comparative example 4: the preparation of epoxy carboxylic acids's ester cpds (A)
Test example 1: the storage stability of epoxy carboxylic acids's ester cpds (A)
Be stored in the refrigeration chamber of lower than freezing point 5 DEG C with reference to the epoxy carboxylic acids's ester cpds solution obtained in example 1 and embodiment 1, compare until produce the time of crystallization, list in table 2.
Table 2
Table 2 test example 1: the storage stability of epoxy carboxylic acids's ester cpds
From above result, along with the importing of compound (c) having more than one hydroxyl and more than one carboxyl in molecule concurrently, the storage stability of resin solution improves.
Reference example 4: utilize the epoxy resin preparation feedback polycarboxylic compounds (B) shown in general formula (2)
The Tetra Hydro Phthalic Anhydride (be called for short THPA) adding the record amount in table 3 in carbonate (A) the solution 299g obtained separately in reference example 1-1,1-2,1-3 is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 DEG C, carry out sour addition reaction, obtain reactive polycarboxylic compounds (B) solution (reference example 4-1,4-2,4-3,4-4) of the present invention.Solids component acid number (mgKOH/g) lists in table 3.
Reference example 5: utilize the epoxy resin preparation feedback polycarboxylic compounds (B) shown in general formula (3)
The Tetra Hydro Phthalic Anhydride of amount that table 3 records is added as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % of reaction solution as solvent in carbonate (A) the solution 299g obtained separately in reference example 2-1,2-2,2-3,2-4, be heated to 100 DEG C, carry out sour addition reaction in 3 hours, obtain reactive polycarboxylic compounds (B) solution (reference example 5-1,5-2,5-3,5-4,5-5) of the present invention.Solids component acid number (mgKOH/g) lists in table 3.
Reference example 6: utilize the epoxy resin shown in general formula (4) to manufacture polycarboxylic compounds (B)
The Tetra Hydro Phthalic Anhydride adding the record amount in table 3 in epoxy carboxylic acids's ester cpds (A) the solution 299g obtained separately in reference example 3-1,3-2,3-3 is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 DEG C, carry out sour addition reaction, obtain polycarboxylic compounds (B) solution (reference example 6-1,6-2,6-3,6-4).Solids component acid number (mgKOH/g) lists in table 3.
Embodiment 5: compare the preparation with reactive polycarboxylic compounds
The Tetra Hydro Phthalic Anhydride of the record amount in the carbonate solution 299g obtained in embodiment 1 in interpolation table 3 is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 DEG C, carry out sour addition reaction, obtain reactive polycarboxylic compounds's solution (embodiment 5-1,5-2).Solids component acid number (mgKOH/g) lists in table 3.
Embodiment 6: compare the preparation with reactive polycarboxylic compounds
The Tetra Hydro Phthalic Anhydride of amount that in the carbonate solution 299g obtained in embodiment 2, interpolation table 3 is recorded is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % of reaction solution as solvent, be heated to 100 DEG C, carry out sour addition reaction in 3 hours, obtain reactive polycarboxylic compounds's solution (embodiment 6-1,6-2).Solids component acid number (mgKOH/g) lists in table 3.
Embodiment 7: compare the preparation with reactive polycarboxylic compounds
The Tetra Hydro Phthalic Anhydride of the record amount in the epoxy carboxylic acids's ester cpds solution 299g obtained in embodiment 3 in interpolation table 3 is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 DEG C, carry out sour addition reaction, obtain polycarboxylic compounds's solution (embodiment 7-1,7-2).Solids component acid number (mgKOH/g) lists in table 3.
Comparative example 8: compare the preparation with reactive polycarboxylic compounds
The Tetra Hydro Phthalic Anhydride of the record amount in the epoxy carboxylic acids's ester cpds solution 299g obtained in comparative example 4-1,4-2 in interpolation table 3 is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 DEG C, carry out sour addition reaction, obtain polycarboxylic compounds's solution (comparative example 8-1,8-2,8-3).Solids component acid number (mgKOH/g) lists in table 3.
Table 3
Table 3 reference example 4,5,6 and embodiment 5,6,7, comparative example 8: the preparation of reactive polycarboxylic compounds (B)
Reference example 7,8,9 and embodiment 9,10,11, comparative example 12: the preparation of hard film composition and cured article thereof and their hardness evaluation test, impact evaluation test
Using 20g reference example 1,2,3 and embodiment 1,2,3, the reactive carbonate (A) of preparation in comparative example 4,4g is as the dipentaerythritol acrylate of the monomer (C) of radical-curable, 1.5g as the Irgacure184 heating for dissolving of ultraviolet response type initiator.(in reference example 7-4,8-4,9-4, then add the UVI-6990 of 1.0g as positively charged ion series initiators.)
They are coated on polycarbonate plate by recycling manual applicator (Ha Application De ア プ リ ケ ー タ), and thickness when being applied to drying reaches 20 microns, implements solvent seasoning at 80 DEG C, 30 minutes in electric oven.After drying, the ultraviolet vertical exposure device (オ ー Network possessing high pressure mercury vapour lamp is utilized to make manufactured) ultraviolet of exposure radiation dose 1000mJ, make it solidify, obtain multilayer material.
According to JISK5600-5-4:1999, measure the hardness (test example 2) of the film of this multilayer material, also implement the test (test example 3) of impact according to ISO6272-1:2002, then implement the test (test example 4) of thermal shock according to JISK5600-7-4:1999.The each test analyte (reference example 7 ~ 9, embodiment 9 ~ 11, comparative example 12) prepared and each evaluation test result (test example 2 ~ 4) list in table 4.
Table 4
Table 4 reference example 7,8,9 and embodiment 9,10,11, comparative example 12: the preparation of dura mater material and evaluation
Shock-resistance, cold-hot impact metewand:
Zero: not damaged, nothing are peeled off, △: slightly damage, ×: peel off
From above result, with do not use in a part the compound (c) that has hydroxyl and carboxyl concurrently and the embodiment 9,10,11 of epoxy group(ing) all acrylate compared, in reference example 7,8,9, the shock-resistance of the dura mater material of preparation is improved.Think after deliberation, the reason that this shock-resistance improves is, along with the importing of compound (c), the density appropriateness of double bond reduces, and along with hydroxyl importing, the loose crosslinking structure brought by hydrogen bond produces desirable influence.
Further, for comparative example 12-1,12-2 of being derived by common difunctional epoxy resin, solidified nature significantly worsens, and shock-resistance is lower.
Reference example 10,11,12 and embodiment 13,14,15, comparative example 16: the preparation of dry-film type anti-corrosion agent composition and cured article thereof
Add reference example 4, 5, 6 and embodiment 5, 6, 7, reactive polycarboxylic compounds (B) 54.44g obtained in comparative example 8, as HX-220 (trade(brand)name: the diacrylate monomer that the Nippon Kayaku K. K manufactures) 3.54g of other reactive compounds (C), as Irgacure907 (CibaSpecialtyChemicals manufacture) 4.72g and KayacureDETX-S (Nippon Kayaku K. K's manufacture) 0.47g of Photoepolymerizationinitiater initiater, as GTR-1800 (Nippon Kayaku K. K's manufacture) 14.83g of cure component, as the trimeric cyanamide 1.05g of thermal curing catalyst and the methyl ethyl ketone 20.95g as concentration adjustment solvent, ball mill is utilized to carry out mixing, make them dispersed, obtain resist resin combination.
Use coiling rod spreader #20; obtained composition is uniformly coated on as on the polyethylene terephthalate film of supporting film; make it by the hot-air drying stove of temperature 70 C; after forming the resin layer of thickness 20 μm; attach the polyethylene film as protective membrane on the resin layer, obtain dry film.While peeled off by the protective membrane of obtained dry film, this resin layer is attached on the whole real estate of polyimide printed base plate (copper circuit is thick: 12 μm, polyimide thickness: 25 μm) by the warming mill that use temperature is 80 DEG C.
It should be noted that, (A), (B) melange used in reference example 10-5,11-6,12-5 is mixed to get with 50:50 (with solution weight gauge) with reference to the polycarboxylic compounds (B) of the epoxy resin of the use correspondence prepared in the sour modified carboxylic acid ester cpds (A) of preparing in routine 1-1,2-1 or 3-1 and reference example 4-1,5-1 or 6-1 respectively.
Next, in order to estimate the mask and sensitivity of drawing circuit pattern, ((strain) オ ー Network makes institute, model HMW-680GW), the optics step-wedge No.2 manufactured by Kodak, irradiates 500mJ/cm to use ultraviolet exposure apparatus according 2ultraviolet.Thereafter, peel off the film on dry film, confirm stripping state.Then spray development is carried out with 1% aqueous sodium carbonate, the resin of removing ultraviolet non-irradiation unit.After washing and drying, make printed base plate carry out the reaction that is heating and curing for 60 minutes with the hot-air driers of 150 DEG C, obtain cured film.
By evaluation method shown below, carry out reference example 10,11,12 and embodiment 13,14,15, the benchmark test (test example 5 ~ 10) of dry-film type resist cured film that obtains in comparative example 16.The evaluation test of each cured film the results are shown in table 5.
Test example 5: folding resistance evaluation
With cured film side for top, the polyimide printed base plate being formed with the cured film of resist is upwards rolled over (mountain folding り), smooth out with the fingers kink fully with finger.Kink is restored, observes resist film with magnifying glass.
Metewand: zero: without be full of cracks, △: observe slightly chap, ×: peel off
Test example 6: cold-hot impact is evaluated
To be formed resist cured film polyimide printed base plate-65 ~ 120 DEG C scope implement cold shock testing.Test method is according to JISC5012-9.1:1993.After off-test, scotch tape (セ ロ Ha ン テ ー プ) (registered trademark) is utilized to implement stripping test.
Metewand: zero: without stripping, △: observe and peel off slightly, ×: peel off
Test example 7: high temperature wet fastness is evaluated
The polyimide printed base plate being formed with the cured film of resist is put into the autoclave 1 hour of 120 DEG C.Take out substrate, after room temperature makes it air-dry, utilize scotch tape (セ ロ Ha ン テ ー プ) (registered trademark) to implement stripping test.
Metewand: zero: without stripping, △: observe and peel off slightly, ×: peel off
Test example 8: sensitivity evaluation
By investigating through in the exposure portion of optics step-wedge, the Concentration portion to which " section lattice " is remaining when developing, and judges sensitivity thus." section lattice " number (value) large person, in the dense portion of optics step-wedge, is judged to be highly sensitive (unit: section).
Test example 9: developability evaluation
For developability, with the evaluation (unit: second) of so-called presentation time (Block レ イ Network タ イ system) (when this time is by exposure portion development through pattern mask, until pattern form portion time of being completely developed out) as developability.
Test example 10: solidified nature evaluation
The pencil hardness of the cured film after solidified nature evaluation terminates with 150 DEG C of heating represents.Evaluation method is according to JISK5600-5-4:1999.
Table 5
Table 5 reference example 10,11,12 and embodiment 13,14,15, comparative example 16: the evaluation of dry film photoresist
From above-mentioned result, the anti-corrosion agent composition in the present invention can obtain the cured article with higher hardness, has good developability and sensitivity as resist.In addition, when reference example 10,11, there is high folding resistance.Further, there is high cold-hot impact and high temperature wet fastness in reference example 12.The anti-corrosion agent composition obtained by comparative example and cured article thereof folding resistance, tolerate produced by thermal distortion impact, do not demonstrate good evaluation result in developability and sensitivity, as dry film photoresist material, performance is unsatisfactory.
Reference example 13 and embodiment 17, comparative example 18: flame retardant resin and the preparation of comparing with resin
By anti-corrosion agent composition, 0.5g phosphoric acid ester flame retardant (four countries the change into SP-703H) mix and blend prepared in 9.5g reference example 10-2 and embodiment 13-1 and comparative example 16-1, obtain curable resin composition.Use coiling rod spreader #20 to be coated on by composition on the polyimide film of thickness 25 microns, make it by the hot-air drying stove of temperature 70 C, form the resin layer of thickness about 15 μm.((strain) オ ー Network makes institute, model HMW-680GW), irradiates 500mJ/cm to use ultraviolet exposure apparatus according 2ultraviolet.After irradiation, make printed base plate carry out the reaction that is heating and curing for 60 minutes with the hot-air driers of 150 DEG C, obtain cured film (being respectively reference example 13, embodiment 17, comparative example 18).
Test example 11: the evaluation of flame retardant resistance
Be cut into the strip of length 20cm, wide 2cm together with polyimide base material film with reference to the cured film obtained in example 13, embodiment 17, comparative example 18.The film cut is sling along lengthwise direction, utilizes lighter for ignition to light a fire from lower end, evaluate flame retardant resistance.In order to carry out and the comparing of folding resistance, as a reference, the folding resistance testing data with reference to routine 10-2, embodiment 13-1 and comparative example 16-1 is recorded in following table 6 in the lump.
Table 6
Table 6 test example 11; The evaluation of the flame retardant resistance of reference example 13 and embodiment 17, comparative example 18
Flame retardant resistance metewand: zero: catch fire, but all burn up front fire and go out.×: all burn up.
From above result, the carbonate of reference example is the material can simultaneously with flame retardant resistance and folding resistance.
Reference example 14,15,16 and embodiment 19,20,21, comparative example 22: the preparation being dispersed with the resin of tinting pigment
Using 20g reference example 4,5,6 and embodiment 5,6,7, the reactive polycarboxylic compounds (B) that obtains in comparative example 8,5.0g as DPHA (trade(brand)name: the acrylate monomer that Nippon Kayaku K. K manufactures), the 10g of other reactive compounds (C) as the propylene glycol methyl ether acetate of organic solvent, 10g is as the Mitsubishi Carbon Black MA-100 mix and blend of tinting pigment.Add the granulated glass sphere of 35g wherein, carry out dispersion in 1 hour with coating rocker.
Dispersion liquid after using coiling rod spreader #2 dispersion to be terminated is coated on polyethylene terephthalate film, utilizes the hot air dryer of 80 DEG C to carry out drying in 10 minutes, is respectively dispersed with the resin of carbon black.
Test example 12: the evaluation relevant to pigment-dispersing
Use 60 ° of reflectance gloss meters (hole field makes institute IG-331 glossmeter), to reference example 14,15,16 and embodiment 19,20,21, the gloss being dispersed with the film coated surface of the resin of carbon black that obtains in comparative example 22 measures, and evaluates the dispersiveness of carbon black.Now, the higher person of gloss, represents that pigment-dispersing is better.The results are shown in table 7.
Table 7
Table 7 reference example 14,15,16 and embodiment 19,20,21, comparative example 22: the evaluation of pigment-dispersing
From above-mentioned result, in the reactive polycarboxylic compounds (B) of reference example, pigment-dispersing is improved.Think after deliberation, due to different from the polycarboxylic acid of embodiment, this pigment-dispersing effect is the difference of the effect that the interpolation of the epoxy resin and compound (c) comprising ad hoc structure in molecule on basic framework brings.
Reference example 17 and embodiment 23, comparative example 24: the preparation being dispersed with the resin of tinting pigment
Using obtain in 20g reference example 4-2 and embodiment 5-1, comparative example 8-1 reactive polycarboxylic compounds (B), 5.0g as DPHA (trade(brand)name: the acrylate monomer that Nippon Kayaku K. K manufactures), the 10g of other reactive compounds (C) as the propylene glycol methyl ether acetate of organic solvent, 10g is as the Mitsubishi Carbon Black MA-100 mix and blend of tinting pigment.Add the granulated glass sphere of 35g wherein, carry out dispersion in 1 hour with coating rocker.By the obtained resin liquid sampling being dispersed with carbon black in sample bottle, obtain tinting pigment dispersion liquid.
Test example 13: the storage stability evaluation of tinting pigment dispersion liquid
In reference example 17 and embodiment 23, comparative example 24, the tinting pigment dispersion liquid of preparation was in 40 DEG C of standing preservations 2 weeks, the state of this dispersion liquid of visual valuation.The results are shown in table 8.
Table 8
The evaluation of the dispersible pigment dispersion storage stability of table 8 reference example 17 and embodiment 23, comparative example 24
Estimation of stability benchmark: zero: uniform solution, △: gradient dispersion, ×: pigment precipitates
From above-mentioned result, though the tinting pigment dispersion liquid of reference example in 40 DEG C through 2 weeks, also maintain uniform state, dispersion liquid is not separated.On the other hand, for embodiment 23, can observe transparent layer (varnish floats (ニ ス floats I)) on upper strata, dispersion state is unstable.In comparative example 24, generate the precipitation of tinting pigment, also cannot become homogeneous state even if be in carry out stirring.
From above-mentioned result, by importing the compound (c) having more than one hydroxyl and more than one carboxyl in the compound (b) and molecule having more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl in molecule concurrently concurrently the epoxy resin (a) taking ad hoc structure as basic framework is upper, in reactive polycarboxylic compounds (B) of the present invention, pigment-dispersing is improved, and the storage stability of its dispersible pigment dispersion is improved simultaneously.
Industrial applicibility
For active energy ray curable resin of the present invention, as the material that solidified nature and flexibility, obdurability, flame retardant resistance have concurrently, can enumerate dura mater material, can alkaline development and with flexibility be necessity anticorrosive additive material, play the purposes of good pigment-dispersing, but such as the printing-ink of active energy ray curable, chromatic photoresist, particularly have the material of the resist such as pigment-dispersing and developability adaptive concurrently, can be particularly suitable for for the chromatic photoresist of LCD, particularly black matrix layer etc.

Claims (5)

1. a reactive polycarboxylic compounds (B) is as the application of the dispersion agent in black matrix layer resist, described dispersion agent does not use the dispersion agent except reactive polycarboxylic compounds (B), and this reactive polycarboxylic compounds (B) makes multi-anhydride (d) and following reactive epoxy carboxylic acids's ester cpds (A) react and obtain; Described reactive epoxy carboxylic acids's ester cpds (A) makes to have concurrently in the epoxy resin (a) shown in general formula (2) and a part compound (b) reaction of more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl and reactive epoxy carboxylic acids's ester cpds of obtaining, or the reactive epoxy carboxylic acids's ester cpds compound (b) having more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl in the epoxy resin (a) shown in general formula (4) and a part concurrently being reacted and obtains;
In general formula (2), R 3mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; O represents the integer of 1 ~ 4; And p represents the positive number of 1 ~ 10 in mean value;
In general formula (4), R 5mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; S represents the integer of 1 ~ 4; And t represents the positive number of 1 ~ 10 in mean value.
2. the application of active energy ray-curable resin composition in black matrix layer resist, it is characterized in that, described composition comprises reactive polycarboxylic compounds (B), and this reactive polycarboxylic compounds (B) makes multi-anhydride (d) and following reactive epoxy carboxylic acids's ester cpds (A) react and obtain; Described reactive epoxy carboxylic acids's ester cpds (A) makes to have concurrently in the epoxy resin (a) shown in general formula (2) and a part compound (b) reaction of more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl and reactive epoxy carboxylic acids's ester cpds of obtaining, or the reactive epoxy carboxylic acids's ester cpds compound (b) having more than one the ethylenic unsaturated group that can be polymerized and more than one carboxyl in the epoxy resin (a) shown in general formula (4) and a part concurrently being reacted and obtains;
In general formula (2), R 3mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; O represents the integer of 1 ~ 4; And p represents the positive number of 1 ~ 10 in mean value;
In general formula (4), R 5mutually identical or mutually different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 4; S represents the integer of 1 ~ 4; And t represents the positive number of 1 ~ 10 in mean value;
This active energy ray-curable resin composition does not comprise the dispersion agent except reactive polycarboxylic compounds (B).
3. the application of active energy ray-curable resin composition in black matrix layer resist as claimed in claim 2, it is characterized in that, described composition also comprises reactive compounds (C).
4. the application of active energy ray-curable resin composition in black matrix layer resist as claimed in claim 3, is characterized in that, described composition is also containing carbon black.
5. the application of the active energy ray-curable resin composition as described in claim 3 or 4 in black matrix layer resist, is characterized in that, described composition also comprises Photoepolymerizationinitiater initiater.
CN201310088076.XA 2007-08-21 2008-08-08 Reactive epoxy carboxylic acids's ester cpds, reactive polycarboxylic compounds, active energy ray-curable resin composition and article Active CN103224609B (en)

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