CN104977805A - Curable resin composition composition for forming permanent coating dry film and printed wiring board - Google Patents

Abstract

To provide: a curable resin composition which has excellent characteristics such as electrical insulation properties, adhesiveness, heat resistance, crack resistance and gold plating resistance, and which is also excellent in terms of electrical insulation properties and adhesiveness in a harsh environment such as a high-temperature high-humidity environment; a curable resin composition for forming a permanent coating film; a dry film; and a printed wiring board. A curable resin composition which contains (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting component and (D) a compound having a urethane bond, and which is characterized in that the carboxyl group-containing resin (A) contains a carboxyl group-containing resin having a novolac skeleton and the thermosetting component (C) contains a maleimide compound.

Description

Hardening resin composition, composition, dry film and printed circuit board (PCB) for the formation of permanent overlay film

Technical field

The present invention relates to hardening resin composition, particularly relate to for the formation of the permanent overlay film used in printed circuit board (PCB) hardening resin composition and use its dry film and printed circuit board (PCB).

Background technology

All the time, printed circuit board (PCB) and flexible printed circuit board are (below, referred to as FPC) to be equipped in the various electronic equipments such as mobile phone, PHS, notebook personal computer, the one-piece type VTR of camera, therefore require the various characteristics such as electrical insulating property, adaptation, thermotolerance, chemical proofing.Thus, same characteristic is also required for the permanent overlay film as these parts.Wherein, FPC is generally polyimide substrate, different from the printed circuit board (PCB) of glass epoxy substrate, is film.But no matter the permanent overlay film formed is that printed circuit board (PCB) or FPC are identical thickness, and when being therefore the FPC of film, the burden of the above-mentioned characteristic of permanent overlay film increases relatively.

As the solder resist of the permanent overlay film of satisfied various like this characteristic, such as, in Japanese Unexamined Patent Publication 2007-41107 publication (patent documentation 1), the aqueous alkaline solution-soluble photosensitive polymer combination containing, for example lower material is proposed: make the reaction product of biphenyl phenolic resin varnish type epoxy resin and unsaturated monocarboxylic and multi-anhydride addition and the aqueous alkaline solution-soluble resin obtained, biphenyl phenolic varnish type photoreactive epoxy resin polymerization initiator as hardening agent.

And then, propose in Japanese Unexamined Patent Publication 2011-123420 publication (patent documentation 2): except above-mentioned characteristic, low warpage, bendability are excellent, most suitable as printed circuit board (PCB), particularly take TAB (winding combines automatically (Tape automated bonding)), COF (covering brilliant film (Chip On Film)) etc. as the use in printed circuit board photosensitive polymer combination of alkali-developable of solder resist of FPC of representative.This photosensitive polymer combination contains: what have biphenyl novolac structure contains carboxyamino formate resin, Photoepolymerizationinitiater initiater and aluminium hydroxide and/or phosphorus-containing compound.

Printed circuit board (PCB) or FPC are used for being installed on various electronic equipment as the aforementioned, therefore, even if require also have patience under the environment that high temperature, high humidity etc. are harsh.Therefore, for permanent overlay film, also require the patience relative to high temperature, high humidity.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2007-41107 publication (claims)

Patent documentation 2: Japanese Unexamined Patent Publication 2011-123420 publication (claims)

Summary of the invention

the problem that invention will solve

Known: the permanent overlay film that obtains of resin combination recorded by aforementioned patent literature 1,2, under the harsh environment such as high temperature, high humidity, sometimes forms material with the substrate such as base material, copper, underfill, particularly can reduce with the adaptation of underfill.

Therefore, the object of the invention is to, the hardening resin composition forming the adaptation of material, the excellent adhesion particularly under high temperature, high humidity relative to substrates such as underfills is provided.

In addition, the object of the invention is to, provide and not only form the excellent adhesion of material relative to substrate, and for the also excellent hardening resin composition of chemical proofing, thermotolerance, the electrical insulating properties such as resistance to gold-plated property, acid resistance, alkali resistance.

And then the object of the invention is to, providing package contains the composition for the formation of permanent overlay film of above-mentioned hardening resin composition and uses dry film and the printed circuit board (PCB) of above-mentioned hardening resin composition.

for the scheme of dealing with problems

Aforementioned object can be solved by following hardening resin composition, the feature of described hardening resin composition is, it comprises (A) containing carboxy resin, (B) inorganic filler, (C) heat curable component and (D) Photoepolymerizationinitiater initiater

Aforementioned (A) containing carboxy resin comprise have novolaks skeleton containing carboxy resin,

Aforementioned (C) heat curable component comprises maleimide compound.

Maleimide compound of the present invention refers to compound, the i.e. maleimide derivatives with dimaleoyl imino.Hardening resin composition of the present invention has the function of both photo-curable and Thermocurable usually.

Below, the preferred implementation of hardening resin composition of the present invention is enumerated.

(1) aforementioned (A) has the person at least arbitrarily in phenol novolacs skeleton and cresol novolak skeleton containing carboxy resin.Thereby, it is possible to maintain the various characteristics such as chemical proofing, thermotolerance, electrical insulating property well, and the adaptation forming material relative to substrates such as underfills is improved.

(2) aforementioned maleimide compound is preferably multifunctional maleimide compound, more preferably bismaleimide compound, is particularly preferably the bismaleimide compound with aromatic ring.Thereby, it is possible to make the adaptation forming material relative to substrates such as underfills improve further.

(3) relative to (A) containing carboxy resin 100 mass parts, aforementioned maleimide compound contains below 15 quality %.Thus, the adaptation raising of material is formed relative to substrates such as underfills.

(4) (C) heat curable component comprises epoxy resin.Thus, the raisings such as excellent resistance to soldering heat performance.

In addition, the present invention is also a kind of hardening resin composition for the formation of permanent overlay film, it is characterized in that, it comprises the hardening resin composition of the invention described above.

The preferred implementation of aforementioned hardening resin composition of the present invention can be applicable to the hardening resin composition for the formation of permanent overlay film of the invention described above.

And then the present invention is also a kind of dry film, it is characterized in that, it has curable resin layer on a carrier film, and this curable resin layer is formed by above-mentioned hardening resin composition.

The solvent residual amount of the curable resin layer of above-mentioned formation is preferably less than 5 % by weight.Thereby, it is possible to the curable resin layer of dry film is transferred on base material well.

The preferred implementation of aforementioned hardening resin composition of the present invention can be applicable to the dry film of the invention described above.

In addition, the present invention is also a kind of printed circuit board (PCB), it is characterized in that, it has curing overlay film, and this curing overlay film is by the hardening resin composition of the invention described above, for the formation of the curable resin layer solidification in the hardening resin composition of permanent overlay film or above-mentioned dry film.

The preferred implementation of aforementioned hardening resin composition of the present invention can be applicable to the printed circuit board (PCB) of the invention described above.

the effect of invention

The feature of hardening resin composition of the present invention is, as (A) containing carboxy resin use have novolaks skeleton containing carboxy resin, use maleimide compound as (C) heat curable component.Thus, the curing overlay film obtained by hardening resin composition of the present invention forms the adaptation of material relative to substrates such as underfills, the adaptation particularly under high temperature, high humidity improves, and then chemical proofing, thermotolerance, the electrical insulating properties such as resistance to gold-plated property, acid resistance, alkali resistance also improve.That is, the curing overlay film of hardening resin composition of the present invention not only above-mentioned excellent adhesion, and the various characteristic such as chemical proofing, thermotolerance, electrical insulating property is also excellent.Can think by combination have novolaks skeleton containing carboxy resin and maleimide compound, the adaptation forming material relative to substrates such as underfills improves and other various characteristics can not be made to reduce.

Thus, the composition for the formation of permanent overlay film of composition of the present invention, dry film and printed circuit board (PCB) is used also to have excellent characteristic as described above.

Embodiment

< hardening resin composition >

Hardening resin composition of the present invention has (A) containing carboxy resin, (B) inorganic filler, (C) heat curable component and (D) Photoepolymerizationinitiater initiater as basis.And, as (A) containing carboxy resin use have novolaks skeleton containing carboxy resin, use maleimide compound as (C) heat curable component.

[(A) is containing carboxy resin]

In the present invention, as (A) containing carboxy resin, main use have novolaks skeleton containing carboxy resin.At this, (A) preferably has the person at least arbitrarily in phenol novolacs skeleton and cresol novolak skeleton containing carboxy resin.(A) when there is containing carboxy resin the phenol novolacs skeleton of more than 3 nucleomes, resistance to soldering heat excellent performance, therefore preferably.It should be noted that, nucleome numerical example is as more than 3 and less than 20.

(A) containing carboxy resin can be have phenol novolacs skeleton containing carboxy resin with have cresol novolak skeleton containing the mixed type of carboxy resin, also can be have in 1 molecule phenol novolacs skeleton and cresol novolak skeleton containing carboxy resin.And have cresol novolak skeleton containing compared with carboxy resin, the adaptation forming material relative to substrate containing carboxy resin with phenol novolacs skeleton is high, therefore preferably.

And then, (A) containing carboxy resin be have phenol novolacs skeleton containing carboxy resin with have cresol novolak skeleton containing the potpourri of carboxy resin time, resistance to soldering heat performance improves, therefore preferably.For above-mentioned have novolaks skeleton containing carboxy resin, the existing known various containing selecting the resin with novolaks skeleton to use in carboxy resin of carboxyl can be had from molecule, but from the aspect of photo-curable, resolution, what particularly preferably have ethylenical unsaturated double bonds in molecule contains carboxyl photoresist.Ethylenical unsaturated double bonds preferred source is from acrylic acid or methacrylic acid or their derivant.

As have novolaks skeleton containing carboxy resin, such as can exemplify out following resin.

(1) epoxy resin making to have novolaks skeleton react with (methyl) acrylic acid, makes to be present in the multi-anhydride additions such as the hydroxyl of side chain and phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride and obtain contain carboxyl photoresist.

(2) make (methyl) acrylic acid and the polyfunctional epoxy resin of the further epoxidation of chloropropylene oxide used for epoxy resin described in (1) reacted, and make the hydroxyl of generation and multi-anhydride addition and obtain contain carboxyl photoresist.

(3) make to have in the epoxy resin described in (1) and 1 molecule the compound of at least 1 alcohol hydroxyl group and 1 phenolic hydroxyl group and (methyl) acrylic acid etc. react containing the monocarboxylic acid of unsaturated group, the multi-anhydride such as the alcohol hydroxyl group of the reaction product obtained and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic acid dianhydride, adipic anhydride is reacted and obtain contain carboxyl photoresist.

(4) reaction product obtained by making to have in 1 molecule the novolac resin of multiple phenolic hydroxyl group and the reaction of the alkylene oxide such as oxirane, epoxypropane, react with the monocarboxylic acid containing unsaturated group such as (methyl) acrylic acid, and make obtained reaction product and multi-anhydride react and obtain contain carboxyl photoresist.

(5) reaction product obtained by making to have in 1 molecule the novolac resin of multiple phenolic hydroxyl group and the reaction of the cyclic carbonate compound such as ethylene carbonate, propylene carbonate, react with the monocarboxylic acid containing unsaturated group, and make obtained reaction product and multi-anhydride react and obtain contain carboxyl photoresist.

(6) make (1) ~ resin of (5) further with 1 molecule in have the compound addition of 1 epoxy radicals and more than 1 (methyl) acryloyl group containing carboxyl photoresist.

At above-mentioned (A) with novolaks skeleton containing in carboxy resin, the preferably resin of (1), (2), (4) ~ (6), as multi-anhydride, preferred tetrabydrophthalic anhydride.

As above-mentioned novolac resin; can enumerate: the polymkeric substance of the polymkeric substance of phenol and/or phenol derivatives and formaldehyde and phenol and/or phenol derivatives and other compounds and formaldehyde (such as; the phenol novolacs condensation product (such as, xenol Novolac) that the Isomers of formoxyl (alkoxy methyl) biphenyl or their potpourri and phenol and/or phenol derivatives react and obtain).

As phenol derivatives, such as can enumerate: the alkyl substituted phenols such as the cresols (quantity of alkyl preferably 1 or 2, for alkyl, carbon number is 1 ~ 18, preferably 1 ~ 4, particularly methyl), the phenol etc. that the aryl-substituted phenols such as phenylphenol (quantity of aryl preferably 1 or 2 is phenyl, alkyl-substituted phenyl, xenyl as aryl), naphthols etc. replace with the group with aromatic condensation ring.And then, combinationally use phenol and/or phenol derivatives, straight-chain triphen phenols, methane type triphen phenols, straight-chain four phenol, radial 6 nucleome oxybenzene compounds, multi-phenol, alkyl also can be used to replace multi-phenol.

As alkyl substituted phenol, such as, can enumerate: orthoresol, paracresol, metacresol, 2,3-xylenols, 2,4-xylenols, 2,5-xylenols, 2,6-xylenols, 3,4-xylenols, 3,5-xylenols.In addition, as multi-phenol, can enumerate: catechol, resorcinol, p-dihydroxy-benzene, methyl hydroquinone, 2,6-dimethyl p-dihydroxy-benzene, Trimethyl Hydroquinone, pyrogallol, phloroglucin.

As phenol and/or phenol derivatives, preferred phenol, cresols, xylenol, particularly preferably phenol, cresols.

As at the example containing the commercially available product of the epoxy resin used in the manufacture of carboxy resin with novolaks skeleton of the present invention, can enumerating: jER152, jER154 that Mitsubishi chemical Co., Ltd manufactures; D.E.N.431, D.E.N.438 that Dow Chemical Company manufactures; EPICLONN-730, EPICLONN-770, EPICLONN-865 that Dainippon Ink Chemicals manufactures; EPOTOHTO YDCN-701, YDCN-704 that Toto Kasei KK manufactures; EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, PCR1170H that Nippon Kayaku Co., Ltd. manufactures; Sumiepoxy ESCN-195X, ESCN-220 that Sumitomo Chemical Co., Ltd. manufactures; A.E.R.ECN-235, ECN-299 etc. (the being trade name) phenolic resin varnish type epoxy resin that Asahi Kasei Corporation manufactures.In addition, particularly as the example with the commercially available product containing carboxy resin of phenol novolacs skeleton of the present invention, can enumerate: PCR1170H (Nippon KayakuCo., Ltd. manufacture).

Have on the basis containing carboxy resin of novolaks skeleton of the present invention, can other be used as required to contain carboxy resin, also can not use.As other containing carboxy resin, can enumerate: using the epoxy resin without novolaks skeleton as initiation material containing carboxy resin, acrylic acid resinoid, using oxetane compound as initiation material containing carboxy resin etc.Contain the concrete example of carboxy resin as other, following compound (oligomer and polymkeric substance) can be enumerated.As other containing carboxy resin, preferably not there is carbamate structures.

(7) make not have novolaks skeleton 2 officials can or 2 officials can react with (methyl) acrylic acid by polyfunctional epoxy resin above, to being present in the hydroxyl addition dibasic acid anhydride of side chain and obtain contain carboxyl photoresist.

(8) hydroxyl without 2 functional epoxy resins of novolaks skeleton is obtained polyfunctional epoxy resin with chloropropylene oxide epoxidation further, this polyfunctional epoxy resin and (methyl) acrylic acid are reacted, and what obtain the hydroxyl addition dibasic acid anhydride generated contains carboxyl photoresist.

(9) what obtained containing the compound copolymerization of unsaturated group by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methyl styrene, (methyl) lower alkyl acrylate, isobutylene etc. contains carboxy resin.

(10) make 2 officials as described later react by the dicarboxylic acid such as oxetane resin and hexane diacid, phthalic acid, hexahydrophthalic acid, carboxy resin is contained to the multi-anhydride such as primary hydroxyl addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride of generation.

(11) make the resin of above-mentioned (7) ~ (10) further with 1 molecule in have the compound addition of 1 epoxy radicals and more than 1 (methyl) acryloyl group containing carboxy resin.

It should be noted that, in this manual, (methyl) acrylate refers to the term being referred to as acrylate, methacrylate and their potpourri, is also same for other similar statements.

Foregoing have multiple carboxyl, therefore, it is possible to utilize dilute alkaline aqueous solution to develop containing carboxy resin on the side chain of trunk polymer (main polymer chain).

In addition, the aforementioned acid number containing carboxy resin is preferably the scope of scope, the more preferably 45 ~ 120mgKOH/g of 40 ~ 200mgKOH/g.If the scope of 40mgKOH/g ~ 200mgKOH/g, then can obtain the adaptation of curing overlay film, alkali development becomes easy, can suppress the dissolving in the exposure portion caused by developer solution, and line carefully to necessity, easily can not describe normal corrosion-resisting pattern.

In addition, the aforementioned weight-average molecular weight containing carboxy resin is different according to resin matrix, is generally the scope of 2000 ~ 150000, more preferably 5000 ~ 100000.If the scope of 2000 ~ 150000, then non-adhesion behavior is good, and the moisture-proof of curing overlay film is good, is difficult to produce film loss during development.In addition, if the scope of above-mentioned weight-average molecular weight, then resolution improves, and developability is good, and storage-stable becomes good.

This compounding amount containing carboxy resin is overall 20 ~ 80 quality % of composition, and preferably the scope of 30 ~ 80 quality % is applicable.If 20 quality % ~ 80 quality %, then the intensity of curing overlay film is good, can reduce the viscosity of composition, the excellences such as coating.

The above-mentioned carboxy resin that contains can be not limited to the resin of aforementioned list and use known resin.That is, for have novolaks skeleton containing carboxy resin, also can be not limited to aforesaid resin and use known resin.Particularly high containing the refractive index in carboxy resin with the resin of aromatic rings at these, excellent in resolution, therefore preferably.What have novolaks skeleton contains carboxy resin not only resolution, PCT (saturated vapour applied voltage test), resistance to anti-thread breakage also excellence.

[(B) inorganic filler]

For photosensitive polymer combination of the present invention, in order to improve physical strength of its curing overlay film etc. and contain (B) inorganic filler.As this (B) inorganic filler, known usual inorganic filler can be used (also referred to as inorganic filler.), but particularly preferably use barium sulphate, spherical silicon dioxide and talcum.And then, in order to obtain outward appearance, the anti-flammability of white, the metal hydroxides such as titanium dioxide, metal oxide also can be used to use as extender pigment filling agent.The mean grain size of above-mentioned inorganic filler is preferably less than 5 μm.Relative to (A) containing carboxy resin 100 mass parts, the compounding amount of these (B) inorganic fillers is preferably set to below 300 mass parts, is preferably set to 0.1 ~ 200 mass parts further, is particularly preferably set to 1 ~ 100 mass parts.By the compounding amount of (B) inorganic filler is set to below 300 mass parts, the viscosity of composition can not become too high, can suppress the reduction of printing, the embrittlement of curing overlay film.

[(C) heat curable component]

Maleimide compound is contained as (C) heat curable component in hardening resin composition of the present invention.

As maleimide compound of the present invention, can enumerate: (C-1) monofunctional aliphatic/alicyclic maleimide, (C-2) monofunctional, aromatic maleimide, (C-3) multifunctional aliphatic/alicyclic maleimide, (C-4) multifunctional aromatic series maleimide.

As monofunctional aliphatic/alicyclic maleimide (C-1), such as, can enumerate: the reactant etc. of maleimide carboxylic acid and tetrahydrofurfuryl alcohol disclosed in N-methylmaleimido, NEM, No. 11-302278, Japanese Unexamined Patent Publication.

As monofunctional, aromatic's maleimide (C-2), such as, can enumerate: N-phenylmaleimide, N-(2-aminomethyl phenyl) maleimide etc.

As multifunctional aliphatic/alicyclic maleimide (C-3), such as can enumerate: N, N '-di-2-ethylhexylphosphine oxide maleimide, N, N '-ethylenebismaleimide, the maleimide ester compounds of the isocyanuric acid ester skeleton that three (hydroxyethyl) isocyanuric acid esters and aliphatics/alicyclic maleimide carboxylic acid obtain through dehydration esterification, the isocyanuric acid skeleton poly maleimide classes such as the maleimide carbamate compounds of the isocyanuric acid ester skeleton that three (carbamate hexyl) isocyanuric acid esters and aliphatics/alicyclic maleimide alcohol obtain through urethane, your ketone double carbamate of different fluorine two (NEM), triethylene glycol two (Mailed Ethyl carbonic ester), aliphatics/alicyclic maleimide carboxylic acid and various aliphatics/alicyclic polyol are through dehydration esterification, or aliphatics/alicyclic poly maleimide ester compounds class that aliphatics/alicyclic maleimide carboxylate and various aliphatics/alicyclic polyol obtain through ester exchange reaction, aliphatics/alicyclic poly maleimide ester compounds class that aliphatics/alicyclic maleimide carboxylic acid and various aliphatics/alicyclic polyepoxide obtain through ether ring-opening reaction, the aliphatics that aliphatics/alicyclic maleimide alcohol and various aliphatics/alicyclic polyisocyanates react through urethane and obtain/alicyclic poly maleimide carbamate compounds class etc.

As multifunctional aromatic series maleimide (C-4), such as can enumerate: N, N '-(4, 4 '-diphenyl methane) bismaleimides, two-(3-ethyl-5-methyl-4-maleimide phenyl) methane, 2, 2 '-bis--(4-(4-maleimidephenoxy) propane, N, N '-(4, 4 '-dipheny oxide base) bismaleimides, N, N '-TOPOT 2,2′ p phenylenebis maleimide, N, N '-meta-phenylene bismaleimide, N, N '-2, 4-toluene bismaleimide, N, N '-2, 6-toluene bismaleimide, the aromatic series poly maleimide ester compounds class that maleimide carboxylic acid and various aromatic polyol carry out ester exchange reaction through dehydration esterification or maleimide carboxylate and various aromatic polyol and obtain, the aromatic series poly maleimide ester compounds class that maleimide carboxylic acid and various aromatic polyepoxide carry out ether ring-opening reaction and obtain, the aromatic series poly maleimide carbamate compounds class etc. that maleimide alcohol and various aromatic polyisocyanate carry out urethane reaction and obtain.

The curability of multifunctional aliphatic/alicyclic maleimide (C-3) is high, irradiates the physical properties excellent of the curing overlay film after active energy beam, therefore preferably.Particularly, for having the alkyl that carbon number is 1 ~ 6, more preferably there is maleimide alkyl carboxylic acid or the maleimide alkyl carboxylic acid ester of straight-chain alkyl, dehydration esterification reaction or ester exchange reaction is carried out and the following general formula (1) obtained and the aliphatics bismaleimide compound shown in general formula (2) with the polytetramethylene glycol of the polyglycol of number-average molecular weight 100 ~ 1000 and/or the polypropylene glycol of number-average molecular weight 100 ~ 1000 and/or number-average molecular weight 100 ~ 1000, the balancing good of the curability of the composition obtained and the physical property of curing overlay film, therefore particularly preferably.

(in formula, m represents the integer of 1 ~ 6, and n represents the value of 2 ~ 23, and R1 represents hydrogen atom or methyl.)

(in formula, m represents the integer of 1 ~ 6, and p represents the value of 2 ~ 14.)

For the present invention, in above-mentioned maleimide compound, more preferably multifunctional aromatic series maleimide (C-4).Wherein, optimization aromatic bismaleimides.Particularly preferably N, N '-(4, 4 '-diphenyl methane) bismaleimides, two-(3-ethyl-5-methyl-4-maleimide phenyl) methane, 2, 2 '-bis--(4-(4-maleimidephenoxy) propane, N, N '-(4, 4 '-dipheny oxide base) bismaleimides, N, N '-TOPOT 2,2′ p phenylenebis maleimide, N, N '-meta-phenylene bismaleimide, N, N '-2, 4-toluene bismaleimide, N, N '-2, 6-toluene bismaleimide, especially preferably N, N '-(4, 4 '-diphenyl methane) bismaleimides is (as BMI (KI Chemical Industry Co., Ltd. manufacture) commercially available), two-(3-ethyl-5-methyl-4-maleimide phenyl) methane is (as BMI-70 (KI Chemical Industry Co., Ltd. manufacture) commercially available), 2, 2 '-bis--(4-(4-maleimidephenoxy) propane is (as BMI-70 (KI Chemical IndustryCo., Ltd. manufacture) commercially available).Think by using multifunctional aromatic series maleimide, particularly aromatic series bismaleimides, easy formation with have novolaks skeleton containing the firmly cross-linked structure of carboxy resin, form the adaptation of material relative to substrates such as underfills and chemical proofing improves and other various characteristics can not be made to reduce.

Relative to (A) containing carboxy resin 100 mass parts, the compounding amount of maleimide compound of the present invention is below 15 mass parts, is preferably 1 ~ 10 mass parts, is particularly preferably 1 ~ 8 mass parts.By being set to below 15 mass parts, the adaptation forming material relative to base material improves.

In hardening resin composition of the present invention, as (C) heat curable component, except above-mentioned maleimide compound, also other heat curable component can be contained.Can expect that thermotolerance improves by adding other heat curable component.As other heat curable component used in the present invention, the known heat-curing resin such as the amino resins such as melamine resin, benzoguanamine resin, melamine derivative, benzoguanamine derivant, blocked isocyanate compounds, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxetane compound, episulfide resin, carbodiimide resin can be used.Particularly preferably there is in molecule at least any one the heat-curing resin in multiple cyclic ether group and cyclic thioether base (hreinafter referred to as ring-type (sulphur) ether).

The heat curable component in above-mentioned molecule with multiple ring-type (sulphur) ether is the compound of any one or the two kinds of groups had in the molecule in ring-type (sulphur) ether of multiple 3,4 or 5 rings, such as can enumerate: the compound in molecule with multiple epoxy radicals, i.e. multi-functional epoxy compound; There is the compound of multiple oxetanyl, i.e. multifunctional oxetane compound in molecule; There is the compound of multiple thioether group, i.e. episulfide resin etc. in molecule.Wherein, preferably as the epoxy resin of multi-functional epoxy compound.

As the example of aforementioned multi-functional epoxy compound, can enumerate: the epoxidized vegetable oil such as Adekacizer O-130P, Adekacizer O-180A, Adekacizer D-32, Adekacizer D-55 that ADEKA manufactures, the jER828 that Mitsubishi chemical Co., Ltd manufactures, jER834, jER1001, jER1004, DAICEL CHEMICAL INDUSTRIES, LTD. the EHPE3150 manufactured, the EPICLON840 that Dainippon Ink Chemicals manufactures, EPICLON850, EPICLON1050, EPICLON2055, the EPOTOHTO YD-011 that Toto Kasei KK manufactures, YD-013, YD-127, YD-128, the D.E.R.317 that Dow Chemical Company manufactures, D.E.R.331, D.E.R.661, D.E.R.664, Sumitomo Chemical Co., Ltd. the SumiepoxyESA-011 manufactured, ESA-014, ELA-115, ELA-128, the A.E.R.330 that Asahi Kasei Corporation manufactures, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin, YDC-1312, p-dihydroxy-benzene type epoxy resin, YSLV-80XY bisphenol-type epoxy resin, YSLV-120TE thioether-type epoxy resin (being Toto Kasei KK to manufacture), the jERYL903 that Mitsubishi chemical Co., Ltd manufactures, EPICLON152, EPICLON165 that Dainippon Ink Chemicals manufactures, EPOTOHTO YDB-400, YDB-500 that Toto Kasei KK manufactures, the D.E.R.542 that Dow ChemicalCompany manufactures, Sumitomo Chemical Co., Ltd. SumiepoxyESB-400, ESB-700 of manufacturing, A.E.R.711, A.E.R.714 etc. (the being trade name) brominated epoxy resin that Asahi Kasei Corporation manufactures, the jER152 that Mitsubishi chemical Co., Ltd manufactures, jER154, the D.E.N.431 that DowChemical Company manufactures, D.E.N.438, the EPICLONN-730 that Dainippon Ink Chemicals manufactures, EPICLONN-770, EPICLONN-865, the EPOTOHTO YDCN-701 that Toto Kasei KK manufactures, YDCN-704, Nippon Kayaku Co., Ltd. the EPPN-201 manufactured, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, SumitomoChemical Co., Ltd. the Sumiepoxy ESCN-195X manufactured, ESCN-220, the A.E.R.ECN-235 that Asahi KaseiCorporation manufactures, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin, the xenol phenolic resin varnish type epoxy resins such as NC-3000, NC-3100 that Nippon Kayaku Co., Ltd. manufactures, the EPICLON830 that Dainippon Ink Chemicals manufactures, the jER807 that Mitsubishi chemical Co., Ltd manufactures, the bisphenol f type epoxy resins such as EPOTOHTO YDF-170, YDF-175, YDF-2004 that Toto Kasei KK manufactures, the bisphenol-A epoxy resins such as EPOTOHTOST-2004, ST-2007, ST-3000 (trade name) that Toto Kasei KK manufactures, the jER604 that Mitsubishi chemical Co., Ltd manufactures, the EPOTOHTO YH-434 that Toto Kasei KK manufactures, (the being trade name) glycidyl amine type epoxy resins such as the Sumiepoxy ELM-120 that Sumitomo Chemical Co., Ltd. manufactures, hydantoins type epoxy resin, (the being trade name) alicyclic epoxy resins such as CELLOXIDE 2021, CY179 that DAICEL CHEMICALINDUSTRIES, LTD. manufacture, the YL-933 that Mitsubishi chemical Co., Ltd manufactures, T.E.N., EPPN-501, EPPN-502 etc. (being trade name) the trihydroxy benzene methylmethane type epoxy resin that Dow Chemical Company manufactures, 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 EBPS-200 that Nippon Kayaku Co., Ltd. manufactures, the EPX-30 that ADEKA Corp. manufactures, the EXA-1514 (trade name) that Dainippon Ink Chemicals manufactures, the bisphenol A novolac type epoxy resin such as the jER157S (trade name) that Mitsubishi chemical Co., Ltd manufactures, the jERYL-931 that Mitsubishi chemical Co., Ltd manufactures etc. (being trade name) four hydroxy phenyl ethane type epoxy resin, (being trade name) hetero ring type epoxy resin such as the TEPIC that Nissan ChemicalIndustries, Ltd. manufacture, the o-phthalic acid diglycidyl ester resins such as the BLEMMER DGT that NOF Corp manufactures, the four glycidyl group xylenol ethane resin such as the ZX-1063 that Toto Kasei KK manufactures, ESN-190, ESN-360 that Nippon Steel ChemicalCo., Ltd. manufacture, HP-4032, EXA-4750, EXA-4700 etc. that Dainippon Ink Chemicals manufactures are containing Naphthol-based Epoxy Resin, HP-7200, HP-7200H etc. that Dainippon Ink Chemicals manufactures have the epoxy resin of dicyclopentadiene skeleton, the glycidyl methacrylate copolymerization system epoxy resin such as CP-50S, CP-50M that NOF Corp manufactures, the copolymerization epoxy resin of further N-cyclohexylmaleimide and glycidyl methacrylate, epoxide modified polybutadiene rubber derivant (such as DAICEL CHEMICAL INDUSTRIES, LTD. the PB-3600 etc. manufactured), CTBN modified epoxy (YR-102, YR-450 etc. that such as Toto Kasei KK manufactures) etc., but be not limited to these.These epoxy resin can be used alone or combinationally use two or more.Wherein, the particularly preferably phenolic resin varnish type epoxy resin of bisphenol A-type or bisphenol-f type, di-first phenol-type epoxy resin, bisphenol-type epoxy resin, xenol phenolic resin varnish type epoxy resin, naphthalene type epoxy resin or their potpourri.

As the example of multifunctional oxetane compound, can enumerate: two [(3-methyl-3-oxetanes methoxyl) methyl] ether, two [(3-ethyl-3-oxetanes methoxyl) methyl] ether, 1, two [(3-methyl-3-oxetanes methoxyl) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanes methoxyl) methyl] benzene of 4-, (3-methyl-3-oxetanes) methacrylate, (3-ethyl-3-oxetanes) methacrylate, (3-methyl-3-oxetanes) methylmethacylate, (3-ethyl-3-oxetanes) methylmethacylate, the multifunctional oxetanes classes such as their oligomer or multipolymer, and oxa-cyclobutanol and novolac resin, poly-(4-Vinyl phenol), Cardo type biphenyl phenols, calixarene kind, resorcinol calixarene kind, or silsesquioxane etc. has the etherate etc. of the resin of hydroxyl.In addition, can also enumerate: there is the unsaturated monomer of oxa-ring fourth ring and the multipolymer etc. of (methyl) alkyl acrylate.

As the compound in molecule with multiple cyclic thioether base, such as, can enumerate: the bisphenol A-type episulfide resin YL7000 etc. that Mitsubishi chemical Co., Ltd manufactures.In addition, also can use and utilize same synthetic method that the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced with the episulfide resin etc. of sulphur atom.

For the compounding amount of heat curable component in molecule with multiple ring-type (sulphur) ether, relative to (A) carboxyl 1 equivalent containing carboxy resin, ring-type (sulphur) ether is preferably the scope of 0.6 ~ 2.5 equivalent.When compounding amount is more than 0.6, the raising such as thermotolerance, alkali resistance, electrical insulating property of curing overlay film.On the other hand, when being below 2.5 equivalents, the raisings such as the intensity of curing overlay film.Be more preferably 0.8 ~ 2.0 equivalent.

And then the example of the amino resins such as melamine derivative, benzoguanamine derivant enumerated as other heat-curing resins is melamine methylol compound, methylolbenzoguanamine compound, methylol glycoluril compound and hydroxymethyl urea compound etc.And then alkoxymethylated melamine compound, aikoxymethytated benzoguanamine compound, aikoxymethytated glycolurils compound and aikoxymethytated urea compounds obtain respectively by the methylol of melamine methylol compound, methylolbenzoguanamine compound, methylol glycoluril compound and hydroxymethyl urea compound is converted to alkoxy methyl.For the kind of this alkoxy methyl, there is no particular limitation, such as, can be set to methoxy, ethoxyl methyl, propoxy methyl, butoxymethyl etc.

As these commercially available products, such as can enumerate: CYMEL 300, CYMEL 301, CYMEL303, CYMEL 370, CYMEL 325, CYMEL 327, CYMEL 701, CYMEL 266, CYMEL 267, CYMEL 238, CYMEL 1141, CYMEL 272, CYMEL 202, CYMEL1156, CYMEL 1158, CYMEL 1123, CYMEL 1170, CYMEL 1174, CYMELUFR65, CYMEL 300 (is MT AquaPolymer, Inc. manufacture), NIKALAC Mx-750, NIKALAC Mx-032, NIKALAC Mx-270, NIKALAC Mx-280, NIKALACMx-290, NIKALAC Mx-706, NIKALAC Mx-708, NIKALAC Mx-40, NIKALAC Mx-31, NIKALAC Ms-11, NIKALAC Mw-30, NIKALACMw-30HM, NIKALAC Mw-390, NIKALAC Mw-100LM, NIKALACMw-750LM (is SANWA CHEMICAL CO., LTD. manufacture) etc.This heat curable component can be used alone or combinationally use two or more.

Relative to aforementioned (A) containing carboxy resin 100 mass parts, the compounding amount of the heat curable component such as these amino resins is preferably below 30 mass parts, more preferably 0.1 ~ 20 mass parts, is particularly preferably 1 ~ 15 mass parts.

[(D) Photoepolymerizationinitiater initiater]

Hardening resin composition of the present invention contains Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, more than a kind Photoepolymerizationinitiater initiater in the group being selected from and being made up of the oxime ester system Photoepolymerizationinitiater initiater with oxime ester base, alkyl phenones system Photoepolymerizationinitiater initiater, alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater, luxuriant titanium system Photoepolymerizationinitiater initiater can be used aptly.

Particularly above-mentioned oxime ester system Photoepolymerizationinitiater initiater also can suppress exhaust less due to addition, to PCT patience, resistance to anti-thread breakage effective, is preferred.

For oxime ester system Photoepolymerizationinitiater initiater, as commercially available product, can enumerate: CGI-325, IRGACURE OXE01, IRGACURE OXE02 that BASF JAPAN LTD. manufactures; N-1919, NCI-831 etc. that ADEKA Corp. manufactures.In addition, also the Photoepolymerizationinitiater initiater with two oxime ester bases can be used in molecule aptly.And then, preferably there is the oxime ester system Photoepolymerizationinitiater initiater of carbazole structure.The compounding amount of this oxime ester system Photoepolymerizationinitiater initiater is preferably set to 0.01 ~ 5 overall quality % of composition, is more preferably set to 0.25 ~ 3 quality %.

As the commercially available product of alkyl phenones system Photoepolymerizationinitiater initiater, can enumerate: the Alpha-hydroxy alkyl phenones types such as IRGACURE184, DAROCUR1173, IRGACURE2959, IRGACURE127 that BASF JAPAN LTD. manufactures.As alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, specifically, can enumerate: 2-methyl isophthalic acid-[4-(methyl thio) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino benzoylformaldoxime etc.As commercially available product, can enumerate: IRGACURE907, IRGACURE369, IRGACURE379 etc. that BASFJAPAN LTD. manufactures.

As acylphosphine oxide system Photoepolymerizationinitiater initiater; specifically; can enumerate: 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 oxides etc.As commercially available product, can enumerate: the IRGACURE819 etc. that LucirinTPO, BASF JAPAN LTD. that BASFJAPAN LTD. manufactures manufactures.

The compounding amount of these alpha-aminoacetophenone system Photoepolymerizationinitiater initiaters, acylphosphine oxide system Photoepolymerizationinitiater initiater is preferably 0.1 ~ 25 overall quality % of composition, is more preferably 1 ~ 20 quality %.

In addition, as Photoepolymerizationinitiater initiater, the IRGACURE389 that BASF JAPAN LTD. manufactures can also be used aptly.The suitable compounding amount of IRGACURE389 is overall 0.1 ~ 20 quality % of composition, and further 1 ~ 15 quality % is suitable.

And, also can use the luxuriant titanium system Photoepolymerizationinitiater initiaters such as IRGACURE784 aptly.The suitable compounding amount of luxuriant titanium system Photoepolymerizationinitiater initiater is overall 0.01 ~ 5 quality % of composition, and further 0.01 ~ 3 quality % is suitable.

By these Photoepolymerizationinitiater initiaters are set to suitable compounding amount, the curing overlay film that the chemical proofing such as photo-curable and excellent in resolution, adaptation, the raising of PCT patience and then the gold-plated property of chemically-resistant is also excellent can be made.

In this hardening resin composition, except Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, sensitizer can be used.As the Photoepolymerizationinitiater initiater that can be suitable in hardening resin composition using, light-initiated auxiliary agent and sensitizer, can enumerate: benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketal compound, benzophenone cpd, tertiary amine compound and xanthone compound etc.

As benzoin compound, such as, can enumerate: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether etc.

As acetophenone compound, such as, can enumerate: acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone etc.

As anthraquinone compounds, such as, can enumerate: 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone etc.

As thioxanthone compounds, such as, can enumerate: 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone etc.

As ketal compound, such as, can enumerate: acetophenone dimethyl ketal, benzil dimethyl ketal etc.

As benzophenone cpd, such as, can enumerate: 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, such as can enumerate: ethanolamine compound, there is the compound of dialkyl amido benzene structure, such as, can enumerate in commercially available product: 4, 4 '-dimethylamino benzophenone (NIPPONSODA CO., LTD. the NISSOCUREMABP manufactured), 4, 4 '-diethylamino benzophenone (HODOGAYA CHEMICAL CO., LTD. the EAB manufactured) etc. dialkyl amido benzophenone, 7-(diethylamino)-4-methyl-2H-1-chromen-2-ones (7-(diethylamino)-4-methylcoumarin) etc. are containing dialkyl amido coumarin compound, EDMAB (Nippon KayakuCo., Ltd. the KAYACURE EPA manufactured), 2-dimethyl amino benzoate (the Quantacure DMB that InternationalBio-Synthetics Corporation manufactures), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (the Quantacure BEA that International Bio-Synthetics Corporation manufactures), ESCAROL 507 isopentyl ethyl ester (Nippon Kayaku Co., Ltd. the KAYACUREDMBI manufactured), 4-dimethylaminobenzoic acid 2-Octyl Nitrite (Esolol507 that Van Dyk Corporation manufactures), 4, 4 '-diethylamino benzophenone (HODOGAYA CHEMICAL CO., LTD. the EAB manufactured) etc.

Wherein, preferred thioxanthone compounds and tertiary amine compound.Particularly from the aspect of deep curability, preferably containing thioxanthone compounds.Wherein, preferably containing thioxanthone compounds such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone.

As the compounding amount of this thioxanthone compounds, be preferably below the 20 quality % that composition is overall.When the compounding amount of thioxanthone compounds is below 20 quality %, thick film curability improves.Be more preferably below 10 quality %.

In addition, as tertiary amine compound, preferably there is the compound of dialkyl amido benzene structure, wherein, particularly preferably dialkyl amido benzophenone cpd, maximum absorption wavelength be 350 ~ 450nm scope in containing dialkyl amido coumarin compound and cumarin ketone.

As dialkyl amido benzophenone cpd, 4,4 '-diethylamino benzophenone is because toxicity is low preferably.Because the maximum absorption wavelength containing dialkyl amido coumarin compound is in the ultraviolet range of 350 ~ 410nm, therefore not only can provide painted less, water white curing overlay film, can also provide and use colorant and react the color solidification overlay film of the color of colorant self.Particularly, from the sensitization effect of the laser display excellence to wavelength 400 ~ 410nm, preferred 7-(diethylamino)-4-methyl-2H-1-chromen-2-one.

As the compounding amount of this tertiary amine compound, be preferably 0.01 ~ 20 quality % that composition is overall.If the compounding amount of tertiary amine compound is lower than 0.01 quality %, then there is the tendency that can not obtain sufficient sensitization effect.On the other hand, when being below 20 quality %, there is the tendency that deep curability improves.Be more preferably 0.5 ~ 10 quality %.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can be used alone or use two or more as a mixture.

The total amount of this Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer is preferably overall below the 30 quality % of composition.

[reactive diluent]

Hardening resin composition of the present invention is preferably containing reactive diluent.As reactive diluent, the preferably compounding compound with ethylenically unsaturated group in the molecule.The compound in molecule with ethylenically unsaturated group carries out photocuring by the irradiation of active energy beam, and photosensitive polymer combination of the present invention can be made to be insoluble to or to help it to be insoluble to the compound of aqueous alkali.As this compound, usual known polyester (methyl) acrylate, polyethers (methyl) acrylate, carbamate (methyl) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate can be used, specifically, can enumerate: the hydroxyalkyl acrylates classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate; 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, tris(2-hydroxy ethyl)isocyanurate 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-claimed cpd, also 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 via diisocyanate and obtain and melamine acrylate and each methyl acrylic ester corresponding with aforesaid propylene acid esters at least any one etc.

And then, can enumerate: the hydroxyl reaction of the Epocryl that the polyfunctional epoxy resin such as acrylic acid and cresol novolak type epoxy resin is reacted and then half carbamate compounds that the diisocyanate such as hydroxy acrylate and isoflurane chalcone diisocyanate such as pentaerythritol triacrylate are formed and this Epocryl and the epoxy amino formic ether acrylate compounds etc. obtained.This epoxy acrylate system resin can improve photo-curable and can not reduce dry to touch.

The compound in molecule as described above with ethylenically unsaturated group can be used alone a kind, also can combinationally use two or more.Particularly from the view point of photoreactivity and resolution, preferably there are in 1 molecule 4 compounds to 6 ethylenically unsaturated groups, and then, if use in 1 molecule the compound with two ethylenically unsaturated groups, then reduces from the thermal linear expansion coefficient of solidfied material, PCT time the aspect that reduces of the generation of peeling off and preferred.

The compounding amount in molecule as described above with the compound of ethylenically unsaturated group is preferably 2 ~ 50 overall quality % of composition.When compounding amount is more than 2 quality %, easily form pattern.On the other hand, when being below 50 quality %, the intensity of curing overlay film improves.Be more preferably 3 ~ 40 quality %.

[isocyanate compound]

Can add in hardening resin composition of the present invention there is in 1 molecule multiple isocyanate group compound and 1 molecule in there is the compound of multiple end-blocking isocyanate group.As the compound in this 1 molecule with multiple isocyanate group or end-blocking isocyanate group, can enumerate: polyisocyanate compound or blocked isocyanate compounds etc.It should be noted that, end-blocking isocyanate group refers to the group of protected by the reaction with end-capping reagent, the temporary transient passivation of isocyanate group, and when heating at the specified temperature, this end-capping reagent dissociates generation isocyanate group.By adding the obdurability of solidfied material that above-mentioned polyisocyanate compound or blocked isocyanate compounds can improve curability and obtain.

As this polyisocyanate compound, such as, can use aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.

As the object lesson of aromatic polyisocyanate, such as can enumerate: 4,4 '-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 dipolymer etc.

As the object lesson of aliphatic polyisocyante, can enumerate: tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate) and isoflurane chalcone diisocyanate etc.

As the object lesson of ester ring type polyisocyanates, norbornane triisocyanate can be enumerated.In addition, that can enumerate the isocyanate compound of listed earlier adds zoarium, biuret body and isocyanuric acid ester body etc.

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, such as, above-mentioned polyisocyanate compound etc. can be enumerated.

As isocyanate-terminated dose, such as, can enumerate: 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, diacetyl monoxime, hexamethylene oxime; The mercaptan system end-capping reagents such as butanethiol, hexyl mercaptans, tert-butyl mercaptan, thiophenol, methyl thio phenol, ethylthiophenol; The acid amides system end-capping reagents such as acetic acid acid amides, benzamide; The imide series such as succinimide 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, such as can enumerate: Sumidule BL-3175, BL-4165, BL-1100, BL-1265, Desmodule TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmodule 2170, Desmodule 2265 (is SUMITOMO BAYERURETHANE CO., LTD. manufacture), Coronate 2512, Coronate 2513, Coronate 2520 (is Nippon Polyurethane Industry Co., Ltd. manufacture), B-830, B-815, B-846, B-870, B-874, B-882 (being MITSUI TAKEDA CHEMICALS INC. to manufacture), TPA-B80E, 17B-60PX, E402-B80T (being Asahi Kasei Chemicals Corporation to manufacture) etc.It should be noted that, Sumidule BL-3175, BL-4265 use Methylethyl oxime to obtain as end-capping reagent.The compound in this 1 molecule with multiple isocyanate group or end-blocking isocyanate group can be used alone or combinationally use two or more.

The compounding amount in this 1 molecule with the compound of multiple isocyanate group or end-blocking isocyanate group is preferably 0.1 ~ 50 overall quality % of composition.When compounding amount is more than 0.1 quality %, the obdurability of sufficient curing overlay film can be obtained.On the other hand, when being below 50 quality %, storage stability improves.Be more preferably 1 ~ 30 quality %.

[organic solvent]

For hardening resin composition of the present invention, above-mentioned containing carboxy resin, modulation group compound in order to synthesize, or be coated with in base material, carrier film to adjust viscosity, can be with an organic solvent.

As this organic solvent, can enumerate: ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, petroleum solvent etc.More specifically, such as can enumerate: the ketone such as MEK, cyclohexanone; Toluene, dimethylbenzene, durene 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 two or more as a mixture.

[curing accelerator]

Curing accelerator (curing catalysts), imidazoles isocyanate addition product that the present invention also can use the curing accelerator (curing catalysts) of heat curable component, heat curable component and react containing carboxy resin.

For curing accelerator, such as, can enumerate: the imdazole derivatives such as derivant, melamine, imidazoles, benzimidazole, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole of dicyandiamide, dicyandiamide; Benzyl dimethyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzylamine, 4-methyl-N, the heterogeneous ring compounds such as the amines such as N-dimethyl benzylamine, benzoxazole, benzothiazole, benzotriazole, such as, can enumerate: the season phosphonium salt such as the tertiary phosphines such as triphenylphosphine, three p-methylphenyl phosphines, tri-o-tolyl phosphine, three tolylphosphine, tetraphenyl boron tetraphenyl phosphine, four p-methylphenyl boron tetraphenyl phosphines, tetraphenyl phosphine thiocyanic ester, tetrabutyl phosphine caprate etc.Wherein, preferred season phosphonium salt.And then, wherein, from the view point of storage-stable, particularly preferably four p-methylphenyl boron tetraphenyl phosphines.

This curing accelerator can be used alone, also can be used in combination two or more.The compounding amount of curing accelerator is generally 0.01 overall quality % ~ 15 quality % of composition, is more preferably 0.1 ~ 10 quality %.

Usually, most of macromolecular material once oxidation just can be in succession chain there is oxidative degradation, the function of macromolecule raw material is caused to reduce, therefore, the radical scavenger that the free radical of generation can be made to lose efficacy can be added in hardening resin composition of the present invention in order to anti-oxidation or/and the material that the peroxide breakdown of generation can be made to become harmless, the antioxidant such as peroxide decomposer that can not generate new free radical.

About the antioxidant played a role as radical scavenger, as concrete compound, can enumerate: quinhydrones, 4-tert-butyl catechol, TBHQ, hydroquinone monomethyl ether, 2, 6-di-t-butyl-paracresol, 2, 2-methylene-bis-(4-methyl-6-tert-butylphenol), 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, 3, 5-tri-(3 ', 5 '-di-tert-butyl-4-hydroxyl benzyl)-guanamine, 4, 6-(1H, 3H, 5H) the phenol system such as triketone, p methoxy phenol (methoquinone), the quinone based compounds such as benzoquinones, two (2, 2, 6, 6-tetramethyl-4-piperidyl)-sebacate, amine compounds such as phenothiazine etc.

Radical scavenger also can be commercially available product, such as can enumerate: ADEKASTAB AO-30, ADEKASTAB AO-330, ADEKASTAB AO-20, ADEKASTAB LA-77, ADEKASTAB LA-57, ADEKASTAB LA-67, ADEKASTAB LA-68, ADEKASTAB LA-87 (more than, ADEKA CORPORATION manufactures, trade name), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (more than, Ciba Specialty Chemicals Inc. manufactures, trade name) etc.

For the antioxidant played a role as peroxide decomposer, as concrete compound, can enumerate: the chalcogenide compounds etc. such as the phosphorus series compounds such as triphenyl phosphite, pentaerythrite four lauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 '-thiodipropionate.

Peroxide decomposer also can be commercially available product, such as can enumerate: (ADEKA CORPORATION manufactures ADEKASTABTPP, trade name), Mark AO-412S (Adeka ArgusChemical Co., Ltd. manufacture, trade name), SumilizerTPS (Sumitomo Chemical Co manufacture, trade name) etc.

Above-mentioned antioxidant can be used alone a kind or combinationally use two or more.

In addition, usual macromolecular material absorbs light, decomposes/deterioration thus, therefore, in hardening resin composition of the present invention, in order to implement, for ultraviolet stabilization countermeasure, can also to use ultraviolet light absorber except above-mentioned antioxidant.

As ultraviolet light absorber, can enumerate: benzophenone derivates, benzoate derivatives, benzotriazole derivatives, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivates, anthranilate derivatives, dibenzoylmethane derivative etc.As the concrete example of benzophenone derivates, can enumerate: ESCALOL 567, Octabenzone, 2,2 '-dihydroxy-4-methoxy benzophenone and 2,4-DihydroxyBenzophenone etc.As the concrete example of benzoate derivatives, can enumerate: BMDBM, phenyl salicylate, salicylic acid are to tert-butyl-phenyl ester, 2,4-bis--tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester and cetyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester etc.As the concrete example of benzotriazole derivatives, can enumerate: 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole and 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole etc.As the concrete example of pyrrolotriazine derivatives, can enumerate: hydroxyphenyltriazinuv, BEMT etc.

Also can be commercially available product as ultraviolet light absorber, such as can enumerate: TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN479 (more than, Ciba Specialty Chemicals Inc. manufactures, trade name) etc.

Above-mentioned ultraviolet light absorber can be used alone or combinationally use two or more, by combinationally using aforementioned antioxidant, can realize the stabilization of the article shaped obtained by photosensitive polymer combination of the present invention.

In hardening resin composition of the present invention, be further used as any composition, can compounding following known additive kind: cyanate ester resin, organic solvent, elastic body, sulfhydryl compound, colorant, antioxidant, ultraviolet light absorber, closely sealed promoter, polymerization inhibitor, fine particle silica, organobentonite, the thickening agents such as smectite, silicon-type, fluorine system, in the defoamers such as macromolecular and levelling agent at least any one, imidazoles system, thiazole system, the silane coupling agents such as triazole system, rust preventive, phosphinates, phosphate derivative, the fire retardants such as phosphorus compound such as phosphazene compound, segmented copolymer.

Hardening resin composition of the present invention is suitable for the curing overlay film being used as to form printed circuit board (PCB), particularly FPC, and preferably being used as forms permanent overlay film, and optimum is used as to form overlayer or solder mask.It should be noted that, hardening resin composition of the present invention also may be used for forming interlayer dielectic, Xi Di (Solder Dam) etc.

< dry film >

Dry film of the present invention has coating hardening resin composition of the present invention and dry and curable resin layer that is that formed.Dry film of the present invention uses with the mode lamination curable resin layer of contact substrate.The solvent residual amount of above-mentioned formed curable resin layer is preferably less than 5 % by weight.Thus, curable resin layer can be transferred on base material well.

Dry film of the present invention can manufacture as follows: pass through the suitable method even spread hardening resin composition such as knife type coater, lip coating machine (lip coater), comma coater (comma coater), film coater on a carrier film, dry, form aforesaid curable resin layer, preferred stacked cover film thereon, thus manufacture.Cover film can be identical membraneous material with carrier film, also can use different films.

In dry film of the present invention, the membraneous material of carrier film, cover film can be used as arbitrarily the known material of the material used in dry film.

As carrier film, such as, thickness can be used to be the thermoplastic films such as the mylar of the polyethylene terephthalate of 2 ~ 150 μm etc.

As cover film, can polyethylene film, polypropylene film etc. be used, but preferably little than carrier film with the bonding force of curable resin layer film.

The thickness of the curable resin layer in carrier film of the present invention is preferably less than 100 μm, is more preferably the scope of 5 ~ 50 μm.

< printed circuit board (PCB) >

Printed circuit board (PCB) of the present invention uses the curable resin layer of the present invention forming hardening resin composition of the present invention or dry film to make.Printed circuit board (PCB) of the present invention preferably press dry film at layers on substrates and makes.Printed circuit board (PCB) of the present invention can pass through the suitable method such as knife type coater, lip coating machine, comma coater, film coater, base material is directly coated with hardening resin composition and forms curing overlay film.

When forming curing overlay film at direct coating dry film or hardening resin composition, to the curable resin layer formed on base material, adopt contact or cordless to make active energy beam pass through to form figuratum photomask and optionally carry out exposing or utilize the direct exposure machine of laser directly to carry out pattern exposure.The exposure portion of curable resin layer, namely by active energy beam irradiate partially cured.

As base material, except being pre-formed with the printed circuit board (PCB) of circuit, flexible printed circuit board, the copper-clad laminated board, Kapton, PET film, glass substrate, ceramic substrate, wafer board etc. of all grades (FR-4 etc.) employing the compound substances such as paper-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 PPO cyanate can also be adopted.

The exposure machine used is irradiated as active energy beam, direct drawing apparatus (such as by utilizing the laser direct imaging device of Direct Laser rendering image from the cad data of computing machine) can be used, be equipped with the exposure machine of metal halide lamp, be equipped with the exposure machine of (surpassing) high-pressure sodium lamp, be equipped with the exposure machine of LED, be equipped with the exposure device of mercury short arc lamp.

As active energy beam, maximum wavelength is preferably used to be in the light of the scope of 350 ~ 410nm.By maximum wavelength is set to this scope, free radical can be generated efficiently by Photoepolymerizationinitiater initiater.In addition, its exposure is different from thickness etc., but usually can be set to 5 ~ 500mJ/cm ², be preferably set to 10 ~ 300mJ/cm ²scope in.

As direct drawing apparatus, such as can use Orbotech Ltd. manufacture, PENTAXCorporation manufacture, OAK Corporation manufacture, SCREEN Holdings Co., Ltd. manufacture waits device, as long as be that the device of the active energy beam of 350 ~ 410nm just can use arbitrary device for irradiating maximum wavelength.

And, so by exposure curing resin bed, exposure portion is solidified, then utilize dilute alkaline aqueous solution (such as, 0.3 ~ 3wt% aqueous sodium carbonate) to develop to unexposed portion, curable resin layer forms pattern.

As developing method, infusion process, elution method, spray-on process, spread coating etc. can be used.In addition, as developer solution, the aqueous alkali of potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc. can be used.

And then curable resin layer solidifies by the temperature such as by being heated to about 140 ~ 180 DEG C, can form the pattern of the curing overlay film forming the various excellent such as adaptation, thermotolerance, chemical proofing, electrical insulating property of material relative to base material.It should be noted that, the pattern of curing overlay film also can by irradiating CO ₂semiconductor lasers such as laser, UV-YAG laser and being formed.

The total film thickness of the curing overlay film in printed circuit board (PCB) of the present invention is preferably less than 100 μm, is more preferably the scope of 1 ~ 50 μm.

Embodiment

Below illustrate that embodiment and comparative example are specifically described the present invention, but the present invention is not limited to following embodiment.It should be noted that, below, " part " and " % " all refers to quality criteria in case of no particular description.

[embodiment 1 ~ 7 and comparative example 1 ~ 2]

(preparation of hardening resin composition)

Various composition according to following table 1 and the ratio shown in table 1 (mass parts) are carried out compounding, after stirring machine premixed, carry out mixing, prepare hardening resin composition with three-roll grinder.

Table 1

The implication of the numeral of writing a Chinese character in simplified form, adding in aforementioned table 1 is as follows.

PN: phenol novolak type epoxy resin

AA: acrylic acid

THPA: tetrabydrophthalic anhydride

CN: cresol novolak type epoxy resin

CA: carbitol acetate

※ 1: acrylated polyacrylate is (containing acid based aery late; Mw=19000 ~ 25000, acid number 58 ?79KOHmg/g; DAICEL-ALLNEX LTD. manufactures)

※ 2: bisphenol A novolac type epoxy resin (Dainippon Ink Chemicals manufactures: epoxide equivalent=200 ~ 210)

※ 3: containing the phenolic resin varnish type epoxy resin (Nippon Kayaku Co., Ltd. manufactures: epoxide equivalent=200 ~ 220) of biphenyl backbone

※ 4:2-methyl 1-[4-(methyl thio) phenyl]-2-morpholino propane-1-ketone

※ 5:2,4-diethyl thioxanthene-9-one

[attribute testing of embodiment 1 ~ 7 and comparative example 1 ~ 2]

< chemically-resistant gold-plated property >

On a printed circuit with after the hardening resin composition of silk screen print method coating the various embodiments described above and comparative example, in heated air circulation type drying oven at 80 DEG C dry 30 minutes.After being cooled to room temperature, at exposure 700mJ/cm ²condition expose, in heated air circulation type drying oven, at 150 DEG C, be cured 60 minutes, obtain assess sample.The assess sample obtained be impregnated in acidic degreasing liquid (the Nippon MacDermid Co. of 30 DEG C, Ltd. manufacture, the 20vol% aqueous solution of METEX L-5B) in 3 minutes, then wash, then at room temperature impregnated in 14.4wt% ammonium persulfate aqueous solution 3 minutes, after washing, at room temperature impregnated in 10vol% aqueous sulfuric acid 1 minute further.Then, (Meltex Inc. manufactures this evaluation substrate to be impregnated in the catalyzer liquid of 30 DEG C, the 10vol% aqueous solution of MelplateActivator350) wash after 5 minutes, (Meltex Inc. manufactures to impregnated in the nickel-plating liquid of 85 DEG C, the 20vol% aqueous solution of MelplateNi-865M, pH=4.6), after within 30 minutes, implementing nickel plating, at room temperature impregnated in 10vol% aqueous sulfuric acid 1 minute, wash.Then, by assess sample substrate being impregnated in gold plating liquid (15vol% of the AurolectrolessUP that Meltex Inc. manufactures and the potassium auricyanide 3vol% aqueous solution of 95 DEG C, pH=6) after within 30 minutes, implementing chemical gilding, wash, impregnated in the warm water 3 minutes of 60 DEG C further, use circulating water to wash.The assess sample glassivation paper adhesive strip gold-plated to the enforcement obtained, confirms the state of curing overlay film when peeling off.Determinating reference is as follows.

Zero: curing overlay film is completely not abnormal.

△: curing overlay film is peeling a little.

×: curing overlay film is peeled off.

Evaluate substrate

Following characteristic uses following evaluation substrate to carry out.

Being applied to the whole face of mode that dry film thickness becomes 20 μm by the hardening resin composition of each embodiment and comparative example by serigraphy is formed on figuratum copper clad laminate, at 80 DEG C dry 30 minutes, is cooled to room temperature.To this substrate, use and carry the exposure device of high-pressure sodium lamp with optimum exposure exposing patterns, then the 1wt% aqueous sodium carbonate of 30 DEG C is carried out under the condition spraying 0.2MPa development 90 second, obtaining pattern.By this substrate at cumulative exposure amount 1000mJ/cm ²condition under carry out Ultraviolet radiation with UV furnace conveyor, then at 150 DEG C heating within 90 minutes, make it solidify, obtain the evaluation substrate of the pattern being formed with curing overlay film.

Use the evaluation substrate obtained, acid resistance, alkali resistance, resistance to soldering heat performance, electrical insulating property are evaluated as follows.

< acid resistance >

Evaluation substrate at room temperature be impregnated in 10vol%H ₂sO ₄aqueous solution 30 minutes, by the visual stripping confirming infiltration and curing overlay film, confirms to peel off by band the stripping caused further.Determinating reference is as follows.

Zero: curing overlay film Dao Bao unconfirmed From.

△: curing overlay film confirms slightly to be peeled off.

×: the stripping of whole of curing overlay film.

< alkali resistance >

Evaluation substrate at room temperature be impregnated in 10vol%NaOH aqueous solution 30 minutes, by the visual stripping confirming infiltration and curing overlay film, confirm further to peel off by band the stripping caused.Determinating reference is as follows.

Zero: curing overlay film is unconfirmed to peeling off.

△: curing overlay film confirms slightly to be peeled off.

×: the stripping of whole of curing overlay film.

< resistance to soldering heat performance >

The Kapton substrate being formed with circuit pattern is formed the pattern of curing overlay film as described above.The evaluation substrate of like this preparation is coated with rosin series solder flux, carries out flooding 5 times 10 seconds being redefined in the solder bath of 260 DEG C, after washing solder flux with modification alcohol, evaluated by the visual expansion to curing overlay film and stripping.Determinating reference is as follows.

◎: unconfirmed to peeling off.

Zero: the part except edge confirms there is small stripping, but within 3.

△: marginal portion confirms stripping.

×: there is expansion, peel off.

< electrical insulating property >

Use the combed B pattern of live width/spacing=50/50 μm, prepare above-mentioned evaluation substrate, carry out the evaluation of electrical characteristics.

Evaluation method is as follows: the process 7 days this comb-type electrode being carried out under the heating and moistening condition of 25 ~ 65 DEG C of circulations, 90%R.H. the bias voltage applying DC100V, after humidification, measures the resistance value (Ω) after applying 500V with the form of 1 minute value.

Zero: 1 × 10 ¹²above.

△: 1 × 10 ¹¹above and lower than 1 × 10 ¹².

×: lower than 1 × 10 ¹¹.

The adaptation > of < underfill

In above-mentioned < chemically-resistant gold-plated property >, by evaluation substrate plasma (the gas Ar/O through chemical gilding ₂power: 350W, vacuum tightness: 300mTorr) carry out process 60 seconds, coating underfill (DENATITE R3003iEX Nagase chemteX Corporation manufactures), solidify 1 hour at 160 DEG C, carry out the Reflow Soldering of 3 260 DEG C of peak values further, and then 121 DEG C, 2 air pressure, 100% humidity under carry out 100 hours pressure cooker test (moisture-proof evaluation) after, measured the adaptation of underfill and curing overlay film by thrust meter (push gauge), evaluate with following benchmark.

◎: more than 100N.

Zero: more than 80N and lower than 100N.

△: more than 60N and lower than 80N.

×: lower than 60N.

[preparation of dry film :]

Use the hardening resin composition of above-described embodiment 1 ~ 7 and comparative example 1 ~ 2, preparation has the dry film of curable resin layer.Dry film is coated with hardening resin composition with coating device on the mylar that the thickness as carrier film is 38 μm, dry 10 minutes and preparation at 80 DEG C.At this, relative to the overall residual organic solvent less than 5% of composition in curable resin layer.

Use this dry film to carry out and aforementioned same physical property test, but obtain same result.

In addition, press the dry film of each embodiment at layers on substrates after, peel off carrier film, judge whether carrier film adheres to the hardening resin composition being derived from curable resin layer by visual.Its result, in the dry film of each embodiment, confirms not adhere to hardening resin composition on a carrier film.

The mensuration > of the residual content (%) of the organic solvent in < hardening resin composition

After peeling off carrier film from the dry film of each embodiment, take the curable resin layer of about 1.2g, put into the container of band sealing-plug and the quality (W) of curable resin layer taked of precise.1 3-ethoxyl ethyl propionate as internal standard material is added to this container, this quality of precise (We) with pipettor.Thereafter, add acetone 5ml by whole pipet and seal, fully rock container and the curable resin layer taked is dissolved.Then, with this liquid of metre filter of perforate 0.5 μm, the composition of filtrate is analyzed by gas chromatography (TRACEGCULTRA that Thermo Fisher Scientific K.K. manufactures), is obtained the quality (Ws) of the organic solvent relative to internal standard material 1g by the calibration curve made in addition.The residual content of organic solvent is calculated according to the following formula by this quality.

Residual content (quality %)=(We × Ws/W) × 100 of organic solvent

It should be noted that, the condition determination of gas chromatography is as follows.The capillary chromatographic column DB-1MS (30m × 0.25mm) that post: AgilentTechnologies manufactures, detecting device: MS (ITQ900), carrier gas: helium, injection temperation: 300 DEG C, detected temperatures: 230 DEG C, column temperature condition: initial temperature 50 DEG C, keeps 2 minutes after sample injects at 50 DEG C, be warming up to 300 DEG C with 10 DEG C/min, keep 10 minutes after arriving 300 DEG C.

utilizability in industry

Various coating material, printing-ink, surface conditioning agent, moulding material, bonding agent, bonding agent, cementing agent, various erosion resistant, color filter manufacture material, the optical waveguide materials etc. such as hardening resin composition Ke Zuo Tu material of the present invention, particularly can be used for forming the solder mask of printed circuit board (PCB), the interlayer insulating film, light waveguide-layer etc. of multilayer board.

Claims (8)

1. a hardening resin composition, it is characterized in that, it is for comprising (A) hardening resin composition containing carboxy resin, (B) inorganic filler, (C) heat curable component and (D) Photoepolymerizationinitiater initiater

Described (A) containing carboxy resin comprise have novolaks skeleton containing carboxy resin,

Described (C) heat curable component comprises maleimide compound.

2. hardening resin composition according to claim 1, is characterized in that, described (A) has the person at least arbitrarily in phenol novolacs skeleton and cresol novolak skeleton containing carboxy resin.

3. hardening resin composition according to claim 1, is characterized in that, described maleimide compound is bismaleimide compound.

4. hardening resin composition according to claim 1, is characterized in that, relative to described (A) containing carboxy resin 100 mass parts, described maleimide compound contains below 15 mass parts.

5. the hardening resin composition according to any one in Claims 1 to 4, is characterized in that, described (C) heat curable component comprises epoxy resin.

6. for the formation of a hardening resin composition for permanent overlay film, it is characterized in that, it comprises the hardening resin composition described in any one in Claims 1 to 5.

7. a dry film, it is characterized in that, it has curable resin layer on a carrier film, and described curable resin layer is formed by the hardening resin composition described in any one in Claims 1 to 5 or the hardening resin composition for the formation of permanent overlay film according to claim 6.

8. a printed circuit board (PCB), it is characterized in that, it has curing overlay film on base material, and described curing overlay film is solidified by the described curable resin layer in the hardening resin composition described in any one in Claims 1 to 5, the hardening resin composition for the formation of permanent overlay film according to claim 6 or dry film according to claim 7.