CN103365082B - Flame-retardant curable resin composition, dry film, anti-flammability overlay film and printed circuit board (PCB) - Google Patents

Flame-retardant curable resin composition, dry film, anti-flammability overlay film and printed circuit board (PCB) Download PDF

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CN103365082B
CN103365082B CN201310102873.9A CN201310102873A CN103365082B CN 103365082 B CN103365082 B CN 103365082B CN 201310102873 A CN201310102873 A CN 201310102873A CN 103365082 B CN103365082 B CN 103365082B
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resin
flammability
flame
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resin composition
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CN103365082A (en
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米田一善
横山裕
有马圣夫
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/84—Flame-proofing or flame-retarding additives

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The invention provides flame-retardant curable resin composition, dry film, anti-flammability overlay film and printed circuit board (PCB), halogen-free composition is specifically provided and the few and anti-flammability of carrying capacity of environment, flexible excellent, high temperature compacting time the flame-retardant curable resin composition, dry film, the anti-flammability overlay film that ooze out without fire retardant and possess the printed circuit board (PCB) of this anti-flammability overlay film.A kind of flame-retardant curable resin composition etc., phosphorus element-containing acrylate resin that at least one in it contains (A) the phosphorus element-containing dicarboxylic acid shown in following general formula (1) and acid anhydrides thereof and acrylate compounds react and obtain (in formula, R 1and R 2separately represent the alkyl of hydrogen atom or carbon number 1 ~ 6, m and n separately represents the integer of 0 ~ 4, and dotted line represents that two carboxyls also can form acid anhydrides), (B-1) have the part-structure being selected from structure of bisphenol A etc. containing carboxy resin, (C) thermosetting component and (D) Photoepolymerizationinitiater initiater.

Description

Flame-retardant curable resin composition, dry film, anti-flammability overlay film and printed circuit board (PCB)
Technical field
The present invention relates to flame-retardant curable resin composition, dry film, anti-flammability overlay film and printed circuit board (PCB), specifically, relate to can obtain halogen-free composition and the few and anti-flammability of carrying capacity of environment, flexible excellent, high temperature compacting time ooze out without fire retardant the flame-retardant curable resin composition of anti-flammability overlay film, the dry film formed by said composition, by carrying out at least any one and the anti-flammability overlay film that obtains and the printed circuit board (PCB) possessing this anti-flammability overlay film in heat curing and photocuring to said composition or this dry film.
Background technology
All the time, about flexible PCB (FPC), carry out punch press process to the insulation film being coated with bonding agent and be laminated to being called as tectal Kapton, and then, utilize compacting to carry out heat curing under an increased pressure, thus make the overlayer on the surface of the flexible base, board being formed with circuit.This overlayer is made up of lower shrinkage heat-curing resin owing to being substrate with Kapton, therefore, warpage after can making lamination and after press curing is very little, and then, after the attaching of stiffening plate thereafter, heat curing can be made, encapsulation backflow time warpage also considerably less, in a large number for FPC purposes.
But, owing to utilizing compacting to carry out punch press process, there is following shortcoming: be difficult to carry out microfabrication, and with when being formed with the circuit board lamination of circuit, position alignment precision is bad.
To this, as photosensitive cover lay, propose alkali-developable photosensitive resin composition, its dry film (with reference to patent documentation 1).
On the other hand, FPC needs anti-flammability owing to being equipped on electronic equipment, also needs the solder resist of this FPC purposes.FPC is generally polyimide substrate, is the film different from the printed circuit board (PCB) of glass epoxy substrate.But owing to no matter being printed circuit board (PCB) or FPC, the solder resist that be coated with is same thickness, therefore, relatively becomes large to the flame-retarded burden of solder resist.To this, propose containing have can with the composition of the FPC solder resist of the compound of the unsaturated double-bond of halogenate aromatic cyclopolymerization (with reference to patent documentation 2), the use of halogen compounds is not preferred from the viewpoint of carrying capacity of environment.
In addition, as the anti-corrosion agent composition of not halogen contained compound, such as, propose containing specific phosphorus element-containing acrylate, composition containing carboxy resin, but flexibility has the leeway (with reference to patent documentation 3) of improvement.
In addition, as the anti-corrosion agent composition of not halogen contained compound, such as, propose the composition containing phenoxy phosphazene oligomer and epoxy acrylate, but when at high temperature suppressing in order to stiffening plate of fitting etc., generation fire retardant oozes out, and becomes problem (with reference to patent documentation 4).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-131836 publication (claims)
Patent documentation 2: Japanese Unexamined Patent Publication 2007-10794 publication (claims)
Patent documentation 3: Japanese Patent No. 4616863 publication (claims)
Patent documentation 4: Japanese Patent No. 3091457 publication (claims)
Summary of the invention
the problem that invention will solve
Thus, the object of the invention is to, provide can obtain halogen-free composition and the few and anti-flammability of carrying capacity of environment, flexible excellent, high temperature compacting time the flame-retardant curable resin composition of anti-flammability overlay film of oozing out without fire retardant and the dry film formed by said composition, by carrying out at least any one and the anti-flammability overlay film that obtains and the printed circuit board (PCB) possessing this anti-flammability overlay film in heat curing and photocuring to said composition or this dry film.
Other object of the present invention is, provide can obtain halogen-free composition and carrying capacity of environment is few and anti-flammability, flexibility, low warpage properties excellent, high temperature compacting time the flame-retardant curable resin composition of anti-flammability overlay film of oozing out without fire retardant and the dry film formed by said composition, by carrying out at least any one and the anti-flammability overlay film that obtains and the printed circuit board (PCB) possessing this anti-flammability overlay film in heat curing and photocuring to said composition or this dry film.
for the scheme of dealing with problems
The present inventor etc. conduct in-depth research to solve the problem, and found that, by compounding specific phosphorus element-containing acrylate resin with specifically containing carboxy resin, can solve the problem, thus complete the present invention.
Namely, the feature of flame-retardant curable resin composition of the present invention is, it contains: the phosphorus element-containing acrylate resin that at least one in the phosphorus element-containing dicarboxylic acid shown in (A) following general formula (1) and acid anhydrides thereof and acrylate compounds react and obtain;
(in formula, R 1and R 2separately represent the alkyl of hydrogen atom or carbon number 1 ~ 6, m and n separately represents the integer of 0 ~ 4, and dotted line represents that two carboxyls also can form acid anhydrides.)
(B-1) what have more than one the part-structure in the group being selected from and being made up of structure of bisphenol A, Bisphenol F structure, biphenol structural, xenol novolac structure, two xylenol structure, biphenyl novolac structure and carbamate structures contains carboxy resin;
(C) thermosetting component; With
(D) Photoepolymerizationinitiater initiater.
Flame-retardant curable resin composition of the present invention is preferably solder resist and forms use.
The feature of dry film of the present invention is, foregoing flame retardant hardening resin composition is applied to also dry on film forming by it.
The feature of anti-flammability overlay film of the present invention is, its by foregoing flame retardant hardening resin composition or aforementioned dry film are carried out in heat curing and photocuring at least any one obtains.
The feature of printed circuit board (PCB) of the present invention is, it possesses foregoing flame retardant overlay film.
In addition, the present inventor etc. conduct in-depth research to solve the problem, and found that, by compounding specific phosphorus element-containing acrylate resin, the epoxy resin with biphenyl novolac structure, can solve the problem, thus complete the present invention.
That is, the feature of other flame-retardant curable resin composition of the present invention is, it contains:
(A) the phosphorus element-containing acrylate resin that at least one in the phosphorus element-containing dicarboxylic acid shown in following general formula (1) and acid anhydrides thereof and acrylate compounds react and obtain;
(in formula, R 1and R 2separately represent the alkyl of hydrogen atom or carbon number 1 ~ 6, m and n separately represents the integer of 0 ~ 4, and dotted line represents that two carboxyls also can form acid anhydrides.)
(B) containing carboxy resin;
(C-1) there is the epoxy resin of biphenyl novolac structure; With
(D) Photoepolymerizationinitiater initiater.
Other flame-retardant curable resin composition of the present invention is preferably solder resist and forms use.
The feature of dry film of the present invention is, foregoing flame retardant hardening resin composition is applied to also dry on film and is formed by it.
The feature of anti-flammability overlay film of the present invention is, its by foregoing flame retardant hardening resin composition or aforementioned dry film are carried out in heat curing and photocuring at least any one obtains.
The feature of printed circuit board (PCB) of the present invention is, it possesses foregoing flame retardant overlay film.
the effect of invention
According to the present invention, can provide can obtain halogen-free composition and the few and anti-flammability of carrying capacity of environment, flexible excellent, high temperature compacting time the flame-retardant curable resin composition of anti-flammability overlay film of oozing out without fire retardant and the dry film formed by said composition, by carrying out at least any one and the anti-flammability overlay film that obtains and the printed circuit board (PCB) possessing this anti-flammability overlay film in heat curing and photocuring to said composition or this dry film.
In addition, according to the present invention, can provide can obtain halogen-free composition and carrying capacity of environment is few and anti-flammability, flexibility, low warpage properties excellent, high temperature compacting time the flame-retardant curable resin composition of anti-flammability overlay film of oozing out without fire retardant and the dry film formed by said composition, by carrying out at least any one and the anti-flammability overlay film that obtains and the printed circuit board (PCB) possessing this anti-flammability overlay film in heat curing and photocuring to said composition or this dry film.
Embodiment
< first embodiment >
Flame-retardant curable resin composition of the present invention contains: the phosphorus element-containing acrylate resin that at least one in the phosphorus element-containing dicarboxylic acid shown in (A) following general formula (1) and acid anhydrides thereof and acrylate compounds react and obtain;
(in formula, R 1and R 2separately represent the alkyl of hydrogen atom or carbon number 1 ~ 6, m and n separately represents the integer of 0 ~ 4, and dotted line represents that two carboxyls also can form acid anhydrides.)
(B-1) what have more than one the part-structure in the group being selected from and being made up of structure of bisphenol A, Bisphenol F structure, biphenol structural, xenol novolac structure, two xylenol structure, biphenyl novolac structure and carbamate structures contains carboxy resin;
(C) thermosetting component; With
(D) Photoepolymerizationinitiater initiater.
Had by compounding above-mentioned (A) phosphorus element-containing acrylate resin and above-mentioned (B-1) more than one the part-structure in the group being selected from and being made up of structure of bisphenol A, Bisphenol F structure, biphenol structural, xenol novolac structure, two xylenol structure, biphenyl novolac structure and carbamate structures containing carboxy resin, halogen-free composition can be obtained and carrying capacity of environment few and anti-flammability, flexible excellent anti-flammability overlay film.
Below each composition is described in detail.
[(A) phosphorus element-containing acrylate resin]
(A) phosphorus element-containing acrylate resin used in the present invention at least any one and the acrylate compounds in the phosphorus element-containing dicarboxylic acid shown in above-mentioned general formula (1) and acid anhydrides thereof is reacted obtain, in molecule containing compound that more than (methyl) is acrylate-based.It should be noted that, in this manual, (methyl) acrylate is the general designation of acrylate, methacrylate and their potpourri, and other similar statement too.
As the R at least any one the general formula (1) represented in above-mentioned phosphorus element-containing dicarboxylic acid and acid anhydrides thereof 1and R 2the alkyl of shown carbon number 1 ~ 6, include, for example out the alkyl of carbon number 1 ~ 6, the thiazolinyl of carbon number 1 ~ 6, naphthenic base, phenyl.As the alkyl of carbon number 1 ~ 6, methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, isobutyl, amyl group, isopentyl, tertiary pentyl, hexyl etc. can be listed, as the thiazolinyl of carbon number 1 ~ 6, vinyl, allyl, 3-butenyl group, isobutenyl, 4-pentenyl, 5-hexenyl etc. can be listed.The alkyl of carbon number 1 ~ 6 also can be side chain and in being substituted at least any one.
As the example of the phosphorus element-containing dicarboxylic acid shown in above-mentioned general formula (1) and acid anhydrides thereof, 9,10-dihydro-9-oxy-10-phosphine of mixing can be listed and to mix the compound and acid anhydrides etc. thereof that phenanthrene-10-oxide and itaconic acid react and obtain.
As aforesaid propylene ester compound, preferably there is the acrylate compounds of the functional group of reacting with the carboxyl of above-mentioned dicarboxylic acid or its acid anhydrides or carboxylic acid anhydrides.By this reaction, can addition acrylate residue.This acrylate compounds can be monofunctional acrylate acrylate-based containing (methyl) in molecule, also can be polyfunctional acrylic ester acrylate-based containing two or more (methyl) in molecule.As above-mentioned functional group, epoxy radicals, hydroxyl, amino etc. can be listed.As the acrylate compounds with epoxy radicals, (methyl) glycidyl acrylate, (methyl) acrylic acid-2-methyl-2,3-polyglycidyl etc. can be listed.As the acrylate compounds with hydroxyl, acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate etc. can be listed.As having amino acrylate compounds, acrylic acid diethylamino ethyl ester etc. can be listed.In above-mentioned functional group, more preferably epoxy radicals, hydroxyl.
Utilize the reaction method of above-mentioned functional group addition can use existing known reaction method.
As the example of above-mentioned (A) phosphorus element-containing acrylate resin, can list: the phosphorus element-containing acrylate resin of 1 or 2 officials' energy that the phosphorus element-containing dicarboxylic acid of the general formula (1) synthesized as above-mentioned example and glycidyl methacrylate are reacted and obtained; The phosphorus element-containing acrylate resin etc. of 2 officials' energy that the reaction of the phosphorus element-containing dicarboxylic acid of general formula (1), (methyl) crylic acid hydroxy ester and glycol is as required obtained.
Be not particularly limited relative to the addition of the aforesaid propylene ester compound of the phosphorus element-containing dicarboxylic acid shown in above-mentioned general formula (1) or its acid anhydrides, preferably, adjust in the mode that the phosphorus concentration of above-mentioned (A) phosphorus element-containing acrylate resin is the scope of 2% ~ 7%, form acrylate compounds.
By using the phosphorus element-containing dicarboxylic acid shown in above-mentioned general formula (1) or its acid anhydrides, the phosphorus element-containing acrylate resin that can easily obtain two terminal acrylate.By using the phosphorus element-containing acrylate resin of the terminal acrylate that obtains thus, can obtain and can obtain that flexibility, low warpage properties are excellent, high temperature compacting time do not produce the flame-retardant curable resin composition of the excellence of the anti-flammability overlay film oozed out.
From the viewpoint of flexibility, phosphorus element-containing acrylate resin of the present invention is preferably the phosphorus element-containing acrylate of 2 officials' energy.When phosphorus element-containing acrylate resin is simple function, there is the tendency of poor heat resistance, phosphorus element-containing acrylate resin be 3 officials can above time, there is the flexible tendency reduced.
In addition, above-mentioned (A) phosphorus element-containing acrylate resin can be used alone one, also can combinationally use two or more.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1) containing carboxy resin, the compounding amount of above-mentioned (A) phosphorus element-containing acrylate resin be preferably more than 10 mass parts and below 100 mass parts, be more preferably more than 20 mass parts and ratio below 80 mass parts.During more than 100 mass parts, thermotolerance, chemical proofing are poor sometimes.On the other hand, during less than 10 mass parts, sometimes cannot obtain sufficient anti-flammability, low warpage properties.
In addition, when taking the phosphorus concentration in anti-flammability solidification compound as mode compounding (A) the phosphorus element-containing acrylate resin of more than 1%, sufficient effect can be played in the characteristic of anti-flammability, but compounding too many time, sometimes therefore resistance to soldering heat poor performance is too much not preferred.In addition, according to kind, the addition of the acrylate compounds used in reaction, sometimes cannot obtain sufficient photo-curable, thus, also can combinationally use existing known photopolymerization monomer/oligomer and improve photo-curable.In addition, in order to improve photo-curable, oxime system described later Photoepolymerizationinitiater initiater also can be added.
[(B-1) is containing carboxy resin]
(B-1) that use in the present invention refers to containing carboxy resin, there is in molecule the compound of more than one part-structure in the group being selected from and being made up of structure of bisphenol A, Bisphenol F structure, biphenol structural, xenol novolac structure, two xylenol structure, biphenyl novolac structure and carbamate structures and carboxyl, existing known various compound can be used.By the existence of carboxyl, resin combination can be made alkali-developable.In addition, from viewpoint flame-retardant curable resin composition of the present invention being made photo-curable, resistance to developability, preferably, except carboxyl, also there is ethylenical unsaturated double bonds in molecule, but also can only use do not have ethylenical unsaturated double bonds containing carboxy resin as (B-1) composition.(B-1) when the resin of composition does not have ethylenical unsaturated double bonds, in order to composition is made photo-curable, need to combinationally use in molecule the compound (photopolymerization monomer/oligomer) with more than one ethylenically unsaturated group.As ethylenical unsaturated double bonds, preferred source is from acrylic acid or methacrylic acid or their derivant.Above-mentioned (B-1) can be used alone one containing carboxy resin, also can combinationally use two or more.
As above-mentioned (B-1) object lesson containing carboxy resin, can list as described below containing in carboxy resin, there is the part-structure be selected from above-mentioned group containing carboxy resin.
(1) what obtained containing the copolymerization of unsaturated group compound by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methyl styrene, (methyl) lower alkyl acrylate, isobutylene etc. contains carboxy resin.
(2) aliphatic diisocyanate is passed through, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, the diisocyanate such as aromatic diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acids etc. are containing carboxyl diatomic alcohol compounds and polycarbonate-based polyvalent alcohol, polyethers system polyvalent alcohol, polyester-based polyols, polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide adds adult glycol, have the diol compounds such as the compound of phenolic hydroxyl group and alcohol hydroxyl group addition polymerization and obtain containing carboxyamino formate resin.
(3) aliphatic diisocyanate will be passed through, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, the diisocyanate cpds such as aromatic diisocyanate and polycarbonate-based polyvalent alcohol, polyethers system polyvalent alcohol, polyester-based polyols, polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide adds adult glycol, there is the addition polymerization of the diol compounds such as the compound of phenolic hydroxyl group and alcohol hydroxyl group and the end of carbamate resins that obtains and anhydride reaction and the end that formed containing carboxyamino formate resin.
(4) by (methyl) acrylate of 2 functional epoxy resins such as diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, di-first phenol-type epoxy resin, united phenol-type epoxy resin or the anhydride modified thing of its part, the photonasty that obtains containing the addition polymerization of carboxyl diatomic alcohol compounds and diol compound containing carboxyamino formate resin.
(5) by add in the synthesis of the resin of above-mentioned (2) or (4) compound in (methyl) dihydroxypropyl alkane ester equimolecular with a hydroxyl and more than one (methyl) acryloyl group and the end (methyl) obtained acrylated contain carboxyamino formate resin.
(6) by have in the reaction with same mole thing equimolecular that adds isophorone diisocyanate and pentaerythritol triacrylate in the synthesis of the resin of above-mentioned (2) or (4) isocyanate group and more than one (methyl) acryloyl group compound and obtain end (methyl) acrylated contain carboxyamino formate resin.
(7) multifunctional (solid-state) described later epoxy resin and (methyl) acrylic acid is made react, the dibasic acid anhydride such as addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride on the hydroxyl being present in side chain and the photonasty that obtains contains carboxy resin.
(8) with epichlorokydrin, 2 officials can reacts by the polyfunctional epoxy resin that obtains of the further epoxidation of hydroxyl of (solid-state) epoxy resin with (methyl) acrylic acid, the photonasty that the hydroxyl of generation and 2 yuan of acid anhydrides additions obtain contains carboxy resin.
(9) by making aftermentioned such multifunctional oxetane resin and dicarboxylic acid react, and make generated primary hydroxyl and dibasic acid anhydride carry out addition and obtain containing carboxyl polyester resin.
(10) reaction product obtained by making to have in 1 molecule the compound of multiple phenolic hydroxyl group and the reaction of the alkylene oxide such as oxirane, epoxypropane, with react containing unsaturated group monocarboxylic acid, and the reaction product of gained and multi-anhydride are reacted and are obtained contain carboxyl photoresist.
(11) reaction product obtained by making to have in 1 molecule the compound of multiple phenolic hydroxyl group and the reaction of the cyclic carbonate compound such as ethylene carbonate, propylene carbonate, with react containing unsaturated group monocarboxylic acid, and the reaction product of gained and multi-anhydride are reacted and are obtained contain carboxyl photoresist.
(12) make to have in 1 molecule the compound in 1 molecules such as the epoxy compound of multiple epoxy radicals and p-hydroxyphenylethanol with at least one alcohol hydroxyl group and a phenolic hydroxyl group and (methyl) acrylic acid etc. react containing unsaturated group monocarboxylic acid, the multi-anhydride such as the alcohol hydroxyl group of the reaction product obtained and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, adipic anhydride is reacted and obtain contain carboxyl photoresist.
(13) the further addition of compound an of epoxy radicals and more than one (methyl) acryloyl group will be had in any one resin in above-mentioned (1) ~ (12) and (methyl) glycidyl acrylate, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester equimolecular and the photonasty that obtains contains carboxy resin.
Above-mentioned containing in carboxy resin, from the viewpoint of the bending resistance folding endurance of the solidfied material obtained, the resin used in the synthesis of above-mentioned resin preferably has the resin of more than one the part-structure in the group being selected from and being made up of structure of bisphenol A, Bisphenol F structure, biphenol structural, xenol novolac structure, two xylenol structure, biphenyl novolac structure and carbamate structures or its plus hydrogenated compound namely containing carboxy resin.
In addition, have carbamate structures containing in carboxy resin, use isocyanate group not with the diisocyanate of phenyl ring Direct Bonding as having the composition (also comprising diisocyanate) of isocyanate group and obtain there is following feature containing carboxyamino formate resin: can not xanthochromia, effective to the covering power of substrate, and UVA is few, thus, excellent in resolution during formation alkali-developable composition is preferred.
Above-mentioned has multiple carboxyl, therefore, it is possible to utilize dilute alkaline aqueous solution to develop containing carboxy resin on the side chain of trunk polymer.
In addition, the above-mentioned acid number containing carboxy resin is preferably the scope of 20 ~ 200mgKOH/g, is more preferably the scope of 40 ~ 150mgKOH/g.During containing the acid number of carboxy resin less than 20mgKOH/g, sometimes become the adaptation that cannot obtain film or alkali development becomes difficulty.On the other hand, when acid number is more than 200mgKOH/g, the dissolving of developer solution to exposure portion can occur, the thin necessity or according to circumstances exposure portion and unexposed portion of must exceeding of line is indistinguishably peeled off by developing solution dissolution, sometimes the description of normal corrosion-resisting pattern becomes difficulty, therefore not preferred.
In addition, (B-1) that use in the present invention is different according to resin matrix containing the weight-average molecular weight of carboxy resin, is usually preferably the scope of 2000 ~ 150000, the more preferably scope of 5000 ~ 100000.During Weight-average molecular quantity not sufficient 2000, non-adhesion behavior is deteriorated sometimes, the moisture-proof of film after exposure is deteriorated, development time produce that film reduces, resolution is greatly deteriorated.On the other hand, when weight-average molecular weight is more than 150000, developability significantly worsens, and storage stability is deteriorated.
Convert in solid constituent, in flame-retardant curable resin composition, above-mentioned (B-1) is 5 ~ 60 quality % containing the compounding amount of carboxy resin, is preferably 10 ~ 60 quality %, is more preferably 20 ~ 60 quality %, is particularly preferably 30 ~ 50 quality %.When being less than above-mentioned scope, coating strength reduces, therefore not preferred.On the other hand, during more than above-mentioned scope, the viscosity of composition uprises or the reduction such as coating sometimes, therefore not preferred.
[(C) thermosetting component]
As (C) of the present invention thermosetting component, as long as the material of thermosetting component can be used as in hot curing resin composition, just known material can be used arbitrarily.As (C) thermosetting component, the known conventional heat-curing resin such as isocyanate compound, blocked isocyanate compounds, amino resins, maleimide compound, benzoxazine colophony, carbodiimide resin, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxetane compound, episulfide resin can be used.Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin, the compounding amount of above-mentioned (C) thermosetting component is preferably 5 ~ 120 mass parts, is more preferably 10 ~ 100 mass parts.During above-mentioned compounding quantity not sufficient 5 mass parts, poor heat resistance is sometimes not preferred.On the other hand, during more than 120 mass parts, developability reduces, therefore not preferred.
Among them, preferred thermosetting component is at least any one the thermosetting component had in 1 molecule in multiple cyclic ether group and cyclic thioether base (hereinafter referred to as ring-type (sulphur) ether).It is a lot of that these have the commercially available kind of the thermosetting component of ring-type (sulphur) ether, can give multifrequency nature by its structure.
The thermosetting component in above-mentioned molecule with multiple ring-type (sulphur) ether is the compound of any one or two kinds of groups had in molecule in the cyclic ether group of multiple 3,4 or 5 rings or cyclic thioether base, include, for example out in molecule the compound and episulfide resin etc. in the compound in the compound with multiple epoxy radicals and multi-functional epoxy compound, molecule with multiple oxetanylmethoxy and multifunctional oxetane compound, molecule with multiple thioether group.
As above-mentioned multi-functional epoxy compound, include, for example out the jER828 that Mitsubishi chemical Co., Ltd manufactures, jER834, jER1001, jER1004, the EPICLON840 that Dainippon Ink Chemicals manufactures, EPICLON850, EPICLON1050, EPICLON2055, the EPOTOHTOYD-011 that Toto Kasei KK manufactures, YD-013, YD-127, YD-128, the D.E.R.317 that Dow Chemical manufactures, D.E.R.331, D.E.R.661, D.E.R.664, the SumiepoxyESA-011 that Sumitomo Chemical Company Ltd manufactures, ESA-014, ELA-115, ELA-128, the A.E.R.330 that Asahi Chemical Industry Co., Ltd manufactures, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin, A.E.R.711, A.E.R.714 etc. (the being trade name) brominated epoxy resin that SumiepoxyESB-400, ESB-700 that the D.E.R.542 that EPOTOHTOYDB-400, YDB-500 that EPICLON152, EPICLON165 that the jERYL903 that Mitsubishi chemical Co., Ltd manufactures, Dainippon Ink Chemicals manufacture, Toto Kasei KK manufacture, Dow Chemical manufacture, Sumitomo Chemical Company Ltd manufacture, Asahi Chemical Industry Co., Ltd manufacture, the jER152 that Mitsubishi chemical Co., Ltd manufactures, jER154, the D.E.N.431 that Dow Chemical manufactures, D.E.N.438, the EPICLONN-730 that Dainippon Ink Chemicals manufactures, EPICLONN-770, EPICLONN-865, the EPOTOHTOYDCN-701 that Toto Kasei KK manufactures, YDCN-704, the EPPN-201 that Nippon Kayaku K. K manufactures, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, the SumiepoxyESCN-195X that Sumitomo Chemical Company Ltd manufactures, ESCN-220, the A.E.R.ECN-235 that Asahi Chemical Industry Co., Ltd manufactures, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin, EPOTOHTOYDF-170, YDF-175, YDF-2004 etc. (the being trade name) bisphenol f type epoxy resin that EPICLON830, Mitsubishi chemical Co., Ltd jER807 that Dainippon Ink Chemicals manufactures, Toto Kasei KK manufacture, the bisphenol-A epoxy resins such as EPOTOHTOST-2004, ST-2007, ST-3000 (trade name) that Toto Kasei KK manufactures, (the being trade name) glycidyl amine type epoxy resins such as the SumiepoxyELM-120 that the EPOTOHTOYH-434 that the jER604 that Mitsubishi chemical Co., Ltd manufactures, Toto Kasei KK manufacture, Sumitomo Chemical Company Ltd manufacture, hydantoins type epoxy resin, CELLOXIDE2021, CY179 etc. (the being trade name) alicyclic epoxy resin that Daisel chemical industry Co., Ltd manufactures, T.E.N., EPPN-501, EPPN-502 etc. (being trade name) three hydroxyphenyl methane type epoxy resin that the YL-933 that Mitsubishi chemical Co., Ltd manufactures, Dow Chemical manufacture, the di-cresols type such as YL-6056, YX-4000, YL-6121 (being trade name) that Mitsubishi chemical Co., Ltd manufactures or united phenol-type epoxy resin or their potpourri, the bisphenol-s epoxy resins such as the EXA-1514 (trade name) that the EPX-30 that EBPS-200, ADEKA company that Nippon Kayaku K. K manufactures manufactures, Dainippon Ink Chemicals manufacture, the bisphenol A novolac type epoxy resin such as the jER157S (trade name) that Mitsubishi chemical Co., Ltd manufactures, (being trade name) 2 such as the jERYL-931 that Mitsubishi chemical Co., Ltd manufactures, 2 ', 2 ' ', 2 ' ' '-[1,2-ethanetetrayl four (4,1-phenylene methylene oxygen)] tetraoxane type epoxy resin (tetraphenylolethanetypeepoxyresin), (being trade name) hetero ring type epoxy resin such as the TEPIC that Nissan Chemical Ind Ltd manufactures, the o-phthalic acid diglycidyl ester resins such as the BLEMMERDGT that Japan Oil Co manufactures, the four glycidyl group xylenol ethane resin such as the ZX-1063 that Toto Kasei KK manufactures, HP-4032, EXA-4750, EXA-4700 etc. that ESN-190, ESN-360 that Nippon Steel Chemical Co., Ltd manufactures, Dainippon Ink Chemicals manufacture are containing Naphthol-based Epoxy Resin, HP-7200, HP-7200H etc. that Dainippon Ink Chemicals manufactures have the epoxy resin of dicyclopentadiene skeleton, the tough epoxy resin of softness of EXA-4816, EXA-4822, EXA-4850 series, the glycidyl methacrylate copolymerization system epoxy resin such as CP-50S, CP-50M that Japan Oil Co manufactures, and the copolymerization epoxy resin etc. of N-cyclohexylmaleimide and glycidyl methacrylate, but be not limited to this.These epoxy resin can be used alone or are used in combination of two or more.Wherein, from the viewpoint of flexibility, be preferably the epoxy resin of 2 officials' energy.From the viewpoint of anti-flammability, particularly preferably biphenyl phenolic resin varnish type epoxy resin, di-first phenol-type epoxy resin or their potpourri.
As above-mentioned multifunctional oxetane compound, two [(3-methyl-3-oxetanylmethoxy methoxyl) methyl] ether can be listed, two [(3-ethyl-3-oxetanylmethoxy methoxyl) methyl] ether, 1, two [(3-methyl-3-oxetanylmethoxy methoxyl) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanylmethoxy methoxyl) methyl] benzene of 4-, (3-methyl-3-oxetanylmethoxy) methacrylate, (3-ethyl-3-oxetanylmethoxy) methacrylate, methacrylic acid (3-methyl-3-oxetanylmethoxy) methyl esters, methacrylic acid (3-ethyl-3-oxetanylmethoxy) methyl esters, the multifunctional oxetanes classes such as their oligomer or multipolymer, and oxetanes alcohol and novolac resin, poly-(4-Vinyl phenol), Cardo type bisphenols, calixarene kind, resorcinol calixarene kind, or silsesquioxane etc. has the etherate etc. of the resin of hydroxyl.In addition, the multipolymer etc. of unsaturated monomer and (methyl) alkyl acrylate with oxetanes ring can also be listed.
As the compound in above-mentioned molecule with multiple ring-type (sulphur) ether, include, for example out the YSLV-120TE etc. of the YL7000 (bisphenol A-type episulfide resin) of Mitsubishi chemical Co., Ltd's manufacture, Toto Kasei KK's manufacture.In addition, the episulfide resin etc. adopting same synthetic method the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin to be replaced to sulphur atom can also be used.
Relative to above-mentioned (B-1) carboxyl 1 equivalent containing carboxy resin, the compounding amount in above-mentioned molecule with the thermosetting component of multiple ring-type (sulphur) ether is preferably 0.3 ~ 2.5 equivalent, is more preferably the scope of 0.5 ~ 2.0 equivalent.When having compounding quantity not sufficient 0.3 equivalent of the thermosetting component of multiple ring-type (sulphur) ether in molecule, carboxyl remains in curing overlay film, the reduction such as thermotolerance, alkali resistance, electrical insulating property sometimes, therefore not preferred.On the other hand, during more than 2.5 equivalent, low-molecular-weight ring-type (sulphur) ether remains in dry coating, thus sometimes makes the reductions such as the intensity of curing overlay film, therefore not preferred.
When using in above-mentioned molecule the thermosetting component with multiple ring-type (sulphur) ether, preferably containing thermal curing catalyst.As this thermal curing catalyst, include, for example out the imdazole derivatives such as imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Dicyandiamide; Benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, the amines such as N-dimethyl benzyl amine; The hydrazide compound such as adipic dihydrazide, sebacic dihydrazide; The phosphorus compounds etc. such as triphenylphosphine.In addition, as commercially available product, include, for example out 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound) that Shikoku Chem manufactures, U-CAT (registered trademark) 3503N, U-CAT3502T (being the trade name of the blocked isocyanate compounds of dimethyl amine) that SAN-APRO Co., Ltd. manufactures, DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc.Be not particularly limited to these compounds, as long as the thermal curing catalyst of epoxy resin, the thermal curing catalyst of oxetane compound or promote the material of reaction of at least any one and carboxyl in epoxy radicals and oxetanyl, can be used alone or mix two or more use.In addition, also guanamines, methyl guanamines, benzoguanamine, melamine, 2 can be used, 4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid adduct, 2, the Striazine derivatives such as 4-diamido-6-methacryloxyethyl-s-triazine isocyanuric acid adduct, preferably combinationally use the compound also worked as adaptation imparting agent and above-mentioned thermal curing catalyst.
Convert in solid constituent, relative to thermosetting component 100 mass parts in molecule with multiple ring-type (sulphur) ether, the compounding amount of these thermal curing catalysts is preferably 0.1 ~ 20 mass parts, is more preferably 0.5 ~ 15.0 mass parts.
As above-mentioned amino resins, the amino resins such as melamine derivative, benzoguanamine derivant can be listed.Such as there are melamine methylol compound, methylolbenzoguanamine compound, methylol glycoluril compound and hydroxymethyl urea compound etc.And then the methylol of melamine methylol compound, methylolbenzoguanamine compound, methylol glycoluril compound and hydroxymethyl urea compound is transformed to alkoxy methyl and obtains by alkoxymethylated melamine compound, aikoxymethytated benzoguanamine compound, aikoxymethytated glycolurils compound and aikoxymethytated urea compounds respectively.To the kind of this alkoxy methyl, there is no particular limitation, such as, can be methoxy, ethoxyl methyl, propoxy methyl, butoxymethyl etc.Be particularly preferably the melamine derivative of less than 0.2% to human body, eco-friendly concentration of formaldehyde.
As the commercially available product of above-mentioned amino resins, include, for example out CYMEL300, with 301, with 303, with 370, with 325, with 327, with 701, with 266, with 267, with 238, with 1141, with 272, with 202, with 1156, with 1158, with 1123, with 1170, with 1174, same UFR65, same 300 (is MitsuiCyanamideCo. above, Ltd. manufacture), NIKALACMx-750, same Mx-032, same Mx-270, same Mx-280, same Mx-290, same Mx-706, same Mx-708, same Mx-40, same Mx-31, same Ms-11, same Mw-30, same Mw-30HM, same Mw-390, same Mw-100LM, same Mw-750LM (is SANWAChemicalCo. above, Ltd. manufacture) etc.
As above-mentioned isocyanate compound, the polyisocyanate compound with multiple isocyanate group can be used in molecule.As polyisocyanate compound, such as, can use aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.As the object lesson of aromatic polyisocyanate, can 4 be listed, 4 '-methyl diphenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, m xylene diisocyanate and 2,4-toluene diisocyanate dimer.As the object lesson of aliphatic polyisocyante, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate) and isophorone diisocyanate can be listed.As the object lesson of ester ring type polyisocyanates, bicycloheptane triisocyanate can be listed.And the adduct of above-named isocyanate compound, biuret body and isocyanuric acid ester body can be listed.
End-blocking isocyanate group contained in above-mentioned blocked isocyanate compounds is that isocyanate group is protected by the reaction with end-capping reagent, thus by the group of temporary transient passivation.When being heated to set point of temperature, this end-capping reagent dissociates, and generates isocyanate group.
As blocked isocyanate compounds, the addition reaction product of isocyanate compound and isocyanate-terminated dose can be used.As the isocyanate compound that can react with end-capping reagent, isocyanuric acid ester type, biuret type can be listed, add mould assembly etc.As the isocyanate compound for the synthesis of blocked isocyanate compounds, include, for example out aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.As the object lesson of aromatic polyisocyanate, aliphatic polyisocyante, ester ring type polyisocyanates, those compounds above-named can be listed.
As isocyanate-terminated dose, include, for example out the phenol system end-capping reagents such as phenol, cresols, xylenol, chlorophenol and ethyl-phenol; The lactams system end-capping reagents such as epsilon-caprolactams, δ-valerolactam, butyrolactam and azetidinone; Ethyl acetoacetate and diacetone isoreactivity methylene base system end-capping reagent; The alcohol system end-capping reagents such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl oxide, methyl glycollate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; The oxime system end-capping reagents such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, biacetyl monoxime, cyclohexanone-oxime; The mercaptan system end-capping reagents such as butanethiol, hexyl mercaptans, tert-butyl mercaptan, benzenethiol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol; The acid amides such as amide, benzamide system end-capping reagent; The imide series such as succimide and maleimide end-capping reagent; The amine system end-capping reagents such as xylidin, aniline, butylamine, dibutylamine; The imidazoles system end-capping reagents such as imidazoles, 2-ethyl imidazol(e); The imines system end-capping reagents etc. such as methylene imine and propylidene imines.
Blocked isocyanate compounds can be commercially available product, include, for example out SumidurBL-3175, BL-4165, BL-1100, BL-1265, DesmodurTPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, DESMOTHERM2170, DESMOTHERM2265 (above SumitomoBayerUrethaneCo., Ltd. manufacture, trade name), CORONATE2512, CORONATE2513, (above Nippon Polyurethane Industry Co., Ltd. manufactures CORONATE2520, trade name), B-830, B-815, B-846, B-870, B-874, (above Mitsui Takeda Chemical Co., Ltd manufactures B-882, trade name), TPA-B80E, 17B-60PX, (above Asahi Chemical Corp manufactures E402-B80T, trade name) etc.In addition, SumiduleBL-3175, BL-4265 use Methylethyl oxime to obtain as end-capping reagent.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin, the compounding amount of above-mentioned polyisocyanate compound or blocked isocyanate compounds is preferably 1 ~ 100 mass parts, is more preferably 2 ~ 70 mass parts.During above-mentioned compounding quantity not sufficient 1 mass parts, sometimes can not obtain the obdurability of sufficient film, be not preferred.On the other hand, during more than 100 mass parts, storage stability reduces sometimes, therefore not preferred.
In flame-retardant curable resin composition of the present invention, in order to promote the curing reaction of hydroxyl, carboxyl and isocyanate group, urethanation catalyst can be added.As urethanation catalyst, preferably use and be selected from by more than one the urethanation catalyst at least any one group formed in tin series catalysts, metal chloride, acetyl acetone salt, metal sulfate, amines and amine salt.
As above-mentioned tin series catalysts, include, for example out organo-tin compound, the inorganic tin compounds etc. such as stannous octoate (Stannousoctoate), dibutyl tin laurate.
As above-mentioned metal chloride, the chloride of the metal in the group being selected from and being made up of Cr, Mn, Co, Ni, Fe, Cu and Al can be listed, such as cobaltic chloride, Nickel Chloride, iron chloride etc.
Above-mentioned acetyl acetone salt is the acetylacetonate of the metal be selected from the group that is made up of Cr, Mn, Co, Ni, Fe, Cu and Al, include, for example out acetylacetone cobalt, nickel acetylacetonate, ferric acetyl acetonade etc.
As above-mentioned metal sulfate, the sulfate of the metal in the group being selected from and being made up of Cr, Mn, Co, Ni, Fe, Cu and Al can be listed, such as copper sulphate etc.
As above-mentioned amines, include, for example and have known triethylene diamine, N, N, N ', N '-tetramethyl-1,6-hexane diamine, two (2-dimethyl aminoethyl) ether, N, N, N ', N ", N " and-pentamethyl-diethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholine base diethyl ether, N-methylimidazole, dimethyl aminopyridine, triazine, N '-(2-hydroxyethyl)-N, N, N '-trimethyl-bis-(2-amino-ethyl) ether, N, N-Exxal8 amine, N, N-dimethyl amino ethoxy ethanol, N, N, N '-trimethyl-N '-(2-hydroxyethyl) ethylene diamine, N-(2-hydroxyethyl)-N, N ', N ", N " and-tetramethyl diethylenetriamine, N-(2-hydroxypropyl)-N, N ', N ", N " and-tetramethyl diethylenetriamine, N, N, N '-trimethyl-N '-(2-hydroxyethyl) propane diamine, N-methyl-N '-(2-hydroxyethyl) piperazine, two (N, N-dimethylaminopropyl) amine, two (N, N-dimethylaminopropyl) isopropanolamine, 2-amino quinine ring, 3-amino quinine ring, 4-amino quinine ring, 2-quinine cyclol, 3-quinine cyclol, 4-quinine cyclol, 1-(2 '-hydroxypropyl) imidazoles, 1-(2 '-hydroxypropyl)-glyoxal ethyline, 1-(2 '-hydroxyethyl) imidazoles, 1-(2 '-hydroxyethyl)-glyoxal ethyline, 1-(2 '-hydroxypropyl)-glyoxal ethyline, 1-(3 '-aminopropyl) imidazoles, 1-(3 '-aminopropyl)-glyoxal ethyline, 1-(3 '-hydroxypropyl) imidazoles, 1-(3 '-hydroxypropyl)-glyoxal ethyline, N, N-dimethylaminopropyl-N '-(2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ', N '-bis-(2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ', N '-bis-(2-hydroxypropyl) amine, N, N-dimethyl aminoethyl-N ', N '-bis-(2-hydroxyethyl) amine, N, N-dimethyl aminoethyl-N ', N '-bis-(2-hydroxypropyl) amine, in melamine and benzoguanamine at least any one etc.
As above-mentioned amine salt, include, for example out the amine salt etc. of the acylate systems such as DBU (1,8-diaza-dicyclo [5.4.0] undecylene-7).
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin, the compounding amount of above-mentioned urethanation catalyst is preferably 0.01 ~ 20 mass parts, is more preferably 0.5 ~ 10.0 mass parts.
[(D) Photoepolymerizationinitiater initiater]
Flame-retardant curable resin composition of the present invention comprises Photoepolymerizationinitiater initiater.As (D) Photoepolymerizationinitiater initiater; known Photoepolymerizationinitiater initiater can be used, such as, suitably can use more than one Photoepolymerizationinitiater initiaters in the group being selected from and being made up of the oxime ester system Photoepolymerizationinitiater initiater with oxime ester base, alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters.
As the commercially available product of oxime ester system Photoepolymerizationinitiater initiater, CGI-325, IRGACUREOXE01, IRGACUREOXE02 that BASFJAPANLTD. manufactures can be listed, N-1919, NCI-831 etc. that ADEKACorporation manufactures.In addition, the Photoepolymerizationinitiater initiater in molecule with two oxime ester bases also can be suitable for, and specifically, can list the oxime ester compound with carbazole structure shown in following general formula.
(in formula, X represents hydrogen atom, the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, phenyl, phenyl is (by the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, amino, alkyl amino or the dialkyl amido with the alkyl of carbon number 1 ~ 8 replace), naphthyl is (by the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, amino, alkyl amino or the dialkyl amido with the alkyl of carbon number 1 ~ 8 replace), Y, Z represents hydrogen atom respectively, the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, halogen group, phenyl, phenyl is (by the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, amino, alkyl amino or the dialkyl amido with the alkyl of carbon number 1 ~ 8 replace), naphthyl is (by the alkyl of carbon number 1 ~ 17, the alkoxy of carbon number 1 ~ 8, amino, alkyl amino or the dialkyl amido with the alkyl of carbon number 1 ~ 8 replace), anthryl, pyridine radicals, benzofuranyl (benzofuryl), benzothienyl (benzothienyl), Ar represents singly-bound, or the alkylidene of carbon number 1 ~ 10, ethenylidene, phenylene, diphenylene, sub-pyridine radicals (pyridylene), naphthylene, thienyl, anthrylene (anthrylene), sub-thienyl (thienylene), furylidene (furylene), 2,5-pyrroles-two base, 4,4 '-talan-two base, 4,2 '-styrene-two base, n represents the integer of 0 or 1.)
Particularly preferably be, in above-mentioned general formula, X, Y are respectively methyl or ethyl, and Z is methyl or phenyl, and n is 0, Ar is singly-bound or phenylene, naphthylene, thienyl or sub-thienyl.
In addition, as preferred carbazole oxime ester compound, the compound that can be represented by following general formula also can be listed.
(in formula, R 3the phenyl representing the alkyl of carbon number 1 ~ 4 or nitro, halogen atom or can be replaced by the alkyl of carbon number 1 ~ 4.
R 4the phenyl representing the alkyl of carbon number 1 ~ 4, the alkoxy of carbon number 1 ~ 4 or can be replaced by the alkyl of carbon number 1 ~ 4 or alkoxy.
R 5the alkyl of the carbon number 1 ~ 20 that expression can be substituted by phenyl, the benzyl that can be replaced by the alkoxy of carbon number 1 ~ 4, the alkyl of the carbon number 1 ~ 20 that wherein can be substituted by phenyl can be connected by oxygen atom or sulphur atom.
R 6represent the acyl group of nitro or X-C (=O)-shown.X represents the structure shown in aryl, thienyl, morpholinyl, thio-phenyl or following formula that can be replaced by the alkyl of carbon number 1 ~ 4.)
In addition, as preferred carbazole oxime ester compound, the carbazole oxime ester compound etc. of Japanese Unexamined Patent Publication 2004-359639 publication, Japanese Unexamined Patent Publication 2005-097141 publication, Japanese Unexamined Patent Publication 2005-220097 publication, Japanese Unexamined Patent Publication 2006-160634 publication, Japanese Unexamined Patent Publication 2008-094770 publication, Japanese Unexamined Patent Application Publication 2008-509967 publication, Japanese Unexamined Patent Application Publication 2009-040762 publication, the record of Japanese Unexamined Patent Publication 2011-80036 publication can be listed.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin, the compounding amount of this oxime ester system Photoepolymerizationinitiater initiater is preferably set to 0.01 ~ 5 mass parts.During less than 0.01 mass parts, photo-curable is not enough, and the coating characteristic such as chemical proofing reduces sometimes.On the other hand, during more than 5 mass parts, the light absorption of film coated surface is had to become violent, the tendency that deep curability reduces.Be more preferably 0.5 ~ 3 mass parts.
As alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, specifically, 2-methyl isophthalic acid-[4-(methyl thio) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino benzoylformaldoxime etc. can be listed.As commercially available product, IRGACURE907, IRGACURE369, IRGACURE379 etc. that BASFJAPANLTD. manufactures can be listed.
As acylphosphine oxide system Photoepolymerizationinitiater initiater; specifically can list 2; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide, two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-Dimethoxybenzoyl)-2; 4,4-trimethyl-pentyl phosphine oxide etc.As commercially available product, the IRGACURE819 etc. of LucirinTPO, BASFJAPANLTD. manufacture that BASFJAPANLTD. manufactures can be listed.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin, the compounding amount of these alpha-aminoacetophenone system Photoepolymerizationinitiater initiaters, acylphosphine oxide system Photoepolymerizationinitiater initiater is preferably 0.01 ~ 15 mass parts.During less than 0.01 mass parts, photo-curable is not enough, and the coating characteristic such as chemical proofing reduces sometimes.On the other hand, during more than 15 mass parts, degassed reduction effect cannot be obtained, and then have the light absorption of film coated surface to become violent, the tendency that deep curability reduces.Be more preferably 0.5 ~ 10 mass parts.
As two luxuriant titanium system Photoepolymerizationinitiater initiaters, specifically, two (cyclopentadienyl group)-two-phenyl-titanium, two (cyclopentadienyl group)-two-chloro-titanium, two (cyclopentadienyl group)-bis-(2 can be listed, 3,4,5,6-pentafluorophenyl group) titanium, two (cyclopentadienyl group)-bis-(the fluoro-3-of 2,6-bis-(pyrroles-1-base) phenyl) titanium etc.As commercially available product, the IRGACURE784 etc. that BASFJAPANLTD. manufactures can be listed.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin, uses compounding amount during above-mentioned two luxuriant titanium system Photoepolymerizationinitiater initiater to be preferably 0.05 ~ 2 mass parts, to be more preferably 0.05 ~ 1 mass parts.During less than 0.05 mass parts, the raising of deep curability cannot be confirmed.On the other hand, during more than 2 mass parts, there is the worry causing large halation, thus not preferred.More preferably 0.1 ~ 1 mass parts.
In addition, as Photoepolymerizationinitiater initiater, the IRGACURE389 that also can BASFJAPANLTD. be used aptly to manufacture.
Except above-mentioned Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, sensitizer can also be used.Be applicable to the Photoepolymerizationinitiater initiater used, light-initiated auxiliary agent and sensitizer as in flame-retardant curable resin composition of the present invention, benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketal compound, benzophenone cpd, tertiary amine compound and xanthone compound etc. can be listed.
As benzoin compound, such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether etc. specifically can be listed.
As acetophenone compound, specifically, include, for example out acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone etc.
As anthraquinone compounds, specifically, include, for example out 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone etc.
As thioxanthone compounds, specifically, include, for example out 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone etc.
As ketal compound, specifically, include, for example out acetophenone dimethyl ketal, benzil dimethyl ketal etc.
As benzophenone cpd; specifically, include, for example out benzophenone, 4-benzoyl diphenyl thioether, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4-benzoyl-4 '-ethyl diphenyl thioether, 4-benzoyl-4 '-propyl group diphenylsulfide etc.
As tertiary amine compound, specifically, include, for example out ethanolamine compound, there is the compound of dialkyl amido benzene structure, such as, commercially available product can list 4, 4 '-dimethylamino benzophenone (NISSOCUREMABP that Tso Tat Co., Ltd., Japan manufactures), 4, the dialkyl amido benzophenone such as 4 '-diethylamino benzophenone (EAB that hodogaya chemical Co., Ltd. manufactures), 7-(diethylamino)-4-methyl-2H-1-chromen-2-ones (7-(diethylamino)-4-methylcoumarin) etc. are containing the coumarin compound of dialkyl amido, EDMAB (KAYACUREEPA that Nippon Kayaku K. K manufactures), 2-dimethyl amino benzoate (QuantacureDMB that InternationalBiosyntheticsLtd. manufactures), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (QuantacureBEA that InternationalBiosyntheticsLtd. manufactures), ESCAROL 507 isopentyl ethyl ester (KAYACUREDMBI that Nippon Kayaku K. K manufactures), 4-dimethylaminobenzoic acid-2-Octyl Nitrite (Esolol507 that VanDyk company manufactures) etc.
In the middle of these, preferred thioxanthone compounds and tertiary amine compound.Especially from the aspect of deep curability, preferably thioxanthone compounds is comprised.Particularly preferably comprise the thioxanthone compounds such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone.
As the compounding amount of this thioxanthone compounds, convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin, is preferably below 20 mass parts.When the compounding amount of thioxanthone compounds is more than 20 mass parts, thick film curability reduces, and the cost of product can be caused to increase.Be more preferably below 10 mass parts.
In addition, as tertiary amine compound, preferably have the compound of dialkyl amido benzene structure, wherein, particularly preferably dialkyl amido benzophenone cpd, maximum absorption wavelength are in the coumarin compound containing dialkyl amido in the scope of 350 ~ 450nm and cumarin ketone.
As dialkyl amido benzophenone cpd, 4, the toxicity of 4 '-diethylamino benzophenone is low, therefore preferably.Maximum absorption wavelength due to the coumarin compound containing dialkyl amido is 350nm ~ 410nm, in ultraviolet range, therefore, can provide painted less, water white curing overlay film is mathematical, also can be provided in the color solidification overlay film of the color reflecting coloring pigment self when employing coloring pigment.Consider from the sensitization effect of the laser display excellence to wavelength 400 ~ 410nm, particularly preferably 7-(diethylamino)-4-methyl-2H-1-chromen-2-one.
As the compounding amount of this tertiary amine compound, convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin, is preferably 0.1 ~ 20 mass parts.When the compounding amount of tertiary amine compound is lower than 0.1 mass parts, there is the tendency that can not obtain sufficient sensitization effect.On the other hand, during more than 20 mass parts, because tertiary amine compound causes becoming strong in the light absorption of film coated surface, there is the tendency that deep curability reduces.Be more preferably 0.1 ~ 10 mass parts.
These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can be used alone one, also can use with the form of two or more potpourris.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin, the total amount of this Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer is preferably below 35 mass parts.During more than 35 mass parts, there is the tendency because their light absorption causes deep curability to reduce.
In addition, Photoepolymerizationinitiater initiater as above, light-initiated auxiliary agent and sensitizer are owing to absorbing specific wavelength, and therefore sensitivity step-down sometimes, can work as ultraviolet light absorber.But they not only use for the object of the sensitivity of raising composition.The light of specific wavelength can be absorbed as required, improve the photoreactivity on surface, make that the wire shaped of etchant resist and opening are changed to vertically, cone-shaped, reverse tapered shape, and the machining precision of live width, opening diameter can be improved.
Flame-retardant curable resin composition of the present invention can comprise following photopolymerization monomer/adjuvant such as oligomer, fire retardant.
< second embodiment >
Flame-retardant curable resin composition of the present invention contains: the phosphorus element-containing acrylate resin that at least any one and acrylate compounds in the phosphorus element-containing dicarboxylic acid shown in (A) following general formula (1) and acid anhydrides thereof react and obtain;
(in formula, R 1and R 2separately represent the alkyl of hydrogen atom or carbon number 1 ~ 6, m and n separately represents the integer of 0 ~ 4, and dotted line represents that two carboxyls also can form acid anhydrides.)
(B) containing carboxy resin;
(C-1) there is the epoxy resin of biphenyl novolac structure; With
(D) Photoepolymerizationinitiater initiater.
Be there is by compounding above-mentioned (A) phosphorus element-containing acrylate resin and above-mentioned (C-1) epoxy resin of biphenyl novolac structure, halogen-free composition can be obtained and carrying capacity of environment is few and anti-flammability, flexibility, low warpage properties excellent, high temperature compacting time the anti-flammability overlay film that oozes out without fire retardant.
Below each composition is described in detail.
[(A) phosphorus element-containing acrylate resin]
(A) phosphorus element-containing acrylate resin used in the present invention as previously mentioned.Wherein, for compounding amount, except (B-1) is replaced to (B) containing carboxy resin containing carboxy resin, other is constant.In addition, in the present invention, phosphorus element-containing acrylate resin be 2 officials can phosphorus element-containing acrylate, being not only preferred from the viewpoint of flexibility, and is also preferred from the viewpoint of low warpage properties.
[(B) is containing carboxy resin]
As (B) that use in the present invention containing carboxy resin, the known resin containing carboxyl can be used.By the existence of carboxyl, resin combination can be made alkali-developable.In addition, from viewpoint flame-retardant curable resin composition of the present invention being made photo-curable, resistance to developability, preferably, except carboxyl, also there is ethylenical unsaturated double bonds in molecule, but also can only use do not have ethylenical unsaturated double bonds containing carboxy resin as (B) composition.(B) when the resin of composition does not have ethylenical unsaturated double bonds, in order to composition is made photo-curable, need to combinationally use in molecule the compound (photopolymerization monomer/oligomer) with more than one ethylenically unsaturated group.As ethylenical unsaturated double bonds, preferred source is from acrylic acid or methacrylic acid or their derivant.Above-mentioned (B) can be used alone one containing carboxy resin, also can combinationally use two or more.
As may be used for flame-retardant curable resin composition of the present invention containing the object lesson of carboxy resin, the following such compound (can be in oligomer and polymkeric substance any one) enumerated can be provided.
(1) what obtained containing the copolymerization of unsaturated group compound by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methyl styrene, (methyl) lower alkyl acrylate, isobutylene etc. contains carboxy resin.
(2) aliphatic diisocyanate is passed through, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, the diisocyanate such as aromatic diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acids etc. are containing carboxyl diatomic alcohol compounds and polycarbonate-based polyvalent alcohol, polyethers system polyvalent alcohol, polyester-based polyols, polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide adds adult glycol, have the diol compounds such as the compound of phenolic hydroxyl group and alcohol hydroxyl group addition polymerization and obtain containing carboxyamino formate resin.
(3) make to pass through aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, the diisocyanate cpds such as aromatic diisocyanate and polycarbonate-based polyvalent alcohol, polyethers system polyvalent alcohol, polyester-based polyols, polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide adds adult glycol, there is the addition polymerization of the diol compounds such as the compound of phenolic hydroxyl group and alcohol hydroxyl group and the end of carbamate resins that obtains and anhydride reaction and the end that formed containing carboxyamino formate resin.
(4) by (methyl) acrylate of 2 functional epoxy resins such as diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, di-first phenol-type epoxy resin, united phenol-type epoxy resin or the anhydride modified thing of its part, the photonasty that obtains containing the addition polymerization of carboxylic diol compound and diatomic alcohol compounds containing carboxyamino formate resin.
(5) by add in the synthesis of the resin of above-mentioned (2) or (4) compound in (methyl) dihydroxypropyl alkane ester equimolecular with a hydroxyl and more than one (methyl) acryloyl group and the end (methyl) obtained acrylated contain carboxyamino formate resin.
(6) by have in the reaction with same mole thing equimolecular that adds isophorone diisocyanate and pentaerythritol triacrylate in the synthesis of the resin of above-mentioned (2) or (4) isocyanate group and more than one (methyl) acryloyl group compound and obtain end (methyl) acrylated contain carboxyamino formate resin.
(7) multifunctional (solid-state) described later epoxy resin and (methyl) acrylic acid is made react, the dibasic acid anhydride such as addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride on the hydroxyl being present in side chain and the photonasty that obtains contains carboxy resin.
(8) with epichlorokydrin, 2 officials can reacts by the polyfunctional epoxy resin that obtains of the further epoxidation of hydroxyl of (solid-state) epoxy resin with (methyl) acrylic acid, the photonasty that the hydroxyl of generation and 2 yuan of acid anhydrides additions obtain contains carboxy resin.
(9) by making aftermentioned such multifunctional oxetane resin and dicarboxylic acid react, and make generated primary hydroxyl and dibasic acid anhydride carry out addition and obtain containing carboxyl polyester resin.
(10) reaction product obtained by making to have in 1 molecule the compound of multiple phenolic hydroxyl group and the reaction of the alkylene oxide such as oxirane, epoxypropane, with react containing unsaturated group monocarboxylic acid, and the reaction product of gained and multi-anhydride are reacted and are obtained contain carboxyl photoresist.
(11) reaction product obtained by making to have in 1 molecule the compound of multiple phenolic hydroxyl group and the reaction of the cyclic carbonate compound such as ethylene carbonate, propylene carbonate, with react containing unsaturated group monocarboxylic acid, and the reaction product of gained and multi-anhydride are reacted and are obtained contain carboxyl photoresist.
(12) make to have in 1 molecule the compound in 1 molecules such as the epoxy compound of multiple epoxy radicals and p-hydroxyphenylethanol with at least one alcohol hydroxyl group and a phenolic hydroxyl group and (methyl) acrylic acid etc. react containing unsaturated group monocarboxylic acid, the multi-anhydride such as the alcohol hydroxyl group of the reaction product obtained and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, adipic anhydride is reacted and obtain contain carboxyl photoresist.
(13) the further addition of compound an of epoxy radicals and more than one (methyl) acryloyl group will be had in any one resin in above-mentioned (1) ~ (12) and (methyl) glycidyl acrylate, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester equimolecular and the photonasty that obtains contains carboxy resin.
Above-mentioned has multiple carboxyl, therefore, it is possible to utilize dilute alkaline aqueous solution to develop containing carboxy resin on the side chain of trunk polymer.
In addition, the above-mentioned acid number containing carboxy resin is preferably the scope of 20 ~ 200mgKOH/g, is more preferably the scope of 40 ~ 150mgKOH/g.During containing the acid number of carboxy resin less than 20mgKOH/g, sometimes become the adaptation that cannot obtain film or alkali development becomes difficulty.On the other hand, when acid number is more than 200mgKOH/g, the dissolving of developer solution to exposure portion can be there is, thus, the thin necessity or according to circumstances exposure portion and unexposed portion of must exceeding of line is indistinguishably peeled off by developing solution dissolution, and the description of normal corrosion-resisting pattern becomes difficulty, therefore not preferred.
In addition, (B) that use in the present invention is different according to resin matrix containing the weight-average molecular weight of carboxy resin, be usually preferably the scope of 2000 ~ 150000, more preferably 5000 ~ 100000 scope.During Weight-average molecular quantity not sufficient 2000, non-adhesion behavior is deteriorated sometimes, the moisture-proof of film after exposure is deteriorated, development time produce that film reduces, resolution is greatly deteriorated.On the other hand, when weight-average molecular weight is more than 150000, developability significantly deterioration sometimes, storage stability are deteriorated.
Above-mentioned containing in carboxy resin, from the viewpoint of the low warpage of the solidfied material obtained, bending resistance folding endurance, the resin used in the synthesis of above-mentioned resin preferably has the resin of more than one the part-structure in the group being selected from and being made up of structure of bisphenol A, Bisphenol F structure, biphenol structural, xenol novolac structure, two xylenol structure, biphenyl novolac structure and carbamate structures or its plus hydrogenated compound namely containing carboxy resin.
In addition, have carbamate structures containing in carboxy resin, use isocyanate group not with the diisocyanate of phenyl ring Direct Bonding as having the composition (also comprising diisocyanate) of isocyanate group and obtain there is following feature containing carboxyamino formate resin: can not xanthochromia, effective to the covering power of substrate, and UVA is few, thus, excellent in resolution during formation alkali-developable composition is preferred.
Convert in solid constituent, in flame-retardant curable resin composition, above-mentioned (B) is 5 ~ 60 quality % containing the compounding amount of carboxy resin, is preferably 10 ~ 60 quality %, is more preferably 20 ~ 60 quality %, is particularly preferably 30 ~ 50 quality %.When being less than above-mentioned scope, coating strength reduces, therefore not preferred.On the other hand, during more than above-mentioned scope, the viscosity of composition uprises or the reduction such as coating sometimes, therefore not preferred.
[(C-1) has the epoxy resin of biphenyl novolac structure]
In the present invention, by having the epoxy resin of biphenyl novolac structure containing (C-1), low warpage properties, anti-flammability can be improved.There is as (C-1) epoxy resin of biphenyl novolac structure, the existing known various epoxy compound with biphenyl novolac structure and epoxy radicals can be used in molecule.As commercially available product, NC-3000-L, NC-3000, NC-3000-H, NC-3100 etc. that Nippon Kayaku K. K manufactures can be listed.The epoxy resin that above-mentioned (C-1) has biphenyl novolac structure can be used alone one, also can combinationally use two or more.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B) is containing carboxy resin, the compounding amount that above-mentioned (C-1) has the epoxy resin of biphenyl novolac structure is more than 5 mass parts and is desirable below 100 mass parts, is preferably more than 10 mass parts and ratio below 70 mass parts.During less than 5 mass parts, sufficient anti-flammability cannot be given, thus not preferred.On the other hand, during more than 100 mass parts, low warpage properties, flexible reduction, thus not preferred.
In addition, in order to improve thermotolerance further, flame-retardant curable resin composition of the present invention also can combinationally use other thermosetting component except the epoxy resin that above-mentioned (C-1) has biphenyl novolac structure.As thermosetting component, the known conventional heat-curing resin such as isocyanate compound, blocked isocyanate compounds, amino resins, maleimide compound, benzoxazine colophony, carbodiimide resin, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxetane compound, episulfide resin can be used.Among them, preferred thermosetting component is at least any one the thermosetting component had in 1 molecule in multiple cyclic ether group and cyclic thioether base (hereinafter referred to as ring-type (sulphur) ether).It is a lot of that these have the commercially available kind of the thermosetting component of ring-type (sulphur) ether, can give multifrequency nature by its structure.
The thermosetting component in above-mentioned molecule with multiple ring-type (sulphur) ether is the compound of any one or two kinds of groups had in molecule in the cyclic ether group of multiple 3,4 or 5 rings or cyclic thioether base, include, for example out in molecule the compound and episulfide resin etc. in the compound in the compound with multiple epoxy radicals and multi-functional epoxy compound, molecule with multiple oxetanylmethoxy and multifunctional oxetane compound, molecule with multiple thioether group.
The example of above-mentioned multi-functional epoxy compound and commercially available product thereof as previously mentioned.
When using other epoxy resin except there is the epoxy resin of biphenyl novolac structure, from viewpoint that is flexible, low warpage properties, the preferably epoxy resin of 2 officials' energy, and then, from the viewpoint of low warpage, the preferred powdered epoxy resin of epoxy resin of 2 officials' energy.
The example of above-mentioned multifunctional oxetane compound as previously mentioned.
There is the example of the episulfide resin of multiple ring-type (sulphur) ether and commercially available product thereof as previously mentioned in above-mentioned molecule.
Relative to above-mentioned (B) carboxyl 1 equivalent containing carboxy resin, the compounding amount in above-mentioned molecule with the thermosetting component of multiple ring-type (sulphur) ether is preferably 0.3 ~ 2.5 equivalent, is more preferably the scope of 0.5 ~ 2.0 equivalent.When having compounding quantity not sufficient 0.3 equivalent of the thermosetting component of multiple ring-type (sulphur) ether in molecule, carboxyl remains in curing overlay film, the reductions such as thermotolerance, alkali resistance, electrical insulating property, therefore not preferred.On the other hand, during more than 2.5 equivalent, low-molecular-weight ring-type (sulphur) ether remains in dry coating, thus sometimes makes the reductions such as the intensity of curing overlay film, therefore not preferred.
When using in above-mentioned molecule the thermosetting component with multiple ring-type (sulphur) ether, preferably containing thermal curing catalyst.The example of this thermal curing catalyst and commercially available product thereof as previously mentioned.Preferably the compound also worked as adaptation imparting agent and described thermal curing catalyst are combinationally used.
Convert in solid constituent, relative to thermosetting component 100 mass parts in molecule with multiple ring-type (sulphur) ether, the compounding amount of these thermal curing catalysts is preferably 0.1 ~ 20 mass parts, is more preferably 0.5 ~ 15.0 mass parts.
The example of above-mentioned amino resins as previously mentioned.Be particularly preferably the melamine derivative of less than 0.2% to human body, eco-friendly concentration of formaldehyde.
The example of the commercially available product of above-mentioned amino resins as previously mentioned.
The example of above-mentioned isocyanate compound as previously mentioned.
End-blocking isocyanate group contained in above-mentioned blocked isocyanate compounds is that isocyanate group is protected by the reaction with end-capping reagent, thus by the group of temporary transient passivation.When being heated to set point of temperature, this end-capping reagent dissociates, and generates isocyanate group.
As blocked isocyanate compounds, the addition reaction product of isocyanate compound and isocyanate-terminated dose can be used.As the isocyanate compound that can react with end-capping reagent, isocyanuric acid ester type, biuret type can be listed, add mould assembly etc.For the synthesis of the isocyanate compound of blocked isocyanate compounds example as previously mentioned.
The example of isocyanate-terminated dose as previously mentioned.
Blocked isocyanate compounds also can be commercially available product, and its example as previously mentioned.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B), containing carboxy resin, the compounding amount of above-mentioned polyisocyanate compound or blocked isocyanate compounds is preferably 1 ~ 100 mass parts, is more preferably 2 ~ 70 mass parts.During above-mentioned compounding quantity not sufficient 1 mass parts, sometimes can not obtain the obdurability of sufficient film, be not preferred.On the other hand, during more than 100 mass parts, storage stability reduces sometimes, therefore not preferred.
In flame-retardant curable resin composition of the present invention, in order to promote the curing reaction of hydroxyl, carboxyl and isocyanate group, urethanation catalyst can be added.As urethanation catalyst, preferably use more than one the urethanation catalyst be selected from the group be made up of at least one in tin series catalysts, metal chloride, acetyl acetone salt, metal sulfate, amines and amine salt.
The example of above-mentioned tin series catalysts as previously mentioned.
The example of above-mentioned slaine compound as previously mentioned.
Above-mentioned acetyl acetone salt is the acetylacetonate of the metal be selected from the group that is made up of Cr, Mn, Co, Ni, Fe, Cu and Al, and its example as previously mentioned.
As above-mentioned metal sulfate, can list the sulfate of the metal in the group being selected from and being made up of Cr, Mn, Co, Ni, Fe, Cu and Al, its example as previously mentioned.
The example of above-mentioned amines as previously mentioned.
The example of above-mentioned amine salt as previously mentioned.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B), containing carboxy resin, the compounding amount of above-mentioned urethanation catalyst is preferably 0.01 ~ 20 mass parts, is more preferably 0.5 ~ 10.0 mass parts.
[(D) Photoepolymerizationinitiater initiater]
(D) Photoepolymerizationinitiater initiater used in the present invention as previously mentioned.Except (D) Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, sensitizer can also be used.Light-initiated auxiliary agent, sensitizer are as previously mentioned.For compounding amount, except (B-1) is replaced with (B) containing carboxy resin containing carboxy resin, other is constant.
Flame-retardant curable resin composition of the present invention can comprise following photopolymerization monomer/adjuvant such as oligomer, fire retardant.
(photopolymerization monomer/oligomer)
Hardening resin composition of the present invention can compounding photopolymerization monomer/oligomer.As photopolymerization monomer/oligomer, the compound in conventional known molecule with more than one ethylenically unsaturated group can be listed, specifically, polyester (methyl) acrylate, polyethers (methyl) acrylate, carbamate (methyl) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate etc. can be listed.More specifically, the hydroxyalkyl acrylates classes such as acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate can be listed; The diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; The acrylic amides such as N,N-DMAA, N hydroxymethyl acrylamide, N, N-dimethylaminopropylacryl acid amides; The acrylate classes such as acrylic acid-N, N-dimethylamino ethyl ester, acrylic acid-N, N-dimethylamino propyl ester; The multicomponent methacrylate classes such as the polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, three-hydroxyethyl isocyanuric acid ester or their ethylene oxide adduct, propylene oxide adduct or 6-caprolactone addition product; The multicomponent methacrylate classes such as the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenols or propylene oxide adduct; The multicomponent methacrylate class of the glycidol ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; Be not limited to above-mentioned, also can list by the direct acroleic acid esterifications of polyvalent alcohol such as polyether glycol, PCDL, C-terminal polybutadiene, polyester polyol or the esters of acrylic acid carrying out urethane acrylate by diisocyanate and obtain and melamine acrylate and each methyl acrylic ester corresponding to aforesaid propylene acid esters at least any one etc.
And then, also can combinationally use the photopolymerization monomer/oligomer such as the Epocryl that the polyfunctional epoxy resins such as cresol novolak type epoxy resin and acrylic acid reacts and obtain and then the epoxy amino formic ether acrylate compounds hydroxyl of this Epocryl being reacted with half carbamate compounds formed by diisocyanate such as hydroxy acrylate and isophorone diisocyanate such as pentaerythritol triacrylates and obtains.Such epoxy acrylate system resin, compound can improve photo-curable and not reduce dry to touch.
In the present invention, the particularly preferably multicomponent methacrylate class such as ethylene oxide adduct or propylene oxide adduct of the multicomponent methacrylate class such as polyvalent alcohol or their ethylene oxide adduct, propylene oxide adduct or 6-caprolactone addition product, phenols, further preferably containing the oligourethane class of (methyl) acrylate, from viewpoint that is flexible or low warpage properties, photopolymerization monomer/oligomer more preferably 2 official's energy of use.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin or (B) containing carboxy resin, the compounding amount of above-mentioned photopolymerization monomer/oligomer is preferably 5 ~ 100 mass parts, is more preferably the ratio of 5 ~ 70 mass parts.During above-mentioned compounding quantity not sufficient 5 mass parts, photo-curable reduces, and is sometimes difficult to form pattern by the postradiation alkali development of active energy beam, therefore not preferred.On the other hand, during more than 100 mass parts, reduce relative to the dissolubility of aqueous alkali, film becomes fragile sometimes, therefore not preferred.
(fire retardant)
In order to improve anti-flammability, flame-retardant curable resin composition of the present invention can also comprise the fire retardants such as phosphorus-containing compound.
(phosphorus-containing compound)
As above-mentioned phosphorus-containing compound, conventional known material can be used, include, for example out phosphate and condensed phosphoric acid esters, cyclic phosphazene compound, Phosphazene oligomers, metal phosphinate, the compound shown in following general formula.
In formula, R 7, R 8and R 9separately represent the substituting group except halogen atom.
In above-mentioned general formula, R 7, R 8be preferably the alkyl of hydrogen atom or carbon number 1 ~ 4, R 9be preferably hydrogen atom, the alkyl of carbon number 1 ~ 4 that can be replaced by cyano group, 2,5-dihydroxy phenyls or 3,5-, bis--tert-butyl-hydroxy phenyl.
As the commercially available product of the phosphorus-containing compound shown in above-mentioned general formula, there are HCA, SANKO-220, M-ESTER, HCA-HQ (being the trade name that Sanko Co., Ltd. manufactures) etc.
R in above-mentioned general formula 7and R 8for hydrogen atom and R 9compound for (methyl) acrylate derivative is also preferred.This compound synthesizes by the Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and known usual multifunctional (methyl) acrylate monomer usually.
As above-mentioned known conventional (methyl) acrylate monomer, the diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol can be listed; The multicomponent methacrylate classes such as the polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, three-hydroxyethyl isocyanuric acid ester or their ethylene oxide adduct, propylene oxide adduct or caprolactone addition product; The multicomponent methacrylate classes such as the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenols or propylene oxide adduct; With the multicomponent methacrylate class of the glycidol ether such as urethane acrylate class, glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester of above-mentioned polyalcohols; With in melamine acrylate and each methyl acrylic ester corresponding to aforesaid propylene acid esters at least any one etc.
Hydrophobicity, the thermotolerance with the phosphorus-containing compound of phenolic hydroxyl group are high, and will electrical characteristics be caused to reduce because of hydrolysis, resistance to soldering heat performance be high.In addition, as the combination be applicable to, when employing the epoxy resin in heat-curing resin, due to epoxy reaction and entered in network by group, therefore can obtain the advantage can not oozed out after hardening.As commercially available product, there is the HCA-HQ etc. that Sanko Co., Ltd. manufactures.
The reduction of the bending caused by the impact of alkyl chain as the phosphorus-containing compound of oligomer or polymkeric substance is few, and molecular weight is large, therefore can obtain the advantage can not oozed out after hardening.As commercially available product, the M-Ester-HP having Sanko Co., Ltd. to manufacture, Japan spin the phosphorous Vylon337 etc. that Co., Ltd. manufactures.
As Phosphazene oligomers, phenoxy phosphazene compound is effective, has the ring of substituted or unsubstituted phenoxy phosphazene oligomer or tripolymer, the tetramer, pentamer, and liquid, pressed powder is all applicable to using.As commercially available product, there are FP-100, FP-300, FP-390 etc. of lying prostrate and seeing manufactured by pharmacy.Wherein, the phenoxy phosphazene oligomer replaced by alkyl or hydroxyl, cyano group isopolarity group, high containing the dissolubility in carboxy resin, even if add in a large number, does not have the bad phenomenon such as recrystallization, therefore preferably yet.
By using metal phosphinate, can anti-flammability be improved and not lose the flexibility of cured coating film.In addition, by using the metal phosphinate of excellent heat resistance, oozing out of the fire retardant under hot pressing when encapsulating can be suppressed.As commercially available product, EXOLITOP930, EXOLITOP935 etc. that Clariant (Japan) K.K. manufactures can be listed.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin or (B) containing carboxy resin, the compounding amount of above-mentioned phosphorus-containing compound is preferably the scope of 1 ~ 40 mass parts, is particularly preferably 5 ~ 30 mass parts.More than 40 mass parts ground a large amount of compounding time, fully can obtain anti-flammability, but sometimes produce and ooze out, therefore not preferred.
(colorant)
Hardening resin composition of the present invention can compounding colorant.As colorant, can use the known usual colorants such as red, blue, green, yellow, can be any one in pigment, dyestuff, pigment.Specifically, can list with Colour Index (COLOURINDEX as described below; C.I.; TheSocietyofDyersandColourists issues) material of numbering.But, from the viewpoint of reduction carrying capacity of environment and the impact on human body, preferably not halogen-containing colorant.
Red stain:
As red stain, there are monoazo system, bisdiazo system, azo lake system, benzimidazolone Xi, perylene system, diketopyrrolopyrrolecocrystals system, condensation azo system, anthraquinone system, quinacridone etc., particularly, following material can be listed.
Monoazo system: paratonere 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269.
Bisdiazo system: pigment red 37,38,41.
Monoazo color lake is: pigment red 4 8:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1,58:4,63:1,63:2,64:1,68.
Benzimidazolone system: paratonere 171, paratonere 175, paratonere 176, paratonere 185, paratonere 208.
Perylene system: solvent of red 135, solvent red 179, pigment red 123, pigment red 149, paratonere 166, paratonere 178, pigment red179, paratonere 190, paratonere 194, paratonere 224.
Diketopyrrolopyrrolecocrystals system: paratonere 254, paratonere 255, paratonere 264, paratonere 270, paratonere 272.
Condensation azo system: paratonere 220, paratonere 144, paratonere 166, pigment red 21 4, paratonere 220, paratonere 221, paratonere 242.
Anthraquinone system: paratonere 168, paratonere 177, pigment red 21 6, solvent red 149, solvent red 150, solvent red 52, solvent red 207.
Quinacridone: pigment red 122, paratonere 202, paratonere 206, Pigment Red 207, paratonere 209.
Blue colorant:
As blue colorant, there are phthalocyanine system, anthraquinone system, pigment system is the compound being classified as pigment (pigment), specifically, pigment blue 15, pigment blue 15 can be listed: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 16, pigment blue 60.
As dyestuff system, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc. can be used.In addition to the foregoing, metal can also be used to replace or unsubstituted phthalocyanine compound.
Green colourant:
As green colourant, have phthalocyanine system, anthraquinone Xi, perylene system equally, specifically, can use that pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc.In addition to the foregoing, metal can also be used to replace or unsubstituted phthalocyanine compound.
Yellow colorants:
As yellow colorants, there are monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc., specifically, following material can be listed.
Anthraquinone system: solvent yellow 16 3, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202.
Isoindolinone system: pigment yellow 110, pigment yellow 109, pigment yellow 13 9, pigment yellow 17 9, pigment yellow 185.
Condensation azo system: pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment Yellow 12 8, pigment yellow 155, pigment yellow 166, pigment yellow 180.
Benzimidazolone system: pigment Yellow 12 0, pigment yellow 151, pigment yellow 154, pigment yellow 156, pigment yellow 17 5, pigment yellow 181.
Monoazo system: pigment yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183.
Bisdiazo system: pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198.
In addition, in order to adjust tone, purple, orange, brown, black etc. colorant can be added.
As object lesson, there is pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73, C.I. pigment brown 23, C.I. pigment brown 25, C.I. pigment black 1, C.I. pigment black 7 etc.
Colorant as above can be suitably compounding, compounding amount is not particularly limited, convert in solid constituent, above-mentioned relative to 100 mass parts (B-1) containing carboxy resin or (B) containing carboxy resin, be sufficient below compounding 10 mass parts, be preferably 0.1 ~ 5 mass parts.
(filler)
Flame-retardant curable resin composition of the present invention, can compounding filler as required in order to improve the physical strength etc. of the solidfied material obtained.As such filler, known usual inorganic or organic filler can be used, especially preferably use barium sulphate, preparing spherical SiO 2 and talcum.In addition, in order to give anti-flammability, also aluminium hydroxide, magnesium hydroxide, boehmite etc. can be used.In addition, NANOPOX (trade name) XP0516, XP0525, XP0314 (being the trade name of product) that NANOCRYL (trade name) XP0396, XP0596, XP0733, XP0746, XP0765, XP0768, XP0953, XP0954, the XP1045 (being the trade name of product) that the Hanse-Chemie company being dispersed with nano silicon in the compound with more than one ethylenically unsaturated group, above-mentioned polyfunctional epoxy resin can also be used to manufacture, Hanse-Chemie company manufacture.They can be used alone or compounding two or more.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin or (B) containing carboxy resin, the compounding amount of above-mentioned filler is preferably below 500 mass parts, is more preferably 0.1 ~ 300 mass parts, is particularly preferably 0.1 ~ 150 mass parts.When the compounding amount of filler is more than 500 mass parts, the viscosity of hardening resin composition uprises sometimes, and printing reduction sometimes, solidfied material become fragile, therefore not preferred.
(binder polymer)
In order to improve flexibility, the dry to touch of the solidfied material obtained, conventional known binder polymer in flame-retardant curable resin composition of the present invention, can be used.As binder polymer, optimum fiber prime system, Polyester, phenoxy resin based polymer.As cellulose-based polymkeric substance, cellulose acetate-butyrate (CAB), cellulose-acetate propionate (CAP) series that Eastman company manufactures can be listed, as Polyester polymkeric substance, the VYLON series that Co., Ltd. manufactures is spun by preferred Japan, as phenoxy resin based polymer, the phenoxy resin of preferred bisphenol-A, Bisphenol F and their plus hydrogenated compound.
Convert in solid constituent, above-mentioned relative to 100 mass parts (B-1), containing carboxy resin or (B) containing carboxy resin, the compounding amount of above-mentioned binder polymer is preferably below 50 mass parts, is more preferably 1 ~ 30 mass parts, is particularly preferably 5 ~ 30 mass parts.When the compounding amount of binder polymer is more than 50 mass parts, the alkali-developable of hardening resin composition is poor, and the mission life sometimes can developed shortens, therefore not preferred.
(elastic body)
In order to give flexibility to the solidfied material obtained, improve the fragility etc. of solidfied material, flame-retardant curable resin composition of the present invention can compounding elastic body.As elastic body, include, for example out polyester-based elastomer, polyurethane series elastic body, polyester urethane based elastomers, polyamide-based elastic body, polyesteramide based elastomers, acrylic elastomer, ethylene series elastic body.In addition, the resin etc. carrying out modification by the epoxy radicals of part or all of two terminal carboxylic's modified version butadiene-propylene nitrile rubbers to the epoxy resin with various skeleton can also be used.And then, the polybutadiene based elastomers containing epoxy radicals, the polybutadiene based elastomers containing acryloyl group, the polybutadiene based elastomers of hydroxyl, the isoprene based elastomers etc. of hydroxyl can be used.Elastic body can be used alone one, also can use with the form of two or more potpourris.
(closely sealed promoter)
In order to improve the adaptation of interlayer or improve the adaptation of photo-sensitive resin and base material, in flame-retardant curable resin composition of the present invention, closely sealed promoter can be used.As closely sealed promoter, such as, there are benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thioketones, 5-amino-3-morpholinomethyl-thiazole-2-thioketones, 2-sulfydryl-5-methyl thio-thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, containing amino benzotriazole, silane coupling agent etc.
(antioxidant)
Often will there is oxidative degradation in rapid succession once oxidation in macromolecular material, the function of macromolecule raw material is caused to reduce, therefore, in order to anti-oxidation, can add in flame-retardant curable resin composition of the present invention (1) make the radical scavenger of the free radical ineffective treatment of generation and (2) make in the superoxide of generation at least any one is decomposed into harmless material, does not produce the antioxidants such as the peroxide decomposer of new free radical.Antioxidant can be used alone one, also can be used in combination of two or more.
(ultraviolet light absorber)
Macromolecular material absorbs light, occur thus to decompose deterioration, therefore, in order to carry out ultraviolet stabilization countermeasure, except above-mentioned antioxidant, can use ultraviolet light absorber in flame-retardant curable resin composition of the present invention.
As ultraviolet light absorber, benzophenone derivates, benzoate derivatives, benzotriazole derivatives, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivates, anthranilate derivatives, dibenzoylmethane derivative etc. can be listed.Ultraviolet light absorber can be used alone one, also can be used in combination of two or more.By combinationally using above-mentioned antioxidant, the stabilization of the molding obtained by hardening resin composition of the present invention can be sought.
(other adjuvant)
Flame-retardant curable resin composition of the present invention can also as required in the defoamer of known conventional thickening agent, silicon-type, fluorine system, the macromolecular etc. such as the known conventional thermal polymerization inhibitor such as compounding quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, phenothiazine, fine silica powder, organobentonite, smectite and levelling agent at least any one, imidazoles system, thiazole system, the known conventional additive kind such as silane coupling agent, rust preventive such as triazole system.
Above-mentioned thermal polymerization inhibitor may be used for preventing flame-retardant curable resin composition less desirable thermal polymerization or through time polymerization.As thermal polymerization inhibitor, include, for example out 4-metoxyphenol, quinhydrones, alkyl or aryl replaces quinhydrones, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, 2-dihydroxy benaophenonel, 4-methoxyl-2-dihydroxy benaophenonel, stannous chloride, phenothiazine, chloranil, naphthylamines, betanaphthol, 2, 6-bis--tert-butyl group-4-cresols, 2, 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitro benzene, picric acid, 4-toluidine, methylene blue, the reaction product of copper and organic sequestering agent, gaultherolin, and phenothiazine, nitroso compound, the chelate etc. of nitroso compound and Al.
(organic solvent)
And then, in order to above-mentioned (B-1) is containing carboxy resin or (B) synthesis containing carboxy resin, the modulation of composition, or in order to the viscosity adjustment for being applied to substrate, carrier film, can be with an organic solvent in flame-retardant curable resin composition of the present invention.
As this organic solvent, ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, petroleum solvent etc. can be listed.More specifically, be the ketone such as MEK, cyclohexanone; Toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; The glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; The ester classes such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters; The alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents etc. such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha.This organic solvent can be used alone one, also can use with the form of two or more potpourris.
Flame-retardant curable resin composition of the present invention preferably can be used as solder resist.In addition, due to anti-flammability, flexible excellent anti-flammability overlay film can be obtained, the flame-retardant curable resin composition of FPC can be particularly preferably used as.
It is upper and dry and is formed that flame-retardant curable resin composition of the present invention is applied to film (carrier film) by dry film of the present invention, possesses carrier film and be formed at the layer be made up of flame-retardant curable resin composition in this carrier film.
During dry film, with above-mentioned organic solvent, flame-retardant curable resin composition of the present invention is diluted to suitable viscosity, be applied on supporter by comma coater, knife type coater, lip coating machine, rod coater, extrusion coating machine, reverse coating machine, transfer roller coating machine (transferrollcoater), gravure coater, flush coater etc. with uniform thickness, usually at the temperature of 50 ~ 130 DEG C dry 1 ~ 30 minute, film can be obtained.To coating film thickness, there is no particular limitation, usually, dried thickness 10 ~ 150 μm, preferably suitably select the scope of 20 ~ 60 μm.
As carrier film, can plastic sheeting be used, preferably use the plastic sheeting of the mylar, Kapton, polyamidoimide film, polypropylene film, plasticon etc. of polyethylene terephthalate etc.To the thickness of carrier film, there is no particular limitation, usually suitably selects in the scope of 10 ~ 150 μm.
On a carrier film after film forming, and then, in order to prevent the surface attachment dust etc. of film, it is desirable to the stacked strippable coverlay on the surface of film.
As strippable coverlay, such as, can use polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper etc., as long as the bonding force of film and coverlay is less than the bonding force of film and supporter when peeling off coverlay.
Anti-flammability overlay film of the present invention by flame-retardant curable resin composition of the present invention or dry film of the present invention are carried out in heat curing and photocuring at least any one obtains.The following object lesson listing the manufacture method of above-mentioned anti-flammability overlay film, but be not limited to this.When the embodiment of above-mentioned flame-retardant curable resin composition, such as, the viscosity being suitable for coating process is adjusted to above-mentioned organic solvent, be applied on base material by methods such as dip coating, flow coat method, rolling method, stick coating method, silk screen print method, heavy curtain rubbing methods, organic solvent volatile dry (predrying) contained in composition is made at the temperature of about 60 ~ 100 DEG C, thus the film that can cannot do not formed stickyly.In addition, when the embodiment of above-mentioned dry film, use hot roll laminator etc. to fit on base material and (fits in the mode that above-mentioned flame-retardant curable resin composition layer contacts with base material).When the flame-retardant curable resin composition layer of above-mentioned film also possesses the dry film of strippable coverlay, after peeling off coverlay, the mode that use hot roll laminator etc. contact with base material with above-mentioned flame-retardant curable resin composition layer is fitted.
Then, during photocuring, the flame-retardant curable resin composition layer of the film of the flame-retardant curable resin composition obtained or the dry film after fitting is exposed (irradiation of active energy beam).For exposure, utilize contact (or cordless) by forming the method for the figuratum photomask method that utilizes active energy beam optionally to expose or the direct pattern exposure that utilizes the direct exposure machine of laser.By this exposure, exposure portion (part by the active energy beam has irradiated) solidification of film (flame-retardant curable resin composition layer).Then, utilized in unexposed portion dilute alkaline aqueous solution (such as 0.3 ~ 3% aqueous sodium carbonate) to develop, form corrosion-resisting pattern, thus the above-mentioned anti-flammability overlay film of the pattern expected can be obtained.In addition, during heat curing, such as containing under the condition of the above-mentioned thermosetting component with ring-type (sulphur) ether as (C) thermosetting component, its heat curing is made by the temperature being heated to about 140 ~ 180 DEG C, carboxyl containing carboxy resin reacts with the thermosetting component with ring-type (sulphur) ether, form cured coating film, thus anti-flammability overlay film can be obtained.
As above-mentioned base material, can adopt make the compound substance such as paper using-phenolics, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth/nonwoven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthon-epoxy resin, fluororesin tygon polyphenylene oxide (polyphenyleneether), polyphenylene oxide (polyphenyleneoxide) cyanate the copper-clad laminated board, Kapton, PET film, glass substrate, ceramic substrate, wafer board etc. of gradational (FR-4 etc.).
The volatile dry carried out after being coated with flame-retardant curable resin composition of the present invention can use heated air circulation type drying oven, IR stove, hot plate, convection oven etc. (use possess utilize the device of the thermal source of the air heat mode of steam and the method that the hot air convection in dryer is contacted, the mode that is blown into supporter by nozzle) to carry out.
As the exposure machine irradiated for above-mentioned active energy beam, as long as be equipped with high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, mercury shot arc lamp etc., with the ultraviolet device of the range illumination of 350 ~ 450nm, and then, also can use direct drawing apparatus (such as utilizing the cad data from computing machine directly to use the laser direct imaging device of laser rendering image).As the lasing light emitter directly retouching machine, as long as use maximum wavelength is the laser of the scope of 350 ~ 410nm, can be any one in gas laser, Solid State Laser.Different according to thickness etc. for the formation of the exposure of image, usually can be 20 ~ 800mJ/cm 2, be preferably 20 ~ 600mJ/cm 2scope in.
As above-mentioned developing method, infusion process, elution method, gunite, spread coating etc. can be used, as developer solution, potassium hydroxide can be used, the aqueous alkali of NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc.
Printed circuit board (PCB) of the present invention possesses at least any one and the anti-flammability overlay film obtained by carrying out flame-retardant curable resin composition of the present invention or dry film of the present invention in heat curing and photocuring.The following object lesson listing the manufacture method of above-mentioned printed circuit board (PCB), but be not limited to this.
After the printed circuit board (PCB) being formed with circuit is formed the film of flame-retardant curable resin composition of the present invention or fit dry film of the present invention and after forming flame-retardant curable resin composition layer (fit above-mentioned dry film time, be laminated to be formed with circuit printed circuit board (PCB) on after, do not peel off supporter), active energy beam is utilized optionally to expose according to pattern direct irradiation laser isoreactivity energy-ray or by forming figuratum photomask, dilute alkaline aqueous solution is utilized to develop in unexposed portion, can be formed corrosion-resisting pattern (fit above-mentioned dry film time, supporter is peeled off after exposure, develop).Thereby, it is possible to obtain the printed circuit board (PCB) of the above-mentioned anti-flammability overlay film of the pattern possessing expectation.In addition, when heat curing, by means of only being heating and curing or finally being solidified (solidifying completely) by the irradiation of active energy beam after being heating and curing after the irradiation of active energy beam or being heating and curing, cured film (solidfied material) can be formed.Thereby, it is possible to obtain the printed circuit board (PCB) possessing above-mentioned anti-flammability overlay film.The formation of pattern is not limited to photoetching process, also can use silk screen print method etc.
The cured coating film formed by optical polymerism resin combination of the present invention and dry film is preferably as the permanent overlay film of printed circuit board (PCB), especially preferred as solder resist, interlayer dielectic.
Embodiment
(synthesis of phosphorus element-containing acrylate resin)
[synthesis example 1]
1384 weight portion 10-(2 are dropped in autoclave, 3-dicarboxypropyl)-9, assorted-10-the phosphine of 10-dihydro-9-oxy is mixed phenanthrene-10-oxide (Sanko Co., Ltd.'s system, M-Acid), 590 weight portion 3-methyl pentanediols, 0.1 weight portion are as the tetra-n-butyl titanate esters of catalyzer, heat at 220 ~ 235 DEG C after 3 hours, be decompressed to 5mmHg with 20 minutes, be warming up to 250 DEG C during this period, at 250 DEG C, implement polycondensation reaction 60 minutes.Then, the reactant obtained is cooled to room temperature, 147g acrylic acid, 19.22g methane-sulforic acid, 0.3g methylnaphthohydroquinone and 1000g toluene are dropped into and possesses the reactor that stirring machine, thermometer and air are blown into pipe, air is blown into the speed of 10ml/ minute, limit is stirred, while react 12 hours at 110 DEG C.The water generated by reacting distills as the azeotropic mixture with toluene and removes.Then, be cooled to room temperature, by the 15% sodium hydrate aqueous solution neutralization of obtained reaction solution 58.92g, then wash.Then, by evaporator by the 529.5g diethylene glycol monoethyl ether acetate displacement limit distillation removing of toluene limit, the phosphorus element-containing acrylic ester resin solution (varnish) of solid constituent 75%, phosphorus concentration 6.3% is obtained.Below, the phosphorus element-containing acrylic ester resin solution obtained is called A-1.
[synthesis example 2]
By 692 weight portion 10-(2,3-dicarboxypropyl)-9, assorted-10-the phosphine of 10-dihydro-9-oxy is mixed phenanthrene-10-oxide (Sanko Co., Ltd.'s system, M-Acid), 284 weight parts of methacrylic acid ethylene oxidic esters, 418 weight portion diethylene glycol monomethyl ether acetic acid esters heating are stirred to 100 DEG C, uniform dissolution.Then, drop into 2.1 weight portion triphenylphosphines, at 115 DEG C, carry out reaction 4 hours, obtain the phosphorus element-containing acrylic ester resin solution (varnish) of solid constituent 65%, phosphorus concentration 4.7%.Below, the phosphorus element-containing acrylic ester resin solution obtained is called A-2.
(synthesis or preparation containing carboxy resin)
[synthesis example 3: the synthesis ((B-1)-1) being equivalent to the above-mentioned resin containing carboxy resin (5)]
2400g (3 moles) is dropped into derived from 1 in the reaction vessel possessing stirring apparatus, thermometer, condenser, 5-pentanediol and 1, PCDL (Asahi Chemical Corp's system of 6-hexanediol, T5650J, number-average molecular weight 800), 603g (4.5 moles) dihydromethyl propionic acid and 238g (2.6 moles) be as the acrylic acid-2-hydroxyl ethyl ester of monohydroxy compound.Then, drop into the isophorone diisocyanate of 1887g (8.5 moles) as polyisocyanates, be heated to 60 DEG C of stoppings while stirring, when temperature in reaction vessel starts to reduce, again heat, continue to stir at 80 DEG C, confirmed the absorption spectrum (2280cm of isocyanate group by infrared absorption spectrum -1) disappear, terminate reaction.Then, adding carbitol acetate makes solid constituent be 50 quality %.The acid number of the solid constituent containing carboxy resin obtained is 50mgKOH/g.Below, the resin solution obtained (varnish) is called (B-1)-1.
[modulation example 1: the preparation ((B-1)-2) being equivalent to the above-mentioned resin containing carboxy resin (8)]
Adopt and use containing photonasty group and the photonasty of the polyfunctional epoxy resin of bisphenol-f type containing carboxy resin (Nippon Kayaku K. K's system, ZFR-1401H (solid constituent 65%, be 98mgKOH/g as the acid number of resin)).Below, this resin solution (varnish) is called (B-1)-2.
[modulation example 2: the preparation ((B-1)-3) being equivalent to the above-mentioned resin containing carboxy resin (4)]
Use containing photonasty group and have carbamate structures containing carboxy resin [Nippon Kayaku K. K's system, UXE-3000 (solid constituent 65%, be 98mgKOH/g as the acid number of resin)].Below, this resin solution (varnish) is called (B-1)-3.
[preparation example 3: the preparation ((B-1)-4) being equivalent to the above-mentioned resin containing carboxy resin (7)]
Adopt and use containing photonasty group and the photonasty of the polyfunctional epoxy resin of biphenyl phenolic varnish type containing carboxy resin (Nippon Kayaku K. K's system, ZCR-1601H (solid constituent 65%, be 98mgKOH/g as the acid number of resin)).Below, this resin solution (varnish) is called (B-1)-4.
[synthesis example 4 (R-1)]
1070g (diglycidyl radix (aromatic rings sum): 5.0 moles) o-cresol phenolic epoxy varnish (Dainippon Ink Chemicals's system is dropped in 600g diethylene glycol monoethyl ether acetic acid esters, EPICLONN-695, softening point 95 DEG C, epoxide equivalent 214, average functionality 7.6), 360g (5.0 moles) acrylic acid and 1.5g quinhydrones, heating is stirred to 100 DEG C, uniform dissolution.Then, drop into 4.3g triphenylphosphine, be heated to 110 DEG C, react after 2 hours, be warming up to 120 DEG C, then carry out reaction 12 hours.415g fragrance family hydrocarbon (SOLVESSO150), 456.0g (3.0 moles) tetrabydrophthalic anhydride is dropped in the reactant liquor obtained, reaction in 4 hours is carried out at 110 DEG C, after cooling, obtain the resin solution of solid constituent acid number 89mgKOH/g, solid constituent 65%.Below, the resin solution obtained (varnish) is called R-1.
[embodiment 1-1 ~ 1-9, comparative example 1-1 ~ 1-4]
By above-mentioned resin solution (varnish), compounding according to ratio shown in table 1 (mass parts) together with the various compositions shown in table 1, use stirring machine premixed, then carry out mixing with 3 roller mills, prepare hardening resin composition.Herein, the particle size analyzer manufactured with ERICHSEN company measures granularity, and evaluating the dispersion degree of each hardening resin composition obtained, is less than 15 μm.
[table 1]
* 1: Mitsubishi chemical Co., Ltd YX4000, solid constituent 100%
* 2: Mitsubishi chemical Co., Ltd jER828, solid constituent 100%
* 3: Dow Chemical D.E.N.438CA90, solid constituent 90%: carbitol acetate 10%
* 4:BASFJAPANLTD. LUCIRINTPO
* 5:BASFJAPANLTD. IRGACURE389
* 6:BASFJAPANLTD. IRGACUREOXE-02
* 7: Otsuka Chemical Co., Ltd SPE-100
* 8: Xin Zhong KCC of village BPE-500
* 9: Nippon Kayaku K. K KAYARADUX-2201
* 10: Showa Denko K. K HigiliteH-42M
* 11:C.I. pigment blue 15: 3
* 12:C.I. pigment yellow 147
* 13: diethylene glycol monoethyl ether acetic acid esters
[performance evaluation]
< optimum exposure >
After the circuit pattern substrate polishing roll of thick for copper 35 μm is ground, washing, drying, again the hardening resin composition of the various embodiments described above 1-1 ~ 1-9 and comparative example 1-1 ~ 1-4 is applied on aforesaid substrate by the whole face of silk screen print method, in the heated air circulation type drying oven of 80 DEG C dry 30 minutes (after dry thickness 20 μm).Use the exposure device (HMW-680-GW20) carrying metal halide lamp, across stage metraster (KodakNo.2) exposure, develop (30 DEG C, 0.2MPa, 1wt%Na will be carried out 2cO 3aqueous solution) pattern of 60 seconds residual afterwards stage metraster is set to optimum exposure when being 6 sections.
< flexibility (folding resistance) >
The whole face of hardening resin composition of the various embodiments described above 1-1 ~ 1-9 and comparative example 1-1 ~ 1-4 is applied to 25 μm of thick Kapton (DUPONT-TORAYCO. by serigraphy, LTD. make, KAPTON100H), drying 30 minutes at 80 DEG C, is cooled to room temperature (after dry thickness 15 μm).To the substrate obtained, use the exposure device (HMW-680-GW20) carrying metal halide lamp with optimum exposure exposure corrosion-resisting pattern, by the 1wt%Na of 30 DEG C 2cO 3aqueous solution carries out development 60 second, after obtaining corrosion-resisting pattern, being heated 60 minutes by this substrate, be cured at 150 DEG C under the condition spraying 0.2Mpa, obtains evaluating substrate.
To the evaluation substrate obtained, repeat to carry out 180 ° of bendings for several times by bending machining, by crackle production that is visual and the observation by light microscope film now of 200 times, measure until the bending number of times that carries out when crackle produces, flexible according to following benchmark evaluation.
More than ◎: 5 times
Zero: 3 ~ 4 times
△: 1 ~ 2 times
×: 0 time
< is high temperature resistant briquettability >
By serigraphy, the whole face of hardening resin composition of the various embodiments described above 1-1 ~ 1-9 and comparative example 1-1 ~ 1-4 is applied on the figuratum Kapton substrate of formation, drying 30 minutes at 80 DEG C, is cooled to room temperature (after dry thickness 20 μm).Obtained substrate use the exposure device (HMW-680-GW20) being equipped with metal halide lamp expose soldering-resistant pattern with optimum exposure, with the 1wt%Na of 30 DEG C 2cO 3aqueous solution is spraying 2kg/cm 2condition under developed for 60 seconds, obtain corrosion-resisting pattern.This substrate is heated at 150 DEG C and within 60 minutes, is cured.The printed base plate obtained (evaluation substrate) is clamped with padded coaming, uses SUS plate to apply 20kgf/cm 2heavy burden, at 150 DEG C, carry out 60 minutes vacuum pressing.The peristome of the substrate after being suppressed by visual and 200 times observation by light microscope, carries out the confirmation of oozing out, according to the high temperature resistant briquettability of following benchmark evaluation.
Zero: peristome is without oozing out.
×: peristome has and oozes out.
< anti-flammability >
The whole face of hardening resin composition of the various embodiments described above 1-1 ~ 1-9 and comparative example 1-1 ~ 1-4 is applied to 25 μm, 12.5 μm thick Kapton (DUPONT-TORAYCO. by serigraphy, LTD. make, KAPTON100H (25 μm)), drying 30 minutes at 80 DEG C, is cooled to room temperature (after dry thickness 20 μm).And then, by serigraphy, whole coating is similarly carried out to the back side, at 80 DEG C, naturally cool to room temperature after dry 30 minutes, obtain double spread substrate.On obtained double-sided substrate, the exposure device (HMW-680-GW20) being equipped with metal halide lamp is used to carry out whole exposure, with the 1wt%Na of 30 DEG C with optimum exposure to solder resist 2cO 3aqueous solution is spraying 2kg/cm 2condition under developed for 60 seconds, at 150 DEG C, carry out heat curing in 60 minutes, make assess sample.The thin material testing vertical flammability of foundation UL94 standard is carried out as flame retardant test to this anti-flammability sample for evaluation.Be evaluated as: be expressed as VTM-0 by qualified for flame retardant test, be expressed as burning by defective.
Above-mentioned each evaluation test be the results are shown in table 2.
[table 2]
(embodiment 1-10 ~ 1-18)
The each hardening resin composition MEK prepared according to the formula removing silicon-type defoamer in the formula from the embodiment 1-1 shown in table 1 ~ 1-9 is diluted, be applied in carrier film (PET), heat drying, form the photosensitive polymer combination layer of thickness 20 μm, coverlay (PE) is fitted on it, obtains dry film.Then, peeling off coverlay, using laminating machine by film adhered to forming figuratum copper clad laminate, making test substrate.The evaluation test of each characteristic is carried out in the same manner as aforementioned test methods and evaluation method.In addition, by embodiment 1-1 form the dry film that obtains and embodiment 1-10, embodiment 1-2 form with embodiment 1-11, embodiment 1-3 form with embodiment 1-12, embodiment 1-4 form with embodiment 1-13, embodiment 1-5 form with embodiment 1-14, embodiment 1-6 form with embodiment 1-15, embodiment 1-7 form with embodiment 1-16, embodiment 1-8 form with embodiment 1-17, embodiment 1-9 form with embodiment 1-18 difference corresponding.Show the result in following table 3.
[table 3]
From the result shown in above-mentioned table 2,3, when the hardening resin composition of embodiment 1-1 ~ 1-18, there is good flexibility, and also have excellent anti-flammability concurrently.On the other hand, known, do not contain the anti-flammability of the hardening resin composition of the comparative example 1-1 of (A) of the present invention phosphoric acrylic ester resin, flexibility is poor.In addition, known, by (B-1) of embodiment 1-1 containing carboxy resin replace with other containing the comparative example 1-2 of carboxy resin compared with embodiment 1-1, flexible poor.Known, phenoxy phosphazene is used to replace the comparative example 1-3 of (A) of the present invention phosphoric acrylic ester resin to possess good flexibility, anti-flammability, but high temperature resistant briquettability is poor, urethane acrylate is used to replace the comparative example 1-4 of (A) of the present invention phosphoric acrylic ester resin to have good flexibility, but poor fire.Known, the flame-retardant curable resin composition of the present invention of above-mentioned excellent preferably can be used as the solder resist of FPC.
(synthesis or preparation containing carboxy resin)
[being equivalent to the synthesis ((B)-1) of the above-mentioned resin containing carboxy resin (5)]
Synthesized by the method identical with above-mentioned synthesis example 3.The acid number of the solid constituent containing carboxy resin obtained is 50mgKOH/g.
Below, the resin solution obtained (varnish) is called (B)-1.
[being equivalent to the preparation ((B)-2) of the above-mentioned resin containing carboxy resin (8)]
Prepared by the method identical with above-mentioned modulation example 1.
Below, this resin solution (varnish) is called (B)-2.
[being equivalent to the preparation ((B)-3) of the above-mentioned resin containing carboxy resin (4)]
Prepared by the method identical with above-mentioned modulation example 2.
Below, this resin solution (varnish) is called (B)-3.
[being equivalent to the synthesis ((B)-4) of the above-mentioned resin containing carboxy resin (6)]
Prepared by the method identical with above-mentioned synthesis example 4, obtain the resin solution of solid constituent acid number 89mgKOH/g, solid constituent 65%.
Below, the resin solution obtained (varnish) is called (B)-4.
(embodiment 2-1 ~ 2-7, comparative example 2-1 ~ 2-4)
By above-mentioned resin solution (varnish), compounding according to ratio shown in table 4 (mass parts) together with the various compositions shown in table 4, use stirring machine premixed, then carry out mixing with 3 roller mills, prepare hardening resin composition.Herein, the particle size analyzer manufactured with ERICHSEN company measures granularity, and evaluating the dispersion degree of each hardening resin composition obtained, is less than 15 μm.
[table 4]
* the varnish modulated with solid constituent 75%, carbitol acetate 25% of 1: Nippon Kayaku K. K NC-3000-L (there is the epoxy resin of biphenyl novolac structure)
* 2: Mitsubishi chemical Co., Ltd YX4000, solid constituent 100%
* 3: Mitsubishi chemical Co., Ltd jER828, solid constituent 100%
* 4:BASFJAPANLTD. LUCIRINTPO
* 5:BASFJAPANLTD. IRGACURE389
* 6:BASFJAPANLTD. IRGACUREOXE-02
* 7: Otsuka Chemical Co., Ltd SPE-100
* 8: Xin Zhong KCC of village BPE-500
* 9: Nippon Kayaku K. K KAYARADUX-2201
* 10: Showa Denko K. K HigiliteH-42M
* 11:C.I. pigment blue 15: 3
* 12:C.I. pigment yellow 147
* 13: diethylene glycol monoethyl ether acetic acid esters
[performance evaluation]
To the hardening resin composition of the various embodiments described above 2-1 ~ 2-7 and comparative example 2-1 ~ 2-4, method evaluation optimum exposure same as described above, flexibility (folding resistance), high temperature resistant briquettability and anti-flammability.
< low warpage properties >
The assess sample same making of evaluation substrate with flexible (folding resistance) obtained cuts out length of side 50mm × 50mm, measures the warpage of 4 jiaos, obtains mean value, according to following benchmark evaluation low warpage properties.
Zero: warpage is less than 4mm
△: warpage is more than 4mm and less than 8mm.
×: warpage is more than 8mm.
Above-mentioned each evaluation test be the results are shown in table 5.
[table 5]
(embodiment 2-8 ~ 2-14)
The each hardening resin composition MEK prepared with the formula removing silicon-type defoamer in the formula from the embodiment 2-1 shown in table 4 ~ 2-7 is diluted, be applied in carrier film (PET), heat drying, form the photosensitive polymer combination layer of thickness 20 μm, coverlay (PE) is fitted on it, obtains dry film.Then, peeling off coverlay, using laminating machine by film adhered to forming figuratum copper clad laminate, making test substrate.The evaluation test of each characteristic is evaluated in the same manner as aforementioned test methods and evaluation method.In addition, by embodiment 2-1 form the dry film that obtains and embodiment 2-8, embodiment 2-2 form with embodiment 2-9, embodiment 2-3 form with embodiment 2-10, embodiment 2-4 form with embodiment 2-11, embodiment 2-5 form with embodiment 2-12, embodiment 2-6 form with embodiment 2-13, embodiment 2-7 form with embodiment 2-14 difference corresponding.Show the result in following table 6.
[table 6]
From the result shown in above-mentioned table 5,6, when the hardening resin composition of embodiment 2-1 ~ 2-14, there is good flexibility, low warpage properties, and, also have excellent anti-flammability concurrently.On the other hand, known, not poor containing the anti-flammability of hardening resin composition of the comparative example 2-1 of (A) of the present invention phosphoric acrylic ester resin, flexibility, low warpage properties.In addition, known, the epoxy resin (C-1) of embodiment 2-1 with biphenyl novolac structure replaces with the comparative example 2-2 of other epoxy resin compared with embodiment 2-1, and low warpage properties is poor.Known, phenoxy phosphazene is used to replace the comparative example 2-3 of (A) of the present invention phosphoric acrylic ester resin to possess good flexibility, low warpage properties, anti-flammability, but high temperature resistant briquettability is poor, urethane acrylate is used to replace the comparative example 2-4 of (A) of the present invention phosphoric acrylic ester resin to have good flexibility, low warpage properties, but poor fire.Known, the flame-retardant curable resin composition of the present invention of above-mentioned excellent preferably can be used as the solder resist of FPC.
(embodiment 2-1 ~ 2-15 and comparative example 2-5,2-6)
Above-mentioned resin solution (varnish) is compounding according to the ratio (mass parts) shown in the various composition shown in table 7 and table 7, after stirring machine premixed, mixing with 3 roller mills, the hardening resin composition of preparation embodiment 2-15, comparative example 2-5 and comparative example 2-6.Herein, the particle size analyzer manufactured with ERICHSEN company measures granularity, and evaluating the dispersion degree of each hardening resin composition obtained, is less than 15 μm.Following evaluation test is carried out to the hardening resin composition of each hardening resin composition and above-described embodiment 2-1.
[performance evaluation]
< low warpage properties >
By method same as described above, at Kapton thickness two conditions (KAPTON100H (25 μm), KAPTON50H (12.5 μm), be DUPONT-TORAYCO., LTD. system), exposure two condition (100mJ/cm 2, 400mJ/cm 2) amount under four conditions and evaluate.
Above-mentioned each evaluation test be the results are shown in table 7.The mean value of the warpage of the numeric representation recorded in the evaluation of low warpage properties 4 jiaos.
[table 7]
* 1: do not implement
* 2: Showa Denko K. K HFA-6065E (phosphorous polyfunctional acrylic ester) (solid constituent 67.5%, diethylene glycol monoethyl ether acetic acid esters 32.5%)
* the varnish modulated with solid constituent 75%, carbitol acetate 25% of 3: Nippon Kayaku K. K NC-3000-L (there is the epoxy resin of biphenyl novolac structure)
* 4: Mitsubishi chemical Co., Ltd YX4000, solid constituent 100%
* 5:BASFJAPANLTD. LUCIRINTPO
* 6:BASFJAPANLTD. IRGACUREOXE-02
* 7: Xin Zhong KCC of village BPE-500
* 8: Showa Denko K. K HigiliteH-42M
* 9:C.I. pigment blue 15: 3
* 10:C.I. pigment yellow 147
* 11: diethylene glycol monoethyl ether acetic acid esters
From the result shown in above-mentioned table 7, when the hardening resin composition of embodiment 2-1,2-15, demonstrate good low warpage properties.On the other hand, known, the phosphorus element-containing acrylate resin containing other replaces the low warpage properties of the hardening resin composition of comparative example 2-5,2-6 of (A) phosphorus element-containing acrylate resin poor.

Claims (12)

1. a flame-retardant curable resin composition for solder resist formation, it is characterized in that, it contains:
(A) the phosphorus element-containing acrylate resin that at least any one and acrylate compounds in the phosphorus element-containing dicarboxylic acid shown in following general formula (1) and acid anhydrides thereof react and obtain,
In formula, R 1and R 2separately represent the alkyl of hydrogen atom or carbon number 1 ~ 6, m and n separately represents the integer of 0 ~ 4, and dotted line represents that two carboxyls also can form acid anhydrides;
(B-1) part-structure be selected from the group that is made up of structure of bisphenol A, Bisphenol F structure, biphenol structural, two xylenol structure, biphenyl novolac structure and carbamate structures more than one containing carboxy resin;
(C) thermosetting component; With
(D) Photoepolymerizationinitiater initiater.
2. a dry film, is characterized in that, it the flame-retardant curable resin composition that solder resist according to claim 1 is formed is applied to also dry on film and is formed.
3. an anti-flammability overlay film, is characterized in that, its by the flame-retardant curable resin composition that solder resist according to claim 1 is formed carry out in heat curing and photocuring at least any one obtains.
4. an anti-flammability overlay film, is characterized in that, its by dry film according to claim 2 is carried out in heat curing and photocuring at least any one obtains.
5. a printed circuit board (PCB), is characterized in that, it possesses anti-flammability overlay film according to claim 3.
6. a printed circuit board (PCB), is characterized in that, it possesses anti-flammability overlay film according to claim 4.
7. a flame-retardant curable resin composition for solder resist formation, it is characterized in that, it contains:
(A) the phosphorus element-containing acrylate resin that at least any one and acrylate compounds in the phosphorus element-containing dicarboxylic acid shown in following general formula (1) and acid anhydrides thereof react and obtain,
In formula, R 1and R 2separately represent the alkyl of hydrogen atom or carbon number 1 ~ 6, m and n separately represents the integer of 0 ~ 4, and dotted line represents that two carboxyls also can form acid anhydrides;
(B) containing carboxy resin;
(C-1) there is the epoxy resin of biphenyl novolac structure; With
(D) Photoepolymerizationinitiater initiater.
8. a dry film, is characterized in that, it the flame-retardant curable resin composition that solder resist according to claim 7 is formed is applied to also dry on film and is formed.
9. an anti-flammability overlay film, is characterized in that, its by the flame-retardant curable resin composition that solder resist according to claim 7 is formed carry out in heat curing and photocuring at least any one obtains.
10. an anti-flammability overlay film, is characterized in that, its by dry film according to claim 8 is carried out in heat curing and photocuring at least any one obtains.
11. 1 kinds of printed circuit board (PCB)s, is characterized in that, it possesses anti-flammability overlay film according to claim 9.
12. 1 kinds of printed circuit board (PCB)s, is characterized in that, it possesses anti-flammability overlay film according to claim 10.
CN201310102873.9A 2012-03-27 2013-03-27 Flame-retardant curable resin composition, dry film, anti-flammability overlay film and printed circuit board (PCB) Active CN103365082B (en)

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CN103730207B (en) * 2013-11-26 2016-08-17 沃太能源南通有限公司 A kind of preparation method of monocrystaline silicon solar cell aluminium paste
TWI675256B (en) * 2015-03-13 2019-10-21 日商三菱製紙股份有限公司 Process for forming solder resist patterns
CN106279764B (en) * 2015-05-26 2018-09-21 三晃股份有限公司 Metal mold crosslinking auxiliary, its preparation method and the resin combination comprising it
JP6967508B2 (en) * 2016-03-31 2021-11-17 太陽インキ製造株式会社 Curable resin composition, dry film, cured product and printed wiring board
CN113759663B (en) * 2021-09-15 2023-07-14 广东硕成科技股份有限公司 Modified acrylic resin composition, preparation method and dry film solder resist thereof

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CN101432330A (en) * 2006-04-28 2009-05-13 日立化成工业株式会社 Resin composition, prepreg, laminate, and wiring board
CN101320213A (en) * 2007-06-04 2008-12-10 太阳油墨制造株式会社 Light sensitive resin composition and flexible printed circuit board produced with the same
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