CN102112920A - Flame-retardant photocurable resin composition, dry film and cured product of same, and printed circuit board using composition thereof - Google Patents

Abstract

Disclosed is a flame-retardant photocurable resin composition which has a halogen-free composition and thus places little burden on the environment. The flame-retardant photocurable resin composition has excellent flame retardancy and is capable of forming a cured coating film having excellent flexibility. A dry film and cured product of the composition, and a printed wiring board provided with a flame-retardant cured coating film such as a solder resist obtained by using the composition, dry film or cured product are also disclosed. The flame-retardant photocurable resin composition contains (A) an organic solvent-soluble phosphorus-containing polyester, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator. Preferably, the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin. Preferably, the flame-retardant photocurable resin composition additionally contains (D) a photopolymerizable monomer or (E) a thermosetting resin. The flame-retardant photocurable resin composition, particularly a flame-retardant photocurable/thermosetting resin composition containing the thermosetting resin (E) can be suitably used as a solder resist.

Description

Flame retardant photocurable resin composition, its dry film and solidfied material and the printed circuit board (PCB) that uses them

Technical field

The present invention relates to the Photocurable resin composition of the anti-flammability that can develop by dilute alkaline aqueous solution, particularly the solder resist that comes photocuring by ultraviolet exposure or laser explosure is with composition, its dry film and solidfied material and printed circuit board (PCB) with the cured film that uses their formed anti-flammabilitys.

Background technology

All the time, printed circuit board (PCB) and flexible electric circuit board (being designated hereinafter simply as FPC) therefore expect that it has anti-flammability owing to be equipped in the electronic equipment, also require to have anti-flammability for the solder resist of a part as them.Wherein, FPC is made of polyimide substrate usually, so its printed circuit board (PCB) with glass epoxy substrate is different, is film.Yet owing to be printed circuit board (PCB) or FPC no matter, the solder resist that be coated with is same thickness, and therefore, under the situation of FPC that be film, change is greatly relatively to the burden of fire-retardantization of solder resist.

Therefore, all the time, various schemes have been proposed at fire-retardantization of solder resist.For example; the photosensitive polymer combination of the anti-flammability that a kind of FPC uses has been proposed, the phosphorus-containing compound that it contains the optical polymerism compound, (C) Photoepolymerizationinitiater initiater, (D) blocked isocyanate compound of polymerisable ethylenic unsaturated bonds such as halogenated aromatic rings such as having bromophenyl in (A) binder polymer, (B) molecule and (methyl) acryloyl group and (E) has phosphorus atoms in the molecule in the TOHKEMY 2007-10794 communique (patent documentation 1).Yet, consider that from the viewpoint of carrying capacity of environment it is not preferred using the such halogen compounds of compound with halogenated aromatic ring and polymerisable unsaturated double-bond.

Patent documentation 1: TOHKEMY 2007-10794 communique (claims)

Summary of the invention

The problem that invention will solve

The present invention finishes in view of foregoing prior art, its purpose is, is provided as that Halogen is formed, carrying capacity of environment is little and excellent in flame retardance, cured film are rich in the cured film of flexible, as can to form excellences such as the gold-plated property of adaptation, solder heat resistance, chemically-resistant to various base materials, moisture-proof, electrical insulating property fine pattern and are suitable for the flame retardant photocurable resin composition of FPC especially.

And then, the objective of the invention is to, provide by using the dry film and the solidfied material of such Photocurable resin composition anti-flammability that obtain, above-mentioned each excellent, and form the printed circuit board (PCB) that the cured film of anti-flammabilitys such as soldering-resistance layer forms by this dry film, solidfied material.

The scheme that is used to deal with problems

In order to reach aforementioned purpose, according to the present invention, provide a kind of flame retardant photocurable resin composition, it is characterized in that its phosphorus element-containing polyester, (B) that contains (A) organic solvent solubility contains carboxy resin and (C) Photoepolymerizationinitiater initiater.Preferably, the above-mentioned carboxy resin (B) that contains is for containing the carboxyl urethane resin.

In suitable mode, further contain (D) photopolymerization monomer, perhaps further contain (E) heat-curing resin.This heat-curing resin (E) preferably comprises the epoxy resin with biphenyl backbone.Such flame retardant photocurable resin composition, the light solidifying/heat solidifying resin composition that particularly contains the anti-flammability of heat-curing resin (E) can be used as solder resist aptly.

In addition, according to the present invention, also provide by aforementioned flame retardant photocurable resin composition is applied on the carrier film and the dry film of the dry flame retardant photocurable that obtains, by aforementioned flame retardant photocurable resin composition or this dry film are cured the anti-flammability solidfied material that obtains.

And then, according to the present invention, also provide printed circuit board (PCB), it is characterized in that it has by aforementioned flame retardant photocurable resin composition or dry film are cured the anti-flammability cured film that obtains.

The effect of invention

Flame retardant photocurable resin composition of the present invention all use Halogen the organic solvent solubility the phosphorus element-containing polyester and contain carboxy resin, therefore for Halogen is formed, carrying capacity of environment is little and excellent in flame retardance, cured film are rich in flexiblely, can form the cured film of the fine pattern of excellences such as the gold-plated property of adaptation, solder heat resistance, chemically-resistant to various base materials, moisture-proof, electrical insulating property.

Therefore, flame retardant photocurable resin composition of the present invention can advantageously be applicable to the anti-flammability cured films such as soldering-resistance layer that form printed circuit board (PCB), particularly FPC.

Embodiment

As previously mentioned, first of the flame retardant photocurable resin composition of the present invention phosphorus element-containing polyester (A) that is characterised in that the organic solvent solubility of using Halogen.In addition, in this manual, term " Halogen " is meant and does not initiatively use halogen compounds, and do not comprise the situation that it is sneaked into the form of unavoidable impurities.

The phosphorus element-containing polyester (A) of organic solvent solubility is for making following substances carry out the material that copolymerization obtains when making polyester: phosphorus-containing carboxylic acid, its carboxylate, the phosphoric acid based compound, the phosphonic acids based compound, phosphorous acid (phosphorous acid) based compound, phosphonous acid (phosphonous acid) based compound, phosphorus compounds (for example with reference to TOHKEMY 2002-3587 communique, TOHKEMY 2007-204744 communique) such as phosphinous acid (phosphinous acid) based compound.

Be preferably the phosphorus element-containing polyester of the organic solvent solubility of carrying out copolymerization with the phosphorus-containing carboxylic acid shown in the following general formula (I) or its ester compounds and obtaining.

[Chemical formula 1]

In the formula, R ¹And R ²Represent hydrogen atom or alkyl independently of one another,

R ³And R ⁴Represent the alkyl that hydrogen atom, alkyl or hydroxyl replace independently of one another,

L, m represent 0～4 integer.

As the commercially available product of the phosphorus element-containing polyester of aforementioned organic solvent solubility, can list Japan and spin VYLON (registered trademark) 237, the VYLON337 etc. that (strain) makes.

These phosphorus element-containing polyester also can be to use the local polyester-polyurethane structure that imports amino-formate bond and obtain of diisocyanate.For example, as commercially available product, can enumerate Japan and spin UR3570 that (strain) make etc.

As the phosphorus element-containing polyester (A) of organic solvent solubility, can use the various high molecular weight polyester resins compounds that can be dissolved in industrial various organic solvents, there is no particular limitation, preferably has following proterties.

(1) weight-average molecular weight is generally 1000～100000, and then is preferably 5000～50000 scope.Weight-average molecular weight is less than 1000 o'clock, the not viscosity variation that gained is filmed.On the other hand, weight-average molecular weight surpasses at 100000 o'clock, and the dissolubility of various organic solvents is reduced, and in addition, the gained development of filming sometimes can significantly worsen.

(2) phosphorus content in the polyester is generally 0.3～20%, and then is preferably 1～5% scope.Less than 0.3% o'clock, can't obtain sufficient anti-flammability.On the other hand, surpass at 20% o'clock, flexible, the electrical characteristics of cured film can significantly worsen sometimes.

The use level of the phosphorus element-containing polyester (A) of organic solvent solubility be in whole compositions 0.5～50 quality %, be preferably 1～20 quality %.

When being less than above-mentioned scope, the gained cured film can't obtain sufficient anti-flammability, also can't obtain good result in addition on flexible.On the other hand, during more than above-mentioned scope, the not viscosity of filming can reduce or the viscosity of composition can raise, so not preferred.

As the employed industrial various organic solvents of the phosphorus element-containing polyester (A) of organic solvent solubility, can list ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.More specifically, can list ketones such as MEK, cyclohexanone; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; 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; 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, propylene glycol butyl ether acetic acid esters; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc.

Such organic solvent can use separately or use with the form of the potpourri more than 2 kinds, in addition, is preferably the material that can not promote the high molecular weight polyester resins compound hydrolysis.

Contain carboxy resin (B) as flame retardant photocurable resin composition of the present invention comprises, can use the resin compound known commonly used that contains carboxyl in the molecule.And then, if use have ethylenical unsaturated double bonds in the molecule contain carboxyl photoresist (B '), then can give photo-curable, form the composition of alkali-developable, so preferably.And preferably this unsaturated double-bond derives from (methyl) acrylic acid or (methyl) acrylic acid derivative.In addition, only use do not have ethylenical unsaturated double bonds contain carboxy resin the time, be photo-curable in order to make composition, need with molecule described later in have two above olefinic unsaturated groups photopolymerization monomer (D) be used in combination.

As the object lesson that contains carboxy resin (B), enumerate such compound (can be any one in oligomer and the polymkeric substance) below can using aptly.

(1) by diisocyanate such as aliphatic diisocyanates, side chain aliphatic diisocyanate, ester ring type diisocyanate, aromatic diisocyanate, containing carboxylic diol compound and polycarbonate-based polyvalent alcohol, polyethers with dihydromethyl propionic acid, dimethylolpropionic acid etc. is that polyvalent alcohol, polyester are that polyvalent alcohol, polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, bisphenol-A are the alkylene oxide adducts dibasic alcohol, have the addition polymerization of diatomic alcohol compounds such as compound of phenol hydroxyl and alcohol hydroxyl group and obtain contain the carboxyl urethane resin.

(2) by 2 officials such as diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, di-cresols type epoxy resin, united phenol-type epoxy resin can epoxy resin (methyl) acrylate or the photonasty that obtains of the addition polymerization of the anhydride modified thing of its part, carboxylic diol compound and diatomic alcohol compounds contain the carboxyl urethane resin.

(3) by have 1 hydroxyl in adding (methyl) hydroxyalkyl acrylate equimolecular in the resin of above-mentioned (1) or (2) synthetic and the compound of (methyl) acryloyl group obtains more than 1 end (methyl) propylene acidylate contain the carboxyl urethane resin.

(4) have 1 isocyanate group in the reaction with same mole thing equimolecular by adding isophorone diisocyanate and pentaerythritol triacrylate in the resin of above-mentioned (1) or (2) synthetic and the compound of (methyl) acryloyl group obtains more than 1 end (methyl) propylene acidylate contain the carboxyl urethane resin.

(5) by making the carboxy resin that contains that compound copolymerization that unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-Jia Jibenyixi, (methyl) lower alkyl acrylate, isobutylene etc. contain unsaturated group obtains.

(6) make (methyl) acrylic acid and as described later 2 officials can or more than 2 officials can the reaction of multifunctional (solid-state) epoxy resin, the photonasty that 2 yuan of acid anhydrides of hydroxyl addition of being present in side chain are obtained contains carboxy resin.

(7) photonasty of reacting, the 2 yuan of acid anhydrides of hydroxyl addition that generated being obtained with (methyl) acrylic acid by the polyfunctional epoxy resin that is obtained by the further epoxidation of hydroxyl that makes 2 officials energy (solid-state) epoxy resin with chloropropylene oxide contains carboxy resin.

(8) by such 2 officials of aftermentioned can oxetane resin being reacted with dicarboxylic acid, containing carboxyl polyester resin to what the 2 yuan of acid anhydrides of primary hydroxyl addition that generated obtained.

(9) by the photonasty that has 1 epoxy radicals in further addition 1 molecule of the resin of above-mentioned (1)～(8) and the compound of (methyl) acryloyl group obtains more than 1 is contained carboxy resin.

These contain in the carboxy resin, preferably, (X) contain the carboxyl urethane resin, especially the isocyanate group of the composition with isocyanate group (comprising diisocyanate) of this urethane resin not with the phenyl ring Direct Bonding contain the carboxyl urethane resin, from photonasty, flexible viewpoint is considered, be preferred, in addition, (Y) in aforementioned (6), (7) used polyfunctional epoxy resin is to have structure of bisphenol A in resin synthetic, the Bisphenol F structure, the xenol structure, when the compound of two xylenol structures and hydrogenated compound thereof, from thermotolerance, the viewpoint of anti-flammability is considered, is preferred.In addition, in other respects, aforementioned (1), (2), (3), (4) contain the carboxyl urethane resin and their modifier as (9) has amino-formate bond at main chain, are preferred on warpage.And then, in order to take into account characteristic such as flexible and solder heat resistance, what most preferably, be used in combination that aforementioned (1), (2), (3), (4) contain carboxyl urethane resin and they contains carboxy resin and their modifier as (9) as the modifier (9) and aforementioned (5), (6), (7), (8).

In addition, in this manual, (methyl) acrylate is the term of general designation acrylate, methacrylate and their potpourri, and other similar expression too.

The foregoing carboxy resin (B) that contains has a plurality of free carboxyls on the side chain of trunk polymer (backbonepolymer), therefore can utilize dilute alkaline aqueous solution to develop.

In addition,, it is desirable to, be preferably the scope of 40～200mgKOH/g, more preferably the scope of 45～120mgKOH/g for the aforementioned acid number that contains carboxy resin (B).If contain the not enough 40mgKOH/g of the acid number of carboxy resin, then can be difficult to alkali develops, on the other hand, if surpass 200mgKOH/g, the dissolving of the exposure portion that caused by developer solution then can take place, therefore, it is thinner than needed that line can become, sometimes exposure portion and unexposed can be developed the liquid dissolving indistinction and peel off, and are difficult to describe normal corrosion-resisting pattern, so not preferred.

In addition, the aforementioned weight-average molecular weight that contains carboxy resin (B) is according to resin matrix and difference is generally 2000～150000, and then is that 5000～100000 scope is preferred.During weight-average molecular weight less than 2000, the not viscosity variation of filming, the moisture-proof of filming after the exposure worsens, and produces the film decrement during development, and resolution is variation significantly.On the other hand, weight-average molecular weight surpasses at 150000 o'clock, and development significantly worsens, the storage stability variation.

The foregoing use level that contains carboxy resin (B) is 10～60 quality % in whole compositions, is preferably 20～50 quality %.When being less than above-mentioned scope, so coating strength reduction etc. are not preferred.On the other hand, during more than above-mentioned scope, the viscosity of composition uprises or reduction such as coating, so not preferred.

As the Photoepolymerizationinitiater initiater that uses among the present invention (C), can use known compound commonly used.

As particularly preferred Photoepolymerizationinitiater initiater, the phosphorus element-containing Photoepolymerizationinitiater initiater is arranged, can use the acylphosphine oxide with group shown in the following general formula (II-1) aptly is Photoepolymerizationinitiater initiater.

[Chemical formula 2]

In the formula, R ⁵And R ⁶The aryl of representing straight or branched alkoxy, cyclohexyl, cyclopentyl, aryl or the halogen atom of straight or branched alkyl, the carbon number 1～10 of carbon number 1～10 independently of one another, being replaced by alkyl or alkoxy, wherein, R ⁵And R ⁶One of them also can represent R-C (=O)-Ji (here, R is the alkyl of carbon number 1～20).

As the acylphosphine oxide with group shown in the above-mentioned general formula (II-1) is Photoepolymerizationinitiater initiater; can list 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2; 4,4-trimethyl-amyl group phosphine oxide etc.As commercially available product, can list Lucirin TPO, the IRGACURE (registered trademark) 819 that Xiba Special Chemical Product Co.,Ltd makes etc. that BASF AG makes.

As other preferred phosphorus element-containing Photoepolymerizationinitiater initiaters, the initiating agent shown in the following general formula (II-2) is arranged, as commercially available product, the Lucirin TPO-L that has BASF AG to make.

[chemical formula 3]

In the formula, R ⁵Have and aforementioned same implication, R ⁷Be independent of R ⁵Straight or branched alkyl, cyclohexyl, cyclopentyl, aryl or the halogen atom of ground expression carbon number 1～10, by the aryl that alkyl replaces, also can represent R-C (=O)-Ji (here, R is the alkyl of carbon number 1～20).

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the use level of such phosphorus element-containing Photoepolymerizationinitiater initiater can be from 1～80 mass parts, preferably select from the scope of 2～50 mass parts.

As the Photoepolymerizationinitiater initiater that can add except that the phosphorus element-containing Photoepolymerizationinitiater initiater, the alpha-aminoacetophenone that the oxime ester with group shown in the following general formula (III) is arranged is Photoepolymerizationinitiater initiater, have a group shown in the following general formula (IV) is a Photoepolymerizationinitiater initiater.

[chemical formula 4]

In the formula, R ⁸The naphthenic base of the alkyl of expression hydrogen atom, phenyl (can be replaced by the alkyl of carbon number 1～6, phenyl or halogen atom), carbon number 1～20 (can be replaced by the hydroxyl more than 1, can have oxygen atom more than 1 at the alkyl middle-of-chain), carbon number 5～8, the alkanoyl of carbon number 2～20 or benzoyl (can be replaced by the alkyl or phenyl of carbon number 1～6),

R ⁹The alkyl of expression phenyl (can be replaced), carbon number 1～20 (can be replaced by the hydroxyl more than 1, can have oxygen atom more than 1), the naphthenic base of carbon number 5～8, the alkanoyl or the benzoyl (can be replaced) of carbon number 2～20 by the alkyl or phenyl of carbon number 1～6 at the alkyl middle-of-chain by the alkyl of carbon number 1～6, phenyl or halogen atom

R ¹⁰And R ¹¹The alkyl or aryl alkyl of representing carbon number 1～12 independently of one another,

R ¹²And R ¹³The alkyl of representing hydrogen atom, carbon number 1～6 is independently of one another perhaps represented the cyclic alkyl ether that both bondings form.

As the oxime ester with group shown in the aforementioned formula (III) is Photoepolymerizationinitiater initiater, preferably lists compound shown in the 2-shown in the following formula (V) (acetoxyl group iminomethyl) thioxanthene-9-one, the following general formula (VI) and the compound shown in the following general formula (VII).

[chemical formula 5]

[chemical formula 6]

In the formula, R ¹⁴The alkanoyl of the alkyl of expression hydrogen atom, halogen atom, carbon number 1～12, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, carbon number 2～12, the alkoxy carbonyl group of carbon number 2～12 are (under the carbon number of the alkyl that constitutes alkoxy is situation more than 2; alkyl can replace by the hydroxyl more than 1, can have oxygen atom more than 1 at the alkyl middle-of-chain) or carbobenzoxy

R ¹⁵, R ¹⁷Represent the alkyl (can be replaced by the hydroxyl more than 1, can have oxygen atom more than 1) of phenyl (can be replaced), carbon number 1～20, the naphthenic base of carbon number 5～8, the alkanoyl or the benzoyl (can be replaced) of carbon number 2～20 independently of one another by the alkyl or phenyl of carbon number 1～6 by the alkyl of carbon number 1～6, phenyl or halogen atom at the alkyl middle-of-chain

R ¹⁶The alkyl of expression hydrogen atom, phenyl (can be replaced), carbon number 1～20 (can be replaced by the hydroxyl more than 1, can have oxygen atom more than 1), the naphthenic base of carbon number 5～8, the alkanoyl or the benzoyl (can be replaced) of carbon number 2～20 by the alkyl or phenyl of carbon number 1～6 at the alkyl middle-of-chain by the alkyl of carbon number 1～6, phenyl or halogen atom.

[chemical formula 7]

In the formula, R ¹⁸, R ¹⁹And R ²⁴The alkyl of representing carbon number 1～12 independently of one another,

R ²⁰, R ²¹, R ²²And R ²³The alkyl of representing hydrogen atom or carbon number 1～6 independently of one another,

M represents O, S or NH,

N and p represent 0～5 integer independently of one another.

At aforementioned oxime ester is in the Photoepolymerizationinitiater initiater, and the compound shown in (acetoxyl group iminomethyl) thioxanthene-9-one of the 2-shown in the aforementioned formula (V) and the formula (VI) is preferred.As commercially available product, can list CGI-325, IRGACURE OXE01, IRGACURE OXE02 that west crust specialty goods chemical company makes, the N-1919 of Asahi Denka Co., Ltd. etc.These oxime esters are that Photoepolymerizationinitiater initiater can be used alone or in combination of two or more kinds.

As the alpha-aminoacetophenone with group shown in the aforementioned formula (IV) is Photoepolymerizationinitiater initiater, can list 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino acetophenone etc.As commercially available product, can list IRGACURE 907, IRGACURE 369 that Xiba Special Chemical Product Co.,Ltd makes, IRGACURE 379 etc.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the use level of foregoing Photoepolymerizationinitiater initiater (C) can be from 0.01～50 mass parts, preferably select from the scope of 0.5～30 mass parts.During use level less than 0.01 mass parts, the photo-curable deficiency on copper is filmed and is peeled off, and perhaps coating characteristic such as chemical proofing reduces, so not preferred.On the other hand, when surpassing 50 mass parts, Photoepolymerizationinitiater initiater (C) becomes violent in the light absorption of welding resistance film coated surface, and so the tendency that exists the deep curable to reduce is not preferred.

In addition, for being the situation of Photoepolymerizationinitiater initiater for oxime ester with group shown in the aforementioned formula (III), it is desirable to, with respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, its use level is preferably from 0.01～20 mass parts, more preferably select from the scope of 0.01～5 mass parts.

Other Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer as using in Photocurable resin composition of the present invention aptly can list benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthones compound, ketal compound, benzophenone cpd, xanthone compound and tertiary amine compound etc.

If enumerate the object lesson of benzoin compound, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether then for example arranged.

If enumerate the object lesson of acetophenone compound, acetophenone, 2 then for example arranged, 2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone.

If enumerate the object lesson of anthraquinone compounds, 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone then for example arranged.

If enumerate the object lesson of thioxanthones compound, then for example have 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2,4-diisopropyl thioxanthones.

If enumerate the object lesson of ketal compound, acetophenone dimethyl ketal, benzil dimethyl ketal then for example arranged.

If enumerate the object lesson of benzophenone cpd, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4 '-methyldiphenyl thioether, 4-benzoyl-4 '-ethyl diphenyl sulfide, 4-benzoyl-4 '-propyl group diphenyl sulfide then for example arranged.

If enumerate the object lesson of tertiary amine compound, ethanolamine compound is then for example arranged, compound with dialkyl amido benzene structure, for example have 4,4 '-dimethylamino benzophenone (the NISSOCURE MABP that Japanese Cao Da company makes), 4,4 '-lignocaine benzophenone (Hodogaya Chemical Co., the EAB of Zhi Zaoing Ltd.) dialkyl amido benzophenone such as, 7-(lignocaine)-4-methyl-2H-1-chromen-2-one, (7-(lignocaine)-4-methylcoumarin) etc. contains the coumarin compound of dialkyl amido, ethyl 4-dimethy laminobenzoate (the KAYACURE EPA that Japanese chemical drug corporate system is made), 2-dimethylamino ethyl benzoate (the Quantacure DMB that International Bio-Synthetics company makes), 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (the Quantacure BEA that International Bio-Synthetics company makes), to dimethylamino benzoic acid isopentyl ethyl ester (KAYACUREDMBI that Japanese chemical drug corporate system is made), 4-dimethylamino benzoic acid-2-Octyl Nitrite (Esolol 507 that Van Dyk company makes), 4,4 '-lignocaine benzophenone (Hodogaya Chemical Co., the EAB that Ltd. makes).

In the aforesaid compound, preferred thioxanthones compound and tertiary amine compound.Consider from curable aspect, deep, preferably comprise the thioxanthones compound in the composition of the present invention, wherein preferred 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthones compounds such as 4-diisopropyl thioxanthones.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the use level of such thioxanthones compound is preferably below 20 mass parts, and more preferably the following ratio of 10 mass parts is fit to.When the use level of thioxanthones compound is too much, cause the thick film curable to reduce, the cost of goods increases, so not preferred.

As tertiary amine compound, be preferably compound with dialkyl amido benzene structure, wherein, preferred especially dialkyl amido benzophenone cpd, maximum absorption wavelength are the coumarin compound that contains dialkyl amido of 350nm～410nm.As the dialkyl amido benzophenone cpd, 4,4 '-lignocaine benzophenone is low preferred because of toxicity.Because maximum absorption wavelength is that the maximum absorption wavelength of the coumarin compound that contains dialkyl amido of 350nm～410nm is in the ultraviolet range, therefore, can provide painted less, water white photosensitive composite is mathematical, and the painted soldering-resistance layer that uses coloring pigment and reflect the color of coloring pigment itself also can be provided.Consider preferred especially 7-(lignocaine)-4-methyl-2H-1-chromen-2-one from sensitization effect to the laser display excellence of wavelength 400nm～410nm.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the use level of such tertiary amine compound is preferably 0.1～20 mass parts, more preferably the ratio of 0.1～10 mass parts.The use level of tertiary amine compound is 0.1 mass parts when following, and existence can't obtain the tendency of sufficient sensitization effect.When surpassing 20 mass parts, the light absorption on the surface that dry welding resistance is filmed that is caused by tertiary amine compound becomes violent, the tendency that exists the deep curable to reduce.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can use separately or use with the form of the potpourri more than 2 kinds.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the total amount of such Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer is that the following scope of 35 mass parts is preferred.If surpass 35 mass parts, then has the tendency that causes the deep curable to descend by above-mentioned light absorption.

As in composition of the present invention, cooperate, to form image be the photopolymerization monomer (D) of purpose to use up, and can use known (methyl) acrylate monomer commonly used.As known (methyl) acrylate monomer commonly used, can list the diacrylate class of glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; The multicomponent methacrylate class of 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 etc.; The multicomponent methacrylate class of the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenols or propylene oxide adduct etc.; And the urethane acrylate class of above-mentioned polyalcohols, the multicomponent methacrylate class of glycidol ethers such as glycerine diglycidyl ether, glycerine triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; And the melamine acrylate, and/or with corresponding each methyl acrylic ester of aforesaid propylene acid esters etc.

In above-mentioned (methyl) acrylate monomer, consider from the viewpoint of anti-flammability, be preferably the phosphorus element-containing acrylate.For example can enumerate with three acryloxy ethyl phosphonic acid esters is that the phosphate of representative is the polyfunctional acrylic ester class, perhaps specifically can enumerate the phosphorus-containing compound modification acrylate shown in the following general formula (VIII).

[chemical formula 8]

In the formula, R ²⁵Be acrylate residue, R ²⁶And R ²⁷The acrylate derivative of the organic group except that halogen for hydrogen or conduct.Such phosphorus-containing compound modification acrylate usually can be by 9, and the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide carries out Michael addition reaction (Michael additionreaction) with known polyfunctional acrylic ester commonly used and comes synthetic.

In order to give Photocurable resin composition of the present invention, can add heat-curing resin (E) as the Thermocurable composition with thermotolerance.The Thermocurable composition (E) that has 2 above ring-type ethers and/or cyclic thioether base (being designated hereinafter simply as ring-type (sulphur) ether) in the preferred especially molecule.Wherein, the epoxy resin of preferred 2 functionalities also can use diisocyanate, its multi-functional blocked isocyanate in addition.

The Thermocurable composition (E) that has 2 above ring-types (sulphur) ether in such molecule, be to have in the molecule more than 2, three-membered ring, the compound of any in four-membered ring or pentacyclic ring-type ether or the cyclic thioether base or 2 kinds of groups, for example can list the compound that has 2 above epoxy radicals in the molecule at least, be multi-functional epoxy compound (E-1), at least the compound that has 2 above oxetanyls in the molecule, be multifunctional oxetane compound (E-2), have the compound of 2 above thioether groups in the molecule, it is episulfide resin (E-3) etc.

As aforementioned multi-functional epoxy compound (E-1), for example can list JapanEpoxy Resins Co., Ltd. the jER828 of Zhi Zaoing, jER834, jER1001, jER1004, the EPICLON 840 that big Japanese ink chemical industrial company makes, EPICLON 850, EPICLON 1050, EPICLON 2055, Dongdu changes into the Epo Tohto YD-011 that company makes, YD-013, YD-127, YD-128, the D.E.R.317 that TheDow Chemical Company makes, D.E.R.331, D.E.R.661, D.E.R.664, the Araldite6071 that Xiba Special Chemical Product Co.,Ltd makes, Aral dite 6084, Araldite GY250, Araldite GY260, the Sumiepoxy ESA-011 that Sumitomo Chemical Co. Ltd. makes, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial group of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A-type epoxy resins; JapanEpoxy Resins Co., Ltd. the jERYL903 of Zhi Zaoing, EPICLON 152, EPICLON 165 that big Japanese ink chemical industrial company makes, Dongdu changes into Epo Tohto YDB-400, the YDB-500 that company makes, the D.E.R.542 that The Dow Chemical Company makes, the Araldite 8011 that Xiba Special Chemical Product Co.,Ltd makes, Sumiepoxy ESB-400, E SB-700 that Sumitomo Chemical Co. Ltd. makes, (being trade name) brominated epoxy resins such as A.E.R.711, A.E.R.714 that industrial group of Asahi Chemical Industry makes; Japan Epoxy Resins Co., Ltd. the jER152 of Zhi Zaoing, jER154, the D.E.N.431 that The Dow Chemical Company makes, D.E.N.438, the EPICLON N-730 that big Japanese ink chemical industrial company makes, EPICLONN-770, EPICLON N-865, Dongdu changes into the Epo TohtoYDCN-701 that company makes, YDCN-704, the AralditeECN1235 that Xiba Special Chemical Product Co.,Ltd makes, Araldite ECN1273, Araldite ECN1299, AralditeXPY307, the EPPN-201 that Japan's chemical drug corporate system is made, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the Sumiepoxy ESCN-195X that Sumitomo Chemical Co. Ltd. makes, ES CN-220, the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry makes, ECN-299 etc. (being trade name) novolaks (novolac) type epoxy resin; The EPICLON 830 that big Japanese ink chemical industrial company makes, Japan Epoxy Resins Co., Ltd. the jER807 of Zhi Zaoing, Dongdu changes into Epo Tohto YDF-170, YDF-175, the YDF-2004 that company makes, (being trade name) bisphenol f type epoxy resins such as Araldite XPY306 that Xiba Special Chemical Product Co.,Ltd makes; Dongdu changes into Epo Tohto ST-2004, ST-2007, the ST-3000 bisphenol-A epoxy resins such as (trade names) that company makes; Japan Epoxy Resins Co., Ltd. the jER604 of Zhi Zaoing, Dongdu changes into the Epo Tohto YH-434 that company makes, the Araldite MY720 that Xiba Special Chemical Product Co.,Ltd makes, (being trade name) glycidyl amine type epoxy resins such as Sumiepoxy ELM-120 that Sumitomo Chemical Co. Ltd. makes; The Araldite CY-350 hydantoins type epoxy resin such as (trade names) that Xiba Special Chemical Product Co.,Ltd makes; DAICEL CHEMICAL INDUSTRIES, the CELLOXIDE 2021 that LTD. makes, (being trade name) alicyclic epoxy resins such as AralditeCY175, CY179 that Xiba Special Chemical Product Co.,Ltd makes; Japan EpoxyResins Co., the YL-933 that Ltd. makes, (being trade name) trihydroxy benzene methylmethane type epoxy resin such as T.E.N., the EPPN-501 that The Dow Chemical Company makes, EPPN-502; Japan Epoxy Resins Co., YL-6056, YX-4000, YL-6121 di-cresols type or united phenol-type epoxy resin or their potpourris such as (being trade name) that Ltd. makes; The EXA-1514 bisphenol-s epoxy resins such as (trade names) that the EPX-30 that the EBPS-200 that Japan's chemical drug corporate system is made, Asahi Electro-Chemical Co. Ltd make, big Japanese ink chemical industrial company make; Japan Epoxy Resins Co., the jER157S bisphenol-A phenolic varnish type epoxy resin such as (trade names) that Ltd. makes; Japan Epoxy Resins Co., the YL-931 that Ltd. makes, Araldite 163 grades (being trade name) the four hydroxyphenyl ethane type epoxy resin that Xiba Special Chemical Product Co.,Ltd makes; The Araldite PT810 that Xiba Special Chemical Product Co.,Ltd makes, (being trade name) hetero ring type epoxy resin such as TEPIC that daily output chemical industrial company makes; Xenol Novolac (biphenyl novolac) resins such as NC-3000, NC-3100 that Japan's chemical drug corporate system is made, the o-phthalic acid diglycidyl ester resins such as BLEMMER DGT that Nof Corp. makes; Dongdu changes into four glycidyl group dimethylbenzene acyl group ethane (the tetraglycidyl xylenoyl ethane) resins such as ZX-1063 that company makes; ESN-190, ESN-360 that chemical company of Nippon Steel makes, big Japanese ink chemical industrial company makes the epoxy resin that HP-4032, EXA-4750, EXA-4700 etc. contain naphthyl; HP-7200, the HP-7200H etc. that big Japanese ink chemical industrial company makes have the epoxy resin of bicyclopentadiene skeleton; The glycidyl methacrylate copolymerization such as CP-50S, CP-50M that Nof Corp. makes are epoxy resin; And, the copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxide modified polybutadiene rubber derivant (DAICEL CHEMICAL INDUSTRIES for example, the PB-3600 that LTD. makes etc.), CTBN modified epoxy (for example Dongdu changes into YR-102, the YR-450 etc. that company makes) etc.; But be not limited to these.These epoxy resin can be used alone or in combination of two or more kinds.Wherein, preferred especially biphenyl phenolic resin varnish type epoxy resin etc. has the epoxy resin of biphenyl backbone.

As aforementioned multifunctional oxetane compound (E-2), can list two [(3-methyl-3-oxetanes ylmethoxy) methyl] ethers, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, 1, two [(3-methyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters, multifunctional oxetanes classes such as their oligomer or multipolymer; And novolac resin, poly-(para hydroxybenzene ethene), cardo type bisphenols, calixarene kind, resorcinol calixarenes (calix resorcin arene) class or silsesquioxane (silsesquioxane) etc. have the resin of hydroxyl and the etherate of oxa-cyclobutanol etc.In addition, can list the multipolymer etc. of unsaturated monomer with oxetanes ring and (methyl) alkyl acrylate.

As the compound (E-3) that has 2 above cyclic thioether bases in the aforementioned molecule, for example can list Japan Epoxy Resins Co., the bisphenol A-type episulfide resin YL7000 that Ltd. makes etc.In addition, also can use and adopt same synthetic method that the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced to episulfide resin that sulphur atom forms etc.

With respect to the aforementioned 1 equivalent carboxyl that contains carboxy resin (B), the use level that has the Thermocurable composition (E) of 2 above ring-types (sulphur) ether in the aforementioned molecule is preferably 0.6～2.5 equivalent, more preferably the scope of 0.8～2.0 equivalent.When having the use level less than 0.6 of Thermocurable composition (E) of 2 above ring-types (sulphur) ether in the molecule, it is residual to have carboxyl in the soldering-resistance layer, and so reductions such as thermotolerance, alkali resistance, electrical insulating property are not preferred.On the other hand, when surpassing 2.5 equivalents, low-molecular-weight ring-type (sulphur) ether can remain in the dry coating, thereby makes the reductions such as intensity of filming, so not preferred.

Photocurable resin composition of the present invention also can further comprise the auxiliary agent of phosphorus-containing compound as anti-flammability.As phosphorus-containing compound, can be commonly used known material as organic phosphorus flame retardant, the compound shown in phosphate and condensed phosphoric acid esters, cyclic phosphazene compound, phosphonitrile oligomer or the following general formula (IX) is arranged.

[chemical formula 9]

In the formula, R ²⁸, R ²⁹And R ³⁰Represent the substituting group except that halogen atom independently of one another.

Commercially available product as the compound shown in the above-mentioned general formula (IX) has HCA, SANKO-220, M-ESTER, HCA-HQ etc.

When using the Thermocurable composition (E) that has 2 above ring-types (sulphur) ether in the aforementioned molecule, preferably contain thermal curing catalyst.As such thermal curing catalyst, for example can list imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole; Dicyandiamide; Benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, amines such as N-dimethyl benzyl amine; Hydrazide compound such as adipic dihydrazide, sebacic dihydrazide; Phosphorus compounds such as triphenylphosphine etc.In addition, as commercially available product, for example can list four countries and change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, the 2P4MHZ (being the trade name of imidazole compound) that industrial group makes, U-CAT (registered trademark) 3503N, U-CAT3502T (being the trade name of the blocked isocyanate compound of dimethyl amine) that SAN-APRO company makes, DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc.Be not limited in these compounds, be the thermal curing catalyst of epoxy resin, the thermal curing catalyst of oxetane compound, or promote the material of epoxy radicals and/or oxetanyl and carboxyl reaction to get final product, can use separately or mix more than 2 kinds and use.In addition, also can use guanamines, methyl guanamines, benzoguanamine, melamine, 2,4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2,4-diamido-6-methacryloxyethyl-Striazine derivatives such as s-triazine isocyanuric acid addition product preferably can also be used in combination these as compound and the aforementioned hot curing catalysts that the adaptation imparting agent works.

The use level of these thermal curing catalysts is that the ratio of common amount is promptly enough, for example, contain the Thermocurable composition (E) that has 2 above ring-types (sulphur) ether in carboxy resin (B) or the molecule with respect to 100 mass parts, be preferably 0.1～20 mass parts, more preferably 0.5～15.0 mass parts.

Photocurable resin composition of the present invention can cooperate colorant.As colorant, can use known colorants commonly used such as red, blue, green, Huang, can be in pigment, dyestuff, the pigment any one.Wherein, from reducing carrying capacity of environment and the viewpoint of the influence of human body being considered, preferably do not contain halogen.

Blue colorant:

As blue colorant, phthalocyanine system, anthraquinone system are arranged, pigment system is the compound that is classified as pigment (Pigment), particularly, can list and has following such Colour Index (C.I.; The Society of Dyers and Colourists distribution) material of sequence number: pigment blue 15, pigment blue 15: 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, can use 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.Except above-mentioned, can also use metal to replace or unsubstituted phthalocyanine compound.

Green colourant:

As green colourant, phthalocyanine system, anthraquinone Xi, perylene system are arranged equally, particularly, can use that pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc.Except above-mentioned, can also use metal to replace or unsubstituted phthalocyanine compound.

Yellow colorants:

As yellow colorants, monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc. are arranged, particularly, can list following material.

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.

Red stain:

As red stain, monoazo system, bisdiazo system, azo lake system, benzimidazolone Xi, perylene system, diketopyrrolopyrrolecocrystals system, condensation azo system, anthraquinone system, quinacridone etc. are arranged, particularly, can list following material.

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 system: 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, paratonere 179, 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.

In addition, in order to adjust tone, can add purple, orange, palm fibre, black etc. colorant.

As particular instantiation, pigment violet 19 is arranged, 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.

There is no particular limitation for the cooperation ratio of aforementioned such colorant, with respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, is preferably 0～10 mass parts, and the ratio that is preferably 0.1～5 mass parts especially is promptly enough.

For physical strength of filming of improving Photocurable resin composition of the present invention etc., as required, can cooperate filler.As such filler, can use to be selected from least a in the group of forming by known inorganic filler commonly used and organic filler, preferably use inorganic filler, especially preferably use barium sulphate, preparing spherical SiO 2 and talcum.And then, can add titanium dioxide as white filler, make white solder resist thus.In addition,, the particulate of metal oxide can also be added, specifically aluminium hydroxide, magnesium hydroxide or boehmite etc. can be listed in order further to give anti-flammability.These fillers can cooperate separately or make up 2 kinds with on cooperate.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the use level of these fillers is preferably below 300 mass parts, and more preferably 0.1～300 mass parts is preferably 0.1～150 mass parts especially.When the use level of filler surpassed 300 mass parts, the viscosity of Photocurable resin composition increased, and printing reduces, and perhaps solidfied material becomes fragile, so not preferred.

And then, for synthetic aforementioned carboxy resin (B), the modulation group compound of containing, perhaps in order to adjust viscosity so that be applied on substrate, the carrier film, Photocurable resin composition of the present invention can be with an organic solvent.

As such organic solvent, can list ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.More specifically, can list ketones such as MEK, cyclohexanone; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; 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; 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, propylene glycol butyl ether acetic acid esters; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc.Such organic solvent can use separately or use as the potpourri more than 2 kinds.

As required, Photocurable resin composition of the present invention can also cooperate known hot polymerization inhibitors commonly used such as quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, phenothiazine, known tackifier commonly used such as fine particle silica, organobentonite, polynite, defoamer and/or levelling agents such as silicon (silicone) is, fluorine system, macromolecular, silane coupling agents such as imidazoles system, thiazole system, triazole system, antioxidant, the additive kind known commonly used that rust preventive etc. are such.

Photocurable resin composition of the present invention can be the form of dry film, described dry film possess carrier film (supporter) and be formed on this carrier film by above-mentioned Photocurable resin composition form the layer.

During dry film, with Photocurable resin composition of the present invention with aforementioned organic solvent diluting to adjust to suitable viscosity, by comma coating machine (comma coater), knife type coater, lip coating machine (lip coater), rod is coated with machine (rod coater), extrusion coating machine (squeeze coater), contrary formula coating machine (reverse caoter), transmit roll coater (transfer roll cater), photogravure coating machine (gravure coater), flush coaters etc. are coated with into homogeneous thickness on carrier film, usually, drying can obtain film in 1～30 minute under 50～130 ℃ temperature.There is no particular limitation to coating film thickness, and usually, dried thickness is at 10～150 μ m, preferably suitably select in the scope of 20～60 μ m.

As carrier film, can use plastic sheeting, preferably use the plastic sheeting of the mylar, Kapton, polyamidoimide film, polypropylene film, plasticon etc. of polyethylene terephthalate etc.There is no particular limitation to the thickness of carrier film, suitably selects in the scope of 10～150 μ m usually.

After film forming on the carrier film, and then, for surface attachment dust of preventing film etc., it is desirable to surperficial stacked strippable coverlay at film.

As strippable coverlay, for example can use polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper etc., as long as the bounding force of film and coverlay is less than the bounding force of film and carrier film when peeling off coverlay.

In addition, Photocurable resin composition of the present invention or this dry film form solidfied material by photocuring on copper.Photocuring can be undertaken by ultraviolet exposure apparatus according, can be that the laser of 350～410nm is cured by wavelength also.

Particularly, as get off to form dry film, solidfied material and printed circuit board (PCB).Promptly, Photocurable resin composition of the present invention is for example adjusted to the viscosity that is fit to coating process with aforementioned organic solvent, utilizing dip coating, flow coat method, rolling method, rod to be coated with methods such as method, silk screen print method, curtain Tu Fa is applied on the base material, the organic solvent volatile dry (preliminarily dried) that composition is comprised, what can cannot not form stickingly thus films.In addition, above-mentioned composition is applied on the carrier film, the dry film that forms is rolled it and is fitted on the base material in the mode that the Photocurable resin composition layer contacts with base material, peels off carrier film then, can form resin insulating barrier thus.Afterwards, adopt contact (or noncontact mode) to make active energy beam carry out the selectivity exposure, with unexposed development, can form corrosion-resisting pattern by dilute alkaline aqueous solution (for example 0.3～3% aqueous sodium carbonate) by forming figuratum photomask.And then, under for the situation of composition that contains Thermocurable composition (E), make its heat curing by for example being heated to about 140～180 ℃ temperature, make Thermocurable composition (E) reaction that has 2 above ring-type ethers and/or cyclic thioether base in aforementioned carboxyl that contains carboxy resin (B) and the molecule, can form the cured coating film of each excellent such as thermotolerance, chemical proofing, anti-hydroscopicity, adaptation, electrical characteristics.In addition, even under the situation that does not contain Thermocurable composition (E), also can heat-treat and when making exposure with the residual ethylenic unsaturated bond generation hot radical polymerization of unreacted state, coating characteristic improves, and therefore also can heat-treat (heat curing) according to purpose and purposes.

As above-mentioned base material, on the basis that is pre-formed the printed circuit board (PCB) of circuit, flexible printed circuit board, can also use copper clad laminate, Kapton, PET film, glass substrate, ceramic substrate, wafer board of all grades (FR-4 etc.) etc., described copper clad laminate is to use 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 to obtain.

The volatile dry that carries out behind coating Photocurable resin composition of the present invention can use heated air circulation type drying oven, IR stove, heating plate, convective oven etc. (use has the device of the thermal source of the air heat mode of utilizing steam, the method that the hot air convection in the dryer is contacted, the mode of blowing supporter by nozzle).

To being coated with expose (the irradiation active energy beam) of filming that obtains behind Photocurable resin composition of the present invention and the volatile dry as described above.The exposure portion of filming (part of being shone by active energy beam) solidifies.

As the used exposure machine of above-mentioned irradiation active energy beam, can use the direct drawing apparatus of laser (laser direct imaging device), be equipped with metal halide lamp exposure machine, be equipped with (surpassing) high-pressure sodium lamp exposure machine, be equipped with the exposure machine of mercury short arc lamp or used the direct drawing apparatus of UV-lamp such as (surpassing) high-pressure sodium lamp.In addition, if use maximum wavelength be the laser of scope of 350～410nm as active energy beam, then can be in gas laser, the Solid State Laser any one.In addition, its exposure is generally 5～200mJ/cm according to thickness etc. and different ², be preferably 5～100mJ/cm ², 5～50mJ/cm more preferably ²Scope in.As above-mentioned direct drawing apparatus, for example can use the device of Orbotech Ltd. manufacturing, PENTAXCORPORATION manufacturing etc., so long as the generation maximum wavelength that can vibrate is the device of the laser of 350～410nm, then can use arbitrary device.

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

Embodiment

Embodiment and comparative example are shown below come the present invention is carried out specific description, but without doubt, the present invention is not limited to following embodiment.

Enforcement 1～3, comparative example 1,2

Each composition shown in the table 1 is cooperated according to the ratio shown in the table 1 (mass parts), use the stirring machine premixed, use 3 roll-type mixing rolls mixing then, modulation solder resist light solidifying/heat solidifying resin composition.Here, the dispersion degree of gained light solidifying/heat solidifying resin composition is estimated with the granulometry of the GRIND METER that makes based on ERICHSEN company, and the result is below the 15 μ m.

[table 1]

Performance evaluation

＜optimum exposure 〉

With copper thick be that the circuit pattern substrate of 35 μ m grinds with polishing roll, then after washing, the drying, by the light solidifying/heat solidifying resin composition of whole aforementioned each embodiment of coating of silk screen print method and comparative example, drying is 30 minutes in 80 ℃ heated air circulation type drying oven.After the drying, use the exposure device (HMW-680-GW20) that is equipped with metal halide lamp to expose by stage metraster (Kodak No.2), will develop (30 ℃, 0.2MPa, 1wt%Na ₂CO ₃Exposure when aqueous solution) pattern of residual stage metraster is 6 sections during 60 seconds is as optimum exposure.

Attribute testing:

The composition of aforementioned each embodiment and comparative example is applied on the figuratum Kapton substrate of formation by the whole face of serigraphy, after under 80 ℃ dry 30 minutes, naturally cools to room temperature.The exposure device (HMW-680-GW20) that use is equipped with metal halide lamp exposes to the soldering-resistant pattern on this substrate with optimum exposure, with 30 ℃ 1wt%Na ₂CO ₃Aqueous solution was developed for 60 seconds under the condition of spray pressure 0.2MPa, obtained corrosion-resisting pattern.The heating under 150 ℃ of this substrate was cured in 60 minutes.Gained printed base plate (evaluation substrate) is carried out following evaluating characteristics.

＜solder heat resistance 〉

The evaluation substrate that is coated with the rosin series solder flux is immersed in the solder bath that is redefined for 260 ℃, with modification alcohol washing solder flux, then with the expansion of visual valuation resist layer with peel off.Judgment standard is as follows.

Zero:, also can't see and peel off even repeat more than 2 times dipping in 10 seconds.

△: when repeating that flood 10 seconds more than 2 times, have a little to peel off.

*: when carrying out flooding 1 time 10 second, resist layer has expansion, peels off.

The gold-plated property of＜chemically-resistant 〉

Use the electroless nickel bath and the chemical gilding of commercially available product to bathe, under the condition of nickel 3 μ m, golden 0.03 μ m, carry out plating, peel off by band and estimate resist layer and have or not the infiltration of peeling off, have or not plating, peel off by band then and estimate resist layer and have or not and peel off.Judgment standard is as follows.

◎: can't see infiltration, peel off.

Zero: can confirm a little infiltration behind the plating, not peel off after band is peeled off.

△: can see a little infiltration behind the plating, also can see after band is peeled off and peeling off.

*: peel off behind the plating.

＜electrical characteristics 〉

The Alloy instead of Copper foil substrate uses the comb-type electrode B sample of IPC B-25, makes under these conditions and estimates substrate, and this comb-type electrode is applied the bias voltage of DC100V, in 85 ℃, the constant temperature and humidity cabinet of 85%R.H., confirm having or not of migration after 1000 hours.Judgment standard is as follows.

Zero: can't see variation fully

△: slight variations is only arranged

*: move

＜acid resistance 〉

To estimate substrate at 10vol%H ₂SO ₄Dipping is 30 minutes in the aqueous solution, under the room temperature, confirms infiltration, the stripping of filming, and then confirms to peel off peeling off of causing by band.Determinating reference is as follows.

Zero: do not infiltrate, stripping, peel off.

△: confirm a little infiltration, stripping or peel off.

*: confirm tangible infiltration, stripping or peel off.

＜anti-flammability 〉

By serigraphy the whole face of the composition of each embodiment and comparative example is applied to the thick Kapton of 25 μ m (Kapton 100H), after under 80 ℃ dry 20 minutes, naturally cools to room temperature.And then, by serigraphy whole coating similarly carried out at the back side, after under 80 ℃ dry 20 minutes, naturally cool to room temperature, obtain the two sided coatings substrate.The exposure device (HMW-680-GW20) that use is equipped with metal halide lamp carries out whole exposure with optimum exposure to the solder resist on this substrate, with 30 ℃ 1wt%Na ₂CO ₃Aqueous solution was developed for 60 seconds under the condition of spray pressure 0.2MPa, 150 ℃ of following heat curings 60 minutes, formed assess sample.This anti-flammability evaluation is carried out thin material testing vertical flammability according to the UL94 standard with sample.Be VTM-0 or VTM-1 based on the UL94 canonical representation during evaluation.

＜flexible

The whole face of the composition of each embodiment and comparative example is applied on the Kapton (Kapton 100H) of 25 μ m by serigraphy, after under 80 ℃ dry 30 minutes, naturally cools to room temperature, obtain the single face coated substrates.The exposure device (HMW-680-GW20) that use is equipped with metal halide lamp carries out whole exposure with optimum exposure to the solder resist on this substrate, with 30 ℃ 1wt%Na ₂CO ₃Aqueous solution was developed for 60 seconds under the condition of spray pressure 0.2MPa, 150 ℃ of following heat curings 60 minutes.So that the soldering-resistance layer of gained sample mode toward the outer side repeats the 180 ° bendings of several based on crimping,, estimate the number of times that does not crack by the crackle production that observation by light microscope visual and multiplying power 200 is filmed at this moment.

Aforementioned each evaluation test the results are shown in table 2.

[table 2]

As above remember shown in the table 2, embodiment 1～3 for the light solidifying/heat solidifying resin composition that uses the phosphorus element-containing polyester that contains the organic solvent solubility of the present invention, the anti-flammability of gained cured film and flexible excellence, solder heat resistance, the gold-plated property of chemically-resistant, electrical characteristics, acid resistance are also excellent in addition; For the comparative example 2 of the photo-curable compositions of thermosetting resin that uses the phosphorus element-containing polyester that does not contain the organic solvent solubility, it does not have anti-flammability.On the other hand, the comparative example 1 of phosphorus element-containing polyester that contains the light solidifying/heat solidifying resin composition replace organic solvent solubility of common phosphonium flame retardant for use, though anti-flammability is no problem, flexible poor, solder heat resistance, electrical characteristics are also insufficient in addition.

Embodiment 4

To dilute with MEK according to the light solidifying/heat solidifying resin composition of the cooperation modulation identical, be applied on the carrier film and heat drying, form the resin combination layer of thickness 20 μ m, with 80 ℃ hot-air driers dryings 30 minutes with embodiment 1.Further fit coverlay thereon and obtain dry film., peel off coverlay, use laminating machine that it is fitted in and form figuratum polyimide film substrate thereafter.The exposure device (HMW-680-GW20) that use is equipped with metal halide lamp exposes to the soldering-resistant pattern on this substrate with optimum exposure, peels off carrier film, uses 30 ℃ 1wt%Na then ₂CO ₃Aqueous solution was developed for 60 seconds under the condition of spray pressure 0.2MPa, obtained being formed with the substrate of corrosion-resisting pattern.After this, carry out 60 minutes being heating and curing, make the test substrate with 150 ℃ hot-air driers.Have the test substrate of cured film for gained, similarly carry out the evaluation test of each characteristic with afore-mentioned test method and evaluation method.

The processing of gained dry film is no problem, and the result of the characteristic of gained dry film and embodiment 1 is equal extent substantially.

Claims (9)

1. a flame retardant photocurable resin composition is characterized in that, its phosphorus element-containing polyester, (B) that contains (A) organic solvent solubility contains carboxy resin and (C) Photoepolymerizationinitiater initiater.

2. flame retardant photocurable resin composition according to claim 1 is characterized in that, it further contains (D) photopolymerization monomer.

3. flame retardant photocurable resin composition according to claim 1 is characterized in that, it further contains (E) heat-curing resin.

4. flame retardant photocurable resin composition according to claim 3 is characterized in that, described heat-curing resin (E) comprises the epoxy resin with biphenyl backbone.

5. flame retardant photocurable resin composition according to claim 1 is characterized in that, the described carboxy resin (B) that contains is for containing the carboxyl urethane resin.

6. according to each the described flame retardant photocurable resin composition in the claim 1～5, it is a solder resist.

7. the dry film of a flame retardant photocurable, it is by being applied to each the described flame retardant photocurable resin composition in the claim 1～5 on the carrier film and dry obtaining.

8. anti-flammability solidfied material, it obtains by each the described flame retardant photocurable resin composition in the claim 1～5 is cured; Perhaps, by being cured, the dry film that described flame retardant photocurable resin composition is applied on the carrier film and drying obtains obtains.

9. a printed circuit board (PCB) is characterized in that, it has the anti-flammability cured film, and described anti-flammability cured film obtains by each the described flame retardant photocurable resin composition in the claim 1～5 is cured; Perhaps, by being cured, the dry film that described flame retardant photocurable resin composition is applied on the carrier film and drying obtains obtains.