CN101846881A - Hardening resin composition, the dry film that uses it and printed circuit board (PCB) - Google Patents

Abstract

Hardening resin composition is provided, uses its dry film and printed circuit board (PCB), hardening resin composition, its dry film are provided specifically and form the printed circuit board (PCB) that anti-flammability cured films such as soldering-resistance layer form by them, said composition contains the colorant and the fire retardant of Halogen, can form low warpage and to because the solder mask of the covering power excellence of the caused bad order of variable color that the oxidation of copper circuit causes.Hardening resin composition contains (A) and contains carboxy resin, (B) titanium dioxide and (C) aluminium hydroxide.Except aforementioned each composition, by also containing the Thermocurable composition that has 2 above ring-type ethers and/or cyclic thioether base in (D) molecule, can become hot curing resin composition, by further containing (F) Photoepolymerizationinitiater initiater and (G) photopolymerization monomer, can become light solidifying/heat solidifying resin composition.Preferably also contain (E) phosphorus-containing compound.

Description

Hardening resin composition, the dry film that uses it and printed circuit board (PCB)

Technical field

The present invention relates to hardening resin composition, relate in particular to the hardening resin composition of the solder resist that can form low warpage and anti-flammability and coloring, covering power excellence.The invention still further relates to the dry film of the described hardening resin composition of use and the printed circuit board (PCB) of anti-flammability.

Background technology

All the time, printed circuit board (PCB) and flexible electric circuit board (below, abbreviate FPC as) be owing to be equipped in the e-machine, thereby wish that it has anti-flammability, also is required anti-flammability as their solder resist of a part.Wherein, FPC is made of polyimide substrate usually, and therefore, its printed circuit board (PCB) with glass epoxy substrate is different, is film.Yet because the solder resist that should be coated with all has identical thickness in printed circuit board (PCB) or in FPC, therefore, during for the FPC of film, the burden of fire-retardantization of solder resist becomes greatly relatively.

Therefore, all the time, various schemes have been proposed for fire-retardantization of solder resist.For example; TOHKEMY 2007-10794 communique (patent documentation 1) has proposed a kind of FPC anti-flammability photosensitive polymer combination, 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 halogenation aromatic rings such as having the bromo phenyl in (a) binder polymer, (b) molecule and (methyl) acryloyl group and (e) has phosphorus atoms in the molecule.Yet from the viewpoint of environmental pressure, it is not preferred using the such halogen compounds of compound with halogenation aromatic rings and polymerisable unsaturated double-bond.

It with FPC the printed base plate of the film of representative produces warpage when also existing in the photocuring of solder resist or heat curing because of cure shrinkage problem.

On the other hand, though the formation of solder resist is the protection that is used for copper circuit, its another effect is that wound, dirt on the heat that makes copper circuit, moisture, electric caused variable color, the copper circuit etc. is difficult for being found (covering power).For this point, usually solder resist is added colorant, make its concentration make that greatly bad being difficult for of outward appearance seen.

About nearest solder resist,, use the phthalocyanine blue of halogen atom-containing not and solder resist that yellow colorants replaces green colourant chlorination phthalocyanine green in the past popularizing (for example, with reference to patent documentation 2) from alleviating the viewpoint of environmental pressure.In addition, owing to advocate clear and definite in appearance Halogen, therefore, also there is human directly to use the solder resist of the blueness of phthalocyanine blue.Yet, compare with the green of phthalocyanine green, the covering power of blue welding resistance China ink, the green welding resistance China ink that obtains by blue colorant and yellow colorants a little less than, can not obtain the function that bad order is difficult for being found this colorant fully sometimes.Make it clearer by following explanation.

That is, existing solder resist forms image by photocuring, can implement heat curing at last and handle.When temperature at this moment is 150 ℃, for about 30～60 minutes be suitable, but in fact, because substrate producer difference, temperature, time are also fixing, all there are some differences in what.When especially temperature height, processing time are long, use the substrate of welding resistance China ink of the blueness of covering power difference, its resist can not cover because the variable color that the oxidation of copper circuit causes, and has the relatively poor problem of outward appearance of substrate.The inventor etc. confirm, state in the use in the blue colorant of Halogen and the green welding resistance China ink that yellow colorants obtains, and this problem exists too, its covering power than phthalocyanine green a little less than.In addition, under the situation that applies mark China ink (marking ink) on the substrate,, cause the variable color of copper circuit to be quickened, make apparent problem further aggravate owing to after solder resist solidifies, also want typographic(al) mark and make its heat curing.And then the warpage of the substrate that produces during for the heat curing of repairing solder resist is exerted pressure and heat sometimes, and there is the problem of circuit variable color equally in this.

Because the worst phenomenon that the variable color of these copper circuits causes is, even be in the state that variable color takes place at the edge (place of etchant resist attenuation) that circuit is also only arranged on same copper circuit.When being in such state, check, during installation base plate, can take place since with inconsistent cause bad of inspection data.On the other hand, but can see variable color but when even, just can not cause this problem with other part on the identification copper circuit.These problems are former also to be in the news, but (colorant non-halogen) is especially remarkable when the colorants such as phthalocyanine blue that use halogen atom-containing replace phthalocyanine green.

The prior art document

Patent documentation

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

Patent documentation 2: TOHKEMY 2000-7974 communique (claims)

Summary of the invention

The problem that invention will solve

The present invention carries out in order to solve foregoing prior art problems, its fundamental purpose is, a kind of colorant of Halogen and hardening resin composition of fire retardant of containing is provided, and this hardening resin composition can form low warpage and the solder mask of the covering power excellence of the caused bad order of variable color that causes for the oxidation of copper circuit.

The present invention also aims to, by using described hardening resin composition, the printed circuit board (PCB) of anti-flammability epithelium that the dry film of low warpage and anti-flammability and coloring, covering power excellence is provided and has the characteristic of such excellence.

The scheme that is used to deal with problems

In order to realize aforementioned purpose, the invention provides a kind of hardening resin composition, it is characterized in that it contains (A) and contains carboxy resin, (B) titanium dioxide and (C) aluminium hydroxide.

In scheme, except aforementioned each composition, also contain the Thermocurable composition that has 2 above ring-type ethers and/or cyclic thioether base in (D) molecule therein, can become hot curing resin composition thus.In other preferred version, also contain (E) phosphorus-containing compound.In other scheme, also contain (F) Photoepolymerizationinitiater initiater and (G) photopolymerization monomer, can become light solidifying/heat solidifying resin composition thus.In other preferred version, also contain the colorant (H) except aforementioned titanium dioxide (B).In preferred scheme, the above-mentioned carboxy resin (A) that contains is the carboxy resin that contains with carbamate skeleton, or has a carboxy resin that contains of xenol Novolac structure and olefinic unsaturated group, in addition, the Thermocurable composition (D) that has 2 above ring-type ethers and/or cyclic thioether base in the above-mentioned molecule is the epoxy resin with xenol Novolac skeleton.Such hardening resin composition is adapted at forming in the solder resist of printed circuit board (PCB) and uses.

In addition, the present invention also provides, to aforementioned hardening resin composition being applied on the film and the dry dry film that forms carries out heat curing and/or photocuring and the solidfied material that obtains, perhaps to aforementioned hardening resin composition or to this hardening resin composition being applied to carrier film and the dry dry film that obtains carry out heat curing and/or photocuring and the solidfied material that obtains.The present invention also provides the printed circuit board (PCB) with aforementioned solidfied material.

The invention effect

Hardening resin composition of the present invention contains (A) and contains carboxy resin and (B) titanium dioxide and (C) aluminium hydroxide, preferably also contain (E) phosphorus-containing compound, thus, can form that Halogen is formed and environmental pressure is little, the epithelium of anti-flammability and low warpage, coloring, covering power excellence.Therefore, the hardening resin composition of the application of the invention, the printed circuit board (PCB) of anti-flammability welding resistance epithelium that the dry film of low warpage and anti-flammability and coloring, covering power excellence can be provided and have the characteristic of such excellence.

Embodiment

The inventor etc. further investigate in order to realize aforementioned problems, found that, with the composition of hardening resin composition of the present invention, promptly contain the titanium dioxide (B) that carboxy resin (A) and aluminium hydroxide (C) contain simultaneously, even when using the Halogen colorant, also have the effect that hides the circuit variable color, and have the effect of the warpage that reduces cured film.The surprising effect that this does not expect before being fully.In addition, with aluminium hydroxide (C) and titanium dioxide (B) when being used in combination, aluminium hydroxide not only has the effect of thermal resistance agent, when consisting of photosensitive polymer combination, compatibility, the refractive index of itself and photoresist are approaching, photocuring can be carried out effectively, the light sensitivity that interpolation brought of titanium dioxide, the reduction of resolution can be significantly suppressed to follow.And then, use to contain the carboxyl urethane resin when containing carboxy resin (A), have the effect of low elasticity, low warpage, have the effect of the warpage of further reduction cured film, by also containing phosphorus-containing compound (E), can further improve anti-flammability.

Below, each constituent of hardening resin composition of the present invention is at length described.

As the contained carboxy resin (A) that contains in the hardening resin composition of the present invention, can use the resin compound known commonly used that contains carboxyl in the molecule.And then, under the situation that is the alkali-developable resin combination, from photo-curable, anti-development aspect, have in the molecule ethylenical unsaturated double bonds to contain carboxyl photoresist (A ') be preferred.And it is preferred that its unsaturated group is derived from the acrylic or methacrylic acid derivative.In addition, do not have under the situation that contains carboxy resin of ethylenical unsaturated double bonds only using, to have photo-curable in order to make composition, need with molecule described later in have 2 above olefinic unsaturated groups photopolymerization monomer (G) be used in combination.

As the object lesson that contains carboxy resin (A), the compound of enumerating below suitable use the (any of oligomer and polymkeric substance all can).

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

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

(3) be 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, addition polymerization with diatomic alcohol compounds such as compound of phenol hydroxyl and alcohol hydroxyl group obtains urethane resin by diisocyanate cpd such as aliphatic diisocyanate, side chain aliphatic diisocyanate, ester ring type diisocyanate, aromatic diisocyanate and polycarbonate-based polyvalent alcohol, polyethers, it is terminal obtain with anhydride reaction contain the terminal carboxyl group urethane resin.

(4) 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-toluene phenol-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.

(5) by have 1 hydroxyl in adding (methyl) hydroxyalkyl acrylate equimolecular in the resin of above-mentioned (2) or (4) synthetic and the compound of (methyl) acryloyl group obtains more than 1 end (methyl) propylene acidylate contain the carboxyl urethane resin.

(6) 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 (2) or (4) synthetic and the compound of (methyl) acryloyl group obtains more than 1 end (methyl) propylene acidylate contain the carboxyl urethane resin.

(7) photonasty that obtains by making the reaction of such multifunctional (solid-state) epoxy resin of aftermentioned and (methyl) acrylic acid, make 2 yuan of acid anhydrides additions such as the hydroxyl that is present in side chain and phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride contains carboxy resin.

(8) polyfunctional epoxy resin and the reaction of (methyl) acrylic acid that obtain with the further epoxidation of epichlorokydrin of the hydroxyl by can (solid-state) epoxy resin with 2 officials, the hydroxyl of generation and 2 yuan of acid anhydrides additions and the photonasty that obtains contains carboxy resin.

(9) by such 2 officials of aftermentioned can be reacted with dicarboxylic acid by oxetane resin, the primary hydroxyl of generation and 2 yuan of acid anhydrides additions and obtain contain carboxyl polyester resin.

(10) resin of above-mentioned by making (1)～(9) further with in (methyl) glycidyl acrylate, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester equimolecular has 1 epoxy radicals and the compound addition of (methyl) acryloyl group obtains more than 1 photonasty contains 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, and (Y) in aforementioned resin synthetic used polyfunctional epoxy resin be to have structure of bisphenol A, the Bisphenol F structure, the xenol structure, xenol Novolac structure, bis-xylene phenol structure, when especially having the compound of xenol Novolac structure and hydrogenated compound thereof, from low warpage, setting out in crooked patience aspect, is preferred.Wherein, preferably, aforesaid copolymer resins, have above-mentioned isocyanate group compound (comprising diisocyanate) isocyanate group not and the formed carboxyl urethane resin that contains of the diisocyanate of phenyl ring Direct Bonding, it is being particularly preferred aspect low warpageization, and its xanthochromia is few, covering power is effective and UVA is few, therefore, has the feature of excellent in resolution during as the alkali-developable composition.

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

The foregoing carboxy resin (A) that contains has a plurality of free carboxyls on the side chain of trunk polymer, the crosslinking points when therefore becoming heat curing.In addition, during as photosensitive composite, can utilize dilute alkaline aqueous solution to develop.

In addition, the aforementioned acid number that contains carboxy resin (A) is preferably the scope of 30～200mgKOH/g, 40～200mgKOH/g more preferably, and the scope that especially is preferably 45～120mgKOH/g is desirable.Viewpoint from alkali-developable, the words that contain the not enough 30mgKOH/g of acid number of carboxy resin, then be difficult to alkali and develop, on the other hand, surpass the words of 200mgKOH/g, the dissolving of developer solution to exposure portion takes place, therefore, it is thinner than needed that line becomes, and is developed the liquid dissolving portion of exposure sometimes and unexposed indistinction and peels off, be difficult to describe normal corrosion-resisting pattern, so not preferred.

In addition, the aforementioned weight-average molecular weight that contains carboxy resin (A) 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, thermotolerance is insufficient.On the other hand, weight-average molecular weight surpasses at 150000 o'clock, the storage stability variation.

The foregoing use level that contains carboxy resin (A) is 5～60 quality % in all compositions, is preferably 10～60 quality %, more preferably 20～60 quality %, be preferably 30～50 quality % especially.When being less than above-mentioned scope, coating strength reduces, so not preferred.On the other hand, during more than above-mentioned scope, the viscosity of composition uprises, and so reductions such as coating are not preferred.

As titanium dioxide used in the hardening resin composition of the present invention (B), can use titanium dioxide by sulfuric acid process, chlorine manufactured, Titanium Dioxide Rutile Top grade, anatase type titanium dioxide or implemented the surface-treated titanium dioxide, implemented the surface-treated titanium dioxide with organic compound with moisture metal oxide.In these titanium dioxide (B), Titanium Dioxide Rutile Top grade is preferred.Anatase type titanium dioxide is because higher and often used than the whiteness of rutile-type.Yet,, can cause the resin variable color in the light solidifying/heat solidifying resin composition because anatase type titanium dioxide has photocatalytic activity.Therewith relatively, the whiteness of Titanium Dioxide Rutile Top grade is weaker than the anatase type, but because it does not have photolytic activity substantially, can obtain stable soldering-resistance layer.As Titanium Dioxide Rutile Top grade, can use known Titanium Dioxide Rutile Top grade.Particularly, TR-600, TR-700, TR-750, the TR-840 that can use FUJI TITANIUM INDUSTRY CO.LTD. to make, R-550, R-580, R-630, R-820, CR-50, CR-60, CR-90, CR-97 that the former industry of stone (strain) is made, KR-270, the KR-310 that FUJI TITANIUMINDUSTRY CO.LTD. makes, KR-380 etc.In these Titanium Dioxide Rutile Top grades, the titanium dioxide that can use the surface to handle with aqueous alumina or aluminium hydroxide, its viewpoint from the dispersiveness composition, storage stability, anti-flammability is particularly preferred.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of these titanium dioxide (B) is that the scope of 0.1～200 mass parts is desirable, is preferably 1～100 mass parts, more preferably 3～80 mass parts.During use level less than 0.1 mass parts of titanium dioxide (B), can not obtain the good covering power and the performance of low warpage properties.On the other hand, when excessive interpolation surpassed 200 mass parts, titanium dioxide had the character of the light of uv reflectance scope, and compares with photoresist, its refractive index is very high, is 2.71, therefore, as solder resist, can not obtain sufficient curing depth, the resolution variation.In addition, when not adding aluminium hydroxide (C) according to the present invention, can see that more obvious resolution reduces.

Known aluminium hydroxide (C) is the adjuvant of anti-flammability, and compatibility, the refractive index of itself and photoresist are approaching, can carry out photocuring effectively, so add.The whiteness of aforementioned titanium dioxide, covering power excellence, but refractive index (2.71) height is also strong to ultraviolet reflection, therefore, during a large amount of the use, the thick film as soldering-resistance layer (about 10～50 μ m) exists the light sensitivity of photosensitive composite of the resolution that lowers the requirement and the problem of resolution.Therefore, aluminium hydroxide and titanium dioxide are used simultaneously, make light see through fully along the depth direction of photoresist.By this method, can when keeping covering power, improve the resolution of alkali developable photosensitive composite.In addition, can also guarantee the desired anti-flammability of solder resist.

As aluminium hydroxide (C), can use known aluminium hydroxide commonly used, can use HIGILITE series, HW, H21, H31, H32, H42M, H43M etc. for example clear and that electrician society makes.In addition, the less aluminium hydroxide of particle diameter is effective aspect folding resistance, therefore, from the anti-flammability of the cured film that obtains, the viewpoint of bendability, reinstate dispersion such as ball mill in advance with solvent, resin one and be machined to primary particle size, by filtrations such as filtration select more than the 3 μ m, more preferably the aluminium hydroxide more than the 1 μ m is preferred.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of these aluminium hydroxide (C) is that the scope of 1～200 mass parts is desirable, is preferably 1～100 mass parts, more preferably 10～80 mass parts.When the use level of aluminium hydroxide (C) is less than 1 mass parts, do not have the effect that improves resolution, anti-flammability is also insufficient.On the other hand, during more than 200 mass parts, anti-flammability is good, but flexible poor, solder heat resistance is variation also.

In order to make composition of the present invention consist of the Thermocurable composition (D) that hot curing resin composition uses to improve characteristic such as thermotolerance, insulating reliability, so long as can with carboxyl reaction that contains carboxy resin and molecule in have 2 above ring-type ethers and/or cyclic thioether base (below, abbreviate ring-type (sulphur) ether as) existing known compound, can use, wherein, the epoxy resin that 2 functionalities are above, the epoxy resin that especially has xenol Novolac skeleton is preferred.As epoxy resin, for example can list NC-3000L, NC-3000, NC-3000H, NC-3100 etc. that Japanese chemical drug (strain) is made with xenol Novolac skeleton.

In addition, in hot curing resin composition of the present invention, can be used as the Thermocurable composition that has 2 above ring-types (sulphur) ether in the molecule that the Thermocurable composition uses, be to have 2 above three-membered rings in the molecule, the compound of any of four-membered ring or pentacyclic ring-type ether or cyclic thioether base or 2 kinds of groups, can list the compound that has 2 above epoxy radicals in the molecule for example is multi-functional epoxy compound (D-1), the compound that has 2 above oxetanyls in the molecule is multifunctional oxetane compound (D-2), the compound that has 2 above thioether groups in the molecule is an episulfide resin (D-3) etc.

As aforementioned multi-functional epoxy compound (D-1), for example can list, bisphenol A type epoxy resin, as Japan Epoxy Resins Co., Ltd. the jER828 of Zhi Zaoing, jER834, jER1001, jER1004, the Epiclon840 that DIC Corporation makes, Epiclon850, Epiclon1050, Epiclon2055, Dongdu changes into the EpototeYD-011 that company makes, YD-013, YD-127, YD-128, the D.E.R.317 that Dow ChemicalCompany makes, D.E.R.331, D.E.R.661, D.E.R.664, the Araldite6071 that Xiba Special Chemical Product Co.,Ltd makes, Araldite6084, AralditeGY250, AralditeGY260, the SumiepoxyESA-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); Brominated epoxy resin, as Japan Epoxy Resins Co., Ltd. the jER YL 903 of Zhi Zaoing, Epiclon152, Epiclon165 that DIC Corporation makes, Dongdu changes into EpototeYDB-400, the YDB-500 that company makes, the D.E.R.542 that Dow Chemical Company makes, the Araldite8011 that Xiba Special Chemical Product Co.,Ltd makes, SumiepoxyESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. makes, (being trade name) such as A.E.R.711, A.E.R.714 that industrial group of Asahi Chemical Industry makes; Phenolic resin varnish type epoxy resin, as Japan Epoxy Resins Co., Ltd. the jER152 of Zhi Zaoing, jER154, the D.E.N.431 that DowChemical Company makes, D.E.N.438, the EpiclonN-730 that DICCorporation makes, EpiclonN-770, EpiclonN-865, Dongdu changes into the EpototeYDCN-701 that company makes, YDCN-704, the AralditeECN1235 that Xiba Special Chemical Product Co.,Ltd makes, AralditeECN1273, AralditeECN1299, AralditeXPY307, the EPPN-201 that Japan's chemical drug corporate system is made, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the SumiepoxyESCN-195X that Sumitomo Chemical Co. Ltd. makes, ESCN-220, the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry makes, ECN-299 etc. (being trade name); Bisphenol f type epoxy resin, Epiclon830 as DIC Corporation manufacturing, Japan Epoxy Resins Co., Ltd. the jER807 of Zhi Zaoing, Dongdu changes into EpototeYDF-170, YDF-175, the YDF-2004 that company makes, (being trade name) such as AralditeXPY306 that Xiba Special Chemical Product Co.,Ltd makes; Bisphenol-A epoxy resin, EpototeST-2004, the ST-2007 that makes as Dongdu company that changes into, ST-3000 (trade name) etc.; Glycidyl amine type epoxy resin, as Japan EpoxyResins Co., Ltd. the jER604 of Zhi Zaoing, Dongdu changes into the EpototeYH-434 that company makes, the AralditeMY720 that Xiba Special Chemical Product Co.,Ltd makes, (being trade name) such as SumiepoxyELM-120 that Sumitomo Chemical Co. Ltd. makes; Hydantoins type epoxy resin, the AralditeCY-350 (trade name) that makes as Xiba Special Chemical Product Co.,Ltd etc.; Alicyclic epoxy resin, as DAICELCHEMICAL INDUSTRIES, the Celoxide2021 that LTD. makes, (being trade name) such as Araldite CY 175, CY 179 that Xiba Special Chemical Product Co.,Ltd makes; Trihydroxy benzene methylmethane type epoxy resin, as Japan Epoxy Resins Co., the YL-933 that Ltd. makes, (being trade name) such as T.E.N., the EPPN-501 that 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 EBPS-200 that Japan's chemical drug corporate system is made, the EPX-30 that Asahi Electro-Chemical Co. Ltd makes, the EXA-1514 bisphenol-s epoxy resins such as (trade names) that DIC Corporation makes; Japan EpoxyResins Co., the jER157S bisphenol-A phenolic varnish type epoxy resin such as (trade names) that Ltd. makes; Japan Epoxy Resins Co., the jERYL-931 that Ltd. makes, four hydroxyphenyl ethane type epoxy resin such as Araldite163 (being trade name) that Xiba Special Chemical Product Co.,Ltd makes; The AralditePT810 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; 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; Chemical company of Nippon Steel makes ESN-190, ESN-360, and DIC Corporation makes the epoxy resin that HP-4032, EXA-4750, EXA-4700 etc. contain naphthyl; HP-7200, the HP-7200H etc. that DIC Corporation 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, especially phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their potpourri are preferred.

As aforementioned multifunctional oxetane compound (D-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 (calixresorcinarene) 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.

Episulfide resin (D-3) as having 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.

Use level about the Thermocurable composition (D) that has 2 above ring-types (sulphur) ether in the aforementioned molecule, with respect to the aforementioned 1 equivalent carboxyl that contains carboxy resin, ring-type (sulphur) ether 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 (D) of 2 above ring-types (sulphur) ether in the molecule, have carboxyl residual in soldering-resistance layer, 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 remains in the dry coating, thereby makes the reductions such as intensity of filming, so not preferred.

In order further to improve thermotolerance, the insulating reliability of cured coating film, in in hardening resin composition of the present invention, cooperating aforementioned molecule, have the Thermocurable composition (D) of 2 above ring-types (sulphur) ether, can also cooperate known heat-curing resins commonly used such as polyimide resin, cyclic carbonate compound, bismaleimides, oxazine compound, oxazoline compound, the inferior diamine resin of carbon such as the compound that has 2 above isocyanate group or closure isocyanate group in 1 molecule, melamine resin, melamine derivative, benzoguanamine resin.

As the compound that has 2 above isocyanate group or closure isocyanate group in aforementioned 1 molecule, can list the compound that has 2 above isocyanate group in 1 molecule is polyisocyanate compound, or the compound that has 2 above closure isocyanate group in 1 molecule is a blocked isocyanate compound etc.

As aforementioned polyisocyanate compound, can use for example aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.Object lesson as aromatic polyisocyanate, can list 4,4 '-'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, m xylene diisocyanate and 2, the 4-toluene diisocyanate dimer.Object lesson as aliphatic polyisocyante, can list tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and isophorone diisocyanate.As the object lesson of ester ring type polyisocyanates, can list the bicycloheptane triisocyanate.And the adduct of the isocyanate compound that lists above, biuret body and isocyanuric acid ester body.

Closure isocyanate group contained in the aforementioned blocked isocyanate compound is that isocyanate group is by protected with the sealer reaction, thus by the group of temporary transient passivation.When being heated to set point of temperature, this sealer dissociates, and generates isocyanate group.

As the blocked isocyanate compound, can use the addition reaction product of isocyanate compound and isocyanates sealer.As can with the isocyanate compound of sealer reaction, can list isocyanuric acid ester type, bisacetal type, add mould assembly etc.As this isocyanate compound, can use for example aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.As the object lesson of aromatic polyisocyanate, aliphatic polyisocyante and ester ring type polyisocyanates, can list above-named those compounds.

As the isocyanates sealer, for example can list, phenol such as phenol, cresols, xylenols, chlorophenol and ethyl-phenol are sealer; Lactams such as epsilon-caprolactams, δ-valerolactam, butyrolactam and azetidinone are sealer; Ethyl acetoacetate and diacetone isoreactivity methylene base system sealer; Alcohol 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, benzylic ether, methyl glycollate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate are sealer; Oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, hexamethylene oxime are sealer; Mercaptan such as butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, benzenethiol, methylbenzene thiophenol, ethyl thiophenol are sealer; Acid amides such as acetamide, benzamide is a sealer; Imide series such as succinimide and maleimide sealer; Amine such as xylidin, aniline, butylamine, dibutylamine are sealer; Imidazoles such as imidazoles, 2-ethyl imidazol(e) are sealer; Imines such as methylene imine and propylidene imines are sealer etc.

The blocked isocyanate compound can use commercially available material, for example can list, SumiduleBL-3175, BL-4165, BL-1100, BL-1265, DesmoduleTPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm2170, Desmotherm2265 (more than, Sumika BayerUrethane Co., Ltd. make, trade name), coronate2512, coronate2513, coronate2520 (more than, Japanese polyurethane industrial group makes, trade name), B-830, B-815, B-846, B-870, B-874, B-882 (Mitsui Takeda Chemical Co., Ltd. make, trade name), TPA-B80E, 17B-60PX, E402-B80T (AsahiKasei Chemicals Corporation makes, trade name) etc.In addition, SumiduleBL-3175, BL-4265 are to use the Methylethyl oxime to obtain as sealer.

The compound that has 2 above isocyanate group or closure isocyanate group in the 1 above-mentioned molecule can be used singly or in combination of two or more thereof.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level that has the compound of 2 above isocyanate group or closure isocyanate group in the 1 such molecule is 1～100 mass parts, more preferably the ratio of 2～70 mass parts is fit to.During aforementioned use level less than 1 mass parts, so the obdurability that can not be filmed fully is not preferred.On the other hand, when surpassing 100 mass parts, the storage stability of composition reduces, so not preferred.

As other Thermocurable composition, can list melamine derivative, benzoguanamine derivant etc.For example melamine methylol compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound etc. are arranged.And then alkoxy methyl melamine compound, alkoxy methyl benzoguanamine compound, alkoxy methyl glycoluril compounds and alkoxy methyl urea compounds are transformed to alkoxy methyl respectively with the methylol of melamine methylol compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound and obtain.There is no particular limitation to the kind of this alkoxy methyl, can be for example methoxy, ethoxyl methyl, propoxyl group methyl, butoxymethyl etc.Especially be that melamine derivative below 0.2% is preferred to human body, eco-friendly formalin concentration.

As these commercially available product, can list for example Cymel 300, Cymel 301, Cymel 303, Cymel 370, Cymel 325, Cymel 327, Cymel 701, Cymel 266, Cymel 267, Cymel 238, Cymel 1141, Cymel 272, Cymel 202, Cymel 1156, Cymel 1158, Cymel 1123, Cymel 1170, Cymel 1174, Cymel UFR65, Cymel 300 (more than, Mitsui CyanamidCo.Ltd makes), NIKALAC Mx-750, NIKALAC Mx-032, NIKALACMx-270, NIKALAC Mx-280, NIKALAC Mx-290, NIKALACMx-706, NIKALAC Mx-708, NIKALAC Mx-40, NIKALACMx-31, NIKALAC Ms-11, NIKALAC Mw-30, NIKALACMw-30HM, NIKALAC Mw-390, NIKALAC Mw-100LM, NIKALAC Mw-750LM (more than, Sanwa Chemical Co.Ltd. makes) etc.Above-mentioned Thermocurable composition can be used alone or in combination of two or more kinds.

When using the Thermocurable composition (D) that has 2 above ring-types (sulphur) ether in the aforementioned molecule, preferably contain thermal curing catalyst.As such thermal curing catalyst, can list for example 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, can list four countries for example 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), DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc. that SAN-APRO company makes.Be not limited in these compounds, so long as the thermal curing catalyst of the thermal curing catalyst of epoxy resin, oxetane compound, or promote the material of the reaction of epoxy radicals and/or oxetanyl and carboxyl to get final product, can use separately or mix more than 2 kinds and use.In addition, also can use guanamines, acetylguanamine, 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 also is 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 for example, with respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, is preferably 0.1～20 mass parts, more preferably 0.5～15.0 mass parts so long as the ratio of common amount is just enough.

Hardening resin composition of the present invention preferably comprises phosphorus-containing compound (E).Phosphorus-containing compound can be the commonly used known material as organic phosphorus flame retardant, and phosphate and condensed phosphoric acid esters are arranged, the compound shown in cyclic phosphazene compound, phosphonitrile oligomer, hypophosphites or the following general formula (I).

[Chemical formula 1]

In the formula, R ¹, R ²And R ³Represent halogen atom substituting group in addition independently of one another.

As the commercially available product of the compound shown in the above-mentioned general formula (I), HCA, SANKO-220, M-ESTER, HCA-HQ (being the trade name of three light (strain)) etc. are arranged.

As the used particularly preferred phosphorus-containing compound (E) of the present invention, can list that (1) has acrylate-based phosphorus-containing compound as reactive group, (2) have phenol hydroxyl phosphorus-containing compound, (3) oligomer or polymkeric substance, (4) phosphonitrile oligomer and (5) hypophosphites as reactive group.

(1) has acrylate-based phosphorus-containing compound

The phosphorus element-containing acrylate can be to have the compound that comprises (methyl) acrylate more than 2 in P elements and the molecule, particularly, can list the R in the aforementioned formula (1) ¹And R ²Be hydrogen atom, R ³Be the compound of acrylate derivative, usually can be by 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide synthesizes by Michael addition reaction (michael addition reaction) with known polyfunctional acrylic ester monomer commonly used.

As above-mentioned known 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.

(2) has the phosphorus-containing compound of phenol hydroxyl

This has hydrophobicity, the thermotolerance height of the phosphorus-containing compound of phenol hydroxyl, can not reduce the solder heat resistance height because of hydrolysis causes electrical characteristics.In addition, as suitable combination, the epoxy resin, other epoxy resin that have biphenyl backbone by use is as (D) composition, itself and epoxy resin are reacted and is included in its network, therefore, can not ooze out this advantage after having curing.As commercially available product, the HCA-HQ of three light (strain) manufacturing etc. is arranged.

(3) oligomer or polymkeric substance

As the phosphorus-containing compound of oligomer or polymkeric substance, to make that bendability reduces less because of the influence of alkyl chain, in addition, because its molecular weight is big, do not ooze out this advantage after can obtaining solidifying.As commercially available product, the M-Ester-HP that has three light (strain) to make, the phosphorous VYLON 337 of (strain) manufacturing etc. spins in Japan.

(4) phosphonitrile oligomer

As the phosphonitrile oligomer, phenoxy phosphazene compound is effectively, and the ring of replacement or unsubstituted phenoxy phosphonitrile oligomer or tripolymer, the tetramer, pentamer is arranged, and liquid, pressed powder all is fit to use.As commercially available product, there is (strain) volt to see FP-100, the FP-300 of pharmacy manufacturing, FP-390 etc.Wherein, the phenoxy phosphazene oligomer that is replaced by alkyl or hydroxyl, cyano group isopolarity group is to containing the dissolubility height of carboxy resin, even a large amount of interpolation does not have adverse effects such as recrystallization yet, so preferably.

(5) hypophosphites

By using hypophosphites, can not damage cured coating film flexibility ground and further improve anti-flammability.In addition, by using the hypophosphites of excellent heat resistance, can suppress oozing out of fire retardant in the hot pressing when mounted.As commercially available product, can list EXOLI TOP 930, EXOLI TOP 935 etc. that Clariant company makes.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of these phosphorus-containing compounds as fire retardant (E) is that the scope of 0～200 mass parts is preferred, especially is preferably 0～100 mass parts.When use level surpassed this scope, so the variation such as flexural property of the cured film that obtains were not preferred.

As the Photoepolymerizationinitiater initiater (F) that constitutes Photocurable resin composition of the present invention, can use and be selected from the oxime ester with oxime ester base is that Photoepolymerizationinitiater initiater, alpha-aminoacetophenone are that Photoepolymerizationinitiater initiater, acylphosphine oxide are the Photoepolymerizationinitiater initiater more than a kind in the group formed of Photoepolymerizationinitiater initiater.

As the oxime ester is the commercially available product of Photoepolymerizationinitiater initiater, can list CGI-325, IRGACURE OXE01, IRGACUREOXE02 that Xiba Special Chemical Product Co.,Ltd makes, N-1919, ADEKA ARKLSNCI-831 etc. that ADEKA Corporation makes.

In addition, the Photoepolymerizationinitiater initiater that has 2 oxime ester bases in the molecule also is to be fit to use, and particularly, can list the oxime ester compound with the carbazole structure shown in the following general formula (II).

[Chemical formula 2]

(in the formula, X represents hydrogen atom, the alkyl of carbon number 1～17, the alkoxy of carbon number 1～8, phenyl, phenyl is (by the alkyl of carbon number 1～17, the alkoxy of carbon number 1～8, amino, alkyl amino or dialkyl amido with alkyl of carbon number 1～8 replace), naphthyl is (by the alkyl of carbon number 1～17, the alkoxy of carbon number 1～8, amino, alkyl amino or dialkyl amido with alkyl of carbon number 1～8 replace), Y, Z represents hydrogen atom respectively, the alkyl of carbon number 1～17, the alkoxy of carbon number 1～8, halogen group, phenyl is (by the alkyl of carbon number 1～17, the alkoxy of carbon number 1～8, amino, alkyl amino or dialkyl amido with alkyl of carbon number 1～8 replace), naphthyl is (by the alkyl of carbon number 1～17, the alkoxy of carbon number 1～8, amino, alkyl amino or dialkyl amido with alkyl of carbon number 1～8 replace), anthryl, pyridine radicals, benzofuranyl (benzofuryl), benzothienyl (benzothienyl), Ar represents the alkylidene of carbon number 1～10, ethenylidene, phenylene, diphenylene, inferior pyridine radicals (pyridylene), naphthylene, thiophene, anthrylene (anthrylene), inferior thienyl (thienylene), furylidene (furylene), 2,5-pyrroles-two base, 4,4 '-talan-two base, 4,2 '-styrene-two base, n represents 0 or 1 integer.

In the aforementioned formula, especially preferredly be, X, Y are respectively methyl or ethyl, and Z is a methyl or phenyl, and n is 0, and Ar is phenylene, naphthylene, thiophene or inferior thienyl.

As alpha-aminoacetophenone 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 particularly) 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.

As acylphosphine oxide is Photoepolymerizationinitiater initiater, can list 2,4 particularly; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.As commercially available product, can list Lucirin TPO, the IRGACURE 819 that Xiba Special Chemical Product Co.,Ltd makes etc. that BASF AG makes.

In the aforesaid Photoepolymerizationinitiater initiater, especially preferred acylphosphine oxide series initiators is considered from the light performance of fading, and its photopermeability preferably and have an effect of anti-flammability.In addition, the efficiency of initiation of oxime ester series initiators is good, and only with just improving light sensitivity effectively on a small quantity, therefore, the degassing when forming epithelium after-baking against corrosion is few, and is effective to the warpage of reduction epithelium, is preferred.Both are used in combination is particularly preferred.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the scope that the use level of foregoing Photoepolymerizationinitiater initiater (F) is 0.01～30 mass parts, be preferably 0.5～15 mass parts is fit to.During use level less than 0.01 mass parts of Photoepolymerizationinitiater initiater (F), the photo-curable deficiency on the copper is filmed and is peeled off, and coating characteristics such as chemical proofing reduce, so not preferred.On the other hand, when surpassing 30 mass parts, Photoepolymerizationinitiater initiater (F) 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 the oxime ester with group shown in the aforementioned formula (II) is the situation of Photoepolymerizationinitiater initiater, with respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, its use level is preferably 0.01～20 mass parts, and more preferably the scope of 0.01～5 mass parts is desirable.

Other Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer as being adapted at using in the Photocurable resin composition of the present invention 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 for example then arranged.

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

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

If enumerate the object lesson of thioxanthones compound, for example then 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 for example then 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 for example then arranged.

If enumerate the object lesson of tertiary amine compound, it then for example is ethanolamine compound, compound with dialkyl amido benzene structure, for example 4,4 '-dimethylamino benzophenone (the NISSOCURE MABP that Japanese Cao Da company makes), 4,4 '-lignocaine benzophenone dialkyl amido benzophenone such as (EAB that Hodogaya Chemical Co.LTD. makes), 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 (KAYACUREEPA 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 (the KAYACURE DMBI that Japanese chemical drug corporate system is made), 4-dimethylamino benzoic acid-2-Octyl Nitrite (Esolol 507 that VanDyk company makes) and 4,4 '-lignocaine benzophenone (EAB that HodogayaChemical Co.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 (A) 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, preferably have the compound of 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, provide painted less, water white photosensitive composite is mathematical, also can be provided in the painted soldering-resistance layer of the color of reflection coloring pigment self when having used coloring pigment.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 (A) 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.During use level less than 0.1 mass parts of tertiary amine compound, existence can not obtain the tendency of sufficient sensitization effect.On the other hand, when surpassing 20 mass parts, tertiary amine compound causes the light absorption on the surface that dry welding resistance is filmed to become violent, the tendency that exists the deep curable to reduce.

Can use N-phenylglycine class known commonly used as chain-transferring agent, phenoxy acetic acids, sulfo-phenoxy acetic acids, thyroidan etc. in the Photocurable resin composition of the present invention in order to improve light sensitivity.If enumerate the object lesson of chain-transferring agent, for example then have, mercapto succinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, halfcystine, thiosalicylic acid and derivant thereof etc. have the chain-transferring agent of carboxyl; Mercaptoethanol, mercaprol, Mercaptobutanol, mercapto-propanediol, sulfydryl butylene glycol, hydroxy benzenes mercaptan and derivant thereof etc. have the chain-transferring agent of hydroxyl; 1-butyl mercaptan, butyl-3-mercaptopropionic acid ester, methyl-3-mercaptopropionic acid ester, 2,2-(ethylidene dioxy base) diethyl mercaptan, ethyl mercaptan, 4-methylbenzene mercaptan, lauryl mercaptan, propanethiol, butyl mercaptan, amyl hydrosulfide, 1-spicy thioalcohol, cyclopentanethiol, cyclohexylmercaptan, thioglycerin, 4,4-thiobis benzenethiol etc.

And then, as the heterogeneous ring compound that chain-transferring agent works, can list for example sulfydryl-4-butyrolactone (another name: 2-sulfydryl-4-butyrolactone) with sulfydryl, 2-sulfydryl-4-methyl-4-butyrolactone, 2-sulfydryl-4-ethyl-4-butyrolactone, 2-sulfydryl-4-fourth mercapto lactone, 2-sulfydryl-4-butyrolactam, N-methoxyl-2-sulfydryl-4-butyrolactam, N-ethoxy-2-sulfydryl-4-butyrolactam, N-methyl-2-sulfydryl-4-butyrolactam, N-ethyl-2-sulfydryl-4-butyrolactam, N-(2-methoxyl) ethyl-2-sulfydryl-4-butyrolactam, N-(2-ethoxy) ethyl-2-sulfydryl-4-butyrolactam, 2-sulfydryl-5-valerolactone, 2-sulfydryl-5-valerolactam, N-methyl-2-sulfydryl-5-valerolactam, N-ethyl-2-sulfydryl-5-valerolactam, N-(2-methoxyl) ethyl-2-sulfydryl-5-valerolactam, N-(2-ethoxy) ethyl-2-sulfydryl-5-valerolactam and 2-sulfydryl-6-caprolactam etc.

As the chain-transferring agent of the development that does not damage Photocurable resin composition, promptly have a heterogeneous ring compound of sulfydryl, especially preferred mercaptobenzimidazole, 3-sulfydryl-4-methyl-4H-1,2,4-triazole, 5-methyl isophthalic acid, 3,4-thiadiazoles-2-mercaptan, 1-phenyl-5-sulfydryl-1H-tetrazolium.These chain-transferring agents can be used alone or in combination of two or more kinds.

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

With respect to the aforementioned carboxy resin (A) 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.When surpassing 35 mass parts, exist because the tendency that their light absorption causes the deep curable to reduce.

The photopolymerization monomer (G) that is used for composition of the present invention is consisted of Photocurable resin composition is, makes Photocurable resin composition of the present invention insoluble or help its thawless material in aqueous alkali by active energy beam irradiation carrying out photocuring.As such compound, 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 or propylene oxide adduct 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.; 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.

And then the hydroxyl that can list Epocryl that the reaction of polyfunctional epoxy resin such as cresols phenolic resin varnish type epoxy resin and acrylic acid obtains and this Epocryl and half urethanes that is formed by diisocyanate such as hydroxy acrylate such as pentaerythritol triacrylate and isophorone diisocyanate react the epoxy polyurethane acrylate compound that obtains etc.Such epoxy acrylate is that resin can not reduce its dry to touch ground raising photo-curable.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level that has the photopolymerization monomer (G) of 2 above olefinic unsaturated groups in such molecule is below 100 mass parts, more preferably the ratio of 5～70 mass parts.During aforementioned use level less than 5 mass parts, photo-curable reduces, and is difficult to develop by the postradiation alkali of active energy beam form pattern, so not preferred.On the other hand, when surpassing 100 mass parts, to the dissolubility reduction of aqueous alkali, filming becomes fragile, so not preferred.

Hardening resin composition of the present invention can cooperate colorant (H).As colorant (H), can use known colorants commonly used such as red, blue, green, Huang, can be any one of pigment, dyestuff, pigment.Particularly, can list and have following color index (C.I.; The Society of Dyers and Colourists distribution) material of sequence number.Wherein, from reducing carrying capacity of environment and, preferably not containing halogen to the viewpoint of the influence of human body.

Red stain:

As red stain, monoazo system, bisdiazo system, monoazo color 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.

Blue colorant:

As blue colorant, phthalocyanine system, anthraquinone system are arranged, pigment system is the compound that is classified as pigment (Pigment), has particularly: 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.

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

The words of 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 foregoing colorant (H), with respect to the aforementioned carboxy resin (A) 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 sufficient.

In order to improve the physical strength of filming of hardening resin composition of the present invention, as required, can cooperate filler.As such filler, can use known inorganic or organic filler commonly used, especially preferably use barium sulphate, preparing spherical SiO 2 and talcum.In addition, be purpose to give anti-flammability, can also use magnesium hydroxide, boehmite etc.And then, NANOCRYL (trade name) XP0396, XP0596, XP0733, XP0746, XP0765, XP0768, XP0953, XP0954, XP1045 (being the trade name of product) that the Hanse-Chemie company that can also use compound with 1 above olefinic unsaturated group, is dispersed with nano silicon in aforementioned polyfunctional epoxy resin makes, NANOPOX (trade name) XP0516, XP0525, XP0314 (being the trade name of product) that Hanse-Chemie company makes.They can use separately or cooperate more than 2 kinds and use.

With respect to the above-mentioned carboxy resin (A) that contains of 100 mass parts, the use level of these fillers is preferably below 500 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 500 mass parts, the viscosity of hardening resin composition increased, and printing reduces, and perhaps solidfied material becomes fragile, so not preferred.

, dry to touch flexible in order to improve can use known binder polymer commonly used in the hardening resin composition of the present invention.As binder polymer, the polymkeric substance of optimum fiber prime system, polyester system, phenoxy resin system.As cellulose-based polymkeric substance, can list butyl acetate cellulose (CAB), propyl acetate cellulose (CAP) series that Eastman company makes, as the polyester based polymer, the VYLON series that company makes is spun by preferred Japan, as the phenoxy resin based polymer, the phenoxy resin of preferred bisphenol-A, Bisphenol F and their hydrogenated compound.With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the addition of these binder polymers be preferably 50 mass parts following, more preferably 1～30 mass parts, be preferably 5～30 mass parts especially.When the use level of binder polymer surpassed 50 mass parts, the alkali-developable of hardening resin composition was poor, and shorten the working life that can develop, so not preferred.

In order to improve the adaptation of interlayer, perhaps improve the adaptation of photo-sensitive resin and base material, can use driving fit promoter in the hardening resin composition of the present invention.If enumerate concrete example, for example benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, morpholinyl methyl isophthalic acid-phenyl-triazole-2-thioketones are then arranged, 5-amino-morpholinyl methylthiazol-2-thioketones, 2-sulfydryl-5-methyl mercapto-thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, contain amino benzotriazole, silane coupling agent etc.

Usually, the oxidation Once you begin of most of macromolecular materials, oxidative degradation then constantly takes place continuously, cause the function of macromolecular material to reduce, therefore, can add (1) that is used for anti-oxidation in the hardening resin composition of the present invention makes the radical scavenger of free radical ineffective treatment of generation or/and (2) are harmless material and the antioxidants such as peroxide decomposer that do not produce new free radical with the peroxide breakdown that produces.

The particular compound of the antioxidant that works as radical scavenger, can list p-dihydroxy-benzene, the 4-tert-butyl catechol, the 2-TBHQ, the hydroquinone monomethyl ether, 2,6-di-t-butyl-paracresol, 2,2-methylene-two (4-methyl-6-tert butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-three (3 ', 5 '-di-tert-butyl-4-hydroxyl benzyl)-guanamine, 4,6-(1H, 3H, 5H) phenol such as triketone system, methylnaphthoquinone, quinone based compounds such as benzoquinones, two (2,2,6,6-tetramethyl 4-piperidyl)-sebacate, amine compounds such as phenothiazine etc.

Radical scavenger can use commercially available material, can list for example ADKSTAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADKSTAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STABLA-68, ADK STAB LA-87 (more than, rising sun electrification company makes, trade name), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN111FDL, TINUVIN123, TINUVIN144, TINUVIN152, TINUVIN292, TINUVIN5100 (more than, Xiba Special Chemical Product Co.,Ltd makes, trade name) etc.

The particular compound of the antioxidant that works as peroxide decomposer, can list phosphorus series compounds such as triphenyl phosphate, pentaerythrite four lauryl thiopropionates, dilauryl thiodipropionate, distearyl 3, chalcogenide compounds such as 3 '-thiodipropionate etc.

Peroxide decomposer can use commercially available material, can list for example ADKSTAB TPP (rising sun electrification company makes trade name), MARKAO-412S (ADEKAARGUS CHEMICAL CO., LTD manufacturing, trade name), SumilizerTPS (sumitomo chemical company manufacturing, trade name) etc.

Above-mentioned antioxidant can be used singly or in combination of two or more thereof.

In addition, therefore macromolecular material, takes measures to make it to ultraviolet stabilization owing to absorbing light takes place to decompose and deterioration usually, except use above-mentioned antioxidant in hardening resin composition of the present invention, can also use ultraviolet light absorber.

As ultraviolet light absorber, can list benzophenone derivates, benzoate derivatives, benzotriazole derivatives, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivant, Anthranilate derivant, dibenzoylmethane derivative etc.As the object lesson of benzophenone derivates, can list 2-hydroxyl-4-methoxy benzophenone, Octabenzone, 2,2 '-dihydroxy-4-methoxy benzophenone and 2,4 dihydroxyl benzophenone etc.Object lesson as benzoate derivatives, can list 2-Ethylhexyl salicylate, phenyl salicylic acid esters, to tert-butyl-phenyl salicylate, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester and cetyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester etc.Object lesson as benzotriazole derivatives, can list 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-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 object lesson of pyrrolotriazine derivatives, can list hydroxyphenyltriazinuv, two ethyl hexyl oxy phenol methoxyphenyl triazines etc.

As ultraviolet light absorber, can use commercially available material, for example can list TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (more than, Xiba Special Chemical Product Co.,Ltd makes, trade name) etc.

Above-mentioned ultraviolet light absorber can use a kind or make up more than 2 kinds and to use separately, by using with aforementioned antioxidant combination, can realize the stabilization of the shaping thing that obtained by hardening resin composition of the present invention.

And then, for synthetic above-mentioned carboxy resin (A), the modulation group compound of containing, perhaps in order to adjust viscosity so that be applied on substrate or the carrier film, hardening 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, hardening resin composition of the present invention can also cooperate known tackifier commonly used such as known hot polymerization inhibitor commonly used, fine particle silica, organobentonite, polynite, defoamer and/or levelling agents such as silicone-based, 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.

The aforementioned hot polymerization inhibitor can be used to prevent aforementioned polymerizable compound thermal polymerization or through the time polymerization.As hot polymerization inhibitor, can list for example 4-metoxyphenol, quinhydrones, the quinhydrones that alkyl or aryl replaces, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, the 2-dihydroxy benaophenonel, 4-methoxyl-2-dihydroxy benaophenonel, protochloride ketone, phenothiazine, chloranil, naphthylamines, betanaphthol, 2,6-di-t-butyl-4-cresols, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), pyridine, nitrobenzene, dinitro benzene, picric acid, the 4-toluidine, methylene blue, the reactant of copper and organic sequestering agent, gaultherolin and phenothiazine, nitroso compound, the chelate of nitroso compound and Al etc.

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

During dry film, with hardening 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, further,, it is desirable at the strippable coverlay of the surface laminated of film for the surface attachment dust that prevents film etc.

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

Hardening resin composition use-case of the present invention organic solvent is as described above adjusted to the viscosity that is fit to coating process, utilize methods such as dip coating, flow coat method, rolling method, scraper rubbing method, silk screen print method, curtain Tu Fa to be applied on the base material, under about 60～100 ℃ temperature, make organic solvent volatile dry contained in the composition (temporary transient dry), can form tack-free film.In addition, above-mentioned composition is applied on the carrier film, drying forms film, and this film rolled when forming dry film, the mode that contacts with base material with cured resin composition layer by laminating machine etc. fits on the base material, peels off carrier film then, can form resin insulating barrier thus.

When being Photocurable resin composition, afterwards, adopt contact (or noncontact mode) to make active energy beam carry out the selectivity exposure or utilize the direct exposure machine of laser directly to carry out pattern exposure by forming figuratum photomask, with unexposed development, can form corrosion-resisting pattern by dilute alkaline aqueous solution (for example 0.3～3wt% aqueous sodium carbonate).And then, under for the situation of composition that contains Thermocurable composition (D), make its heat curing by for example being heated to about 140～180 ℃ temperature, make Thermocurable composition (D) reaction that has 2 above ring-type ethers and/or cyclic thioether base in aforementioned carboxyl that contains carboxy resin (A) 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 (D), also can heat-treat, make when exposing 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, except the printed circuit board (PCB) that is pre-formed circuit, flexible printed circuit board, can list high-frequency circuit with the copper clad laminate of all grades (FR-4 etc.) of copper clad laminate etc., Kapton, PET film, glass substrate, ceramic substrate, wafer board etc., wherein aforementioned copper clad laminate uses material such as phenol paper, epoxy paper, epoxy glass fabric, glass polyimide, glass cloth/epoxy nonwoven fabrics, glass cloth/epoxy paper, synthon epoxy, fluorine tygon PPO cyanate and obtains.

Be coated with the volatile dry that carries out behind the hardening resin composition of the present invention and can use heated air circulation type drying oven, IR stove, hot plate, convective oven etc. (use has the device of the thermal source of the air heat mode of utilizing steam, makes the method for the hot air convection contact in the dryer and the mode of blowing supporter by nozzle).

Under the situation that is Photocurable resin composition,, make exposure portion (part of being shone by active energy beam) solidify to by coating and make expose (irradiation of active energy beam) of filming that obtains after the solvent evaporates drying.

As the used exposure machine of above-mentioned irradiation active energy ray, so long as the ultraviolet device that is equipped with high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, mercury short arc lamp etc. and shines 350～450nm scope gets final product, can also use direct drawing apparatus (for example utilizing the laser direct imaging device of the direct rendering image of laser) by cad data from computing machine.As the lasing light emitter of directly retouching machine, be the laser of the scope of 350～410nm as long as use maximum wavelength, can be any of gas laser, Solid State Laser.Be used for exposure that image forms according to thickness etc. and different, be generally 20～800mJ/cm ², be preferably 20～600mJ/cm ²Scope in.

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

Embodiment

Below, embodiment is shown and comparative example describes particularly to the present invention, but the present invention is not subjected to the qualification of following embodiment.In addition, following " part " and " % " if there is no particular limitation, are meant quality criteria.

Synthesis example 1

(A-1) be equivalent to the synthetic of the aforementioned resin that contains carboxy resin (2):

In the reaction vessel that possesses stirring apparatus, thermometer, condenser, drop into 3600g (4.5 moles) as have 2 above alcohol hydroxyl groups compound by 1,5-pentanediol and 1, the PCDL that the 6-hexanediol is derived (Asahi KaseiChemicals Corporation makes, TJ5650J, number-average molecular weight 800), 814g (5.5 moles) dimethylolpropionic acid and 118g (1.6 moles) adjust the normal butyl alcohol of agent (reaction terminating agent) as molecular weight.Then, drop into 2009g (10.8 moles) as the trimethyl hexamethylene diisocyanate that does not have the isocyanate compound of aromatic rings, stop after being heated to 60 ℃ while stirring, when beginning to reduce, the temperature in reaction vessel heats once more, continue to stir at 80 ℃, confirm the absorption spectra (2280cm of isocyanate group by infrared absorption spectrum ^-1) after the disappearance, finish reaction.Then, adding the carbitol acetic acid esters, to make solid constituent be 60wt%, obtain containing thinning agent thick liquid contain carboxy resin.The acid number of the solid constituent that contains carboxyl polyurethane that obtains is 49.8mgKOH/g.

Synthesis example 2

(A-2) be equivalent to the synthetic of the aforementioned resin that contains carboxy resin (5):

In the reaction vessel that possesses stirring apparatus, thermometer, condenser, drop into 2400g (3 moles) by 1,5-pentanediol and 1, the PCDL that the 6-hexanediol is derived (Asahi Kasei Chemicals Corporation makes, TJ5650J, number-average molecular weight 800), 603g (4.5 moles) dihydromethyl propionic acid and 238g (2.6 moles) are as the 2-hydroxy ethyl methacrylate of monohydroxy compound.Then, drop into the isophorone diisocyanate of 1887g (8.5 moles) as polyisocyanates, stop after being heated to 60 ℃ while stirring, when beginning to reduce, the temperature in reaction vessel heats once more, continue to stir at 80 ℃, confirm the absorption spectra (2280cm of isocyanate group by infrared absorption spectrum ^-1) after the disappearance, finish reaction.Then, add the carbitol acetic acid esters and make that solid constituent is 50 quality %.The acid number of the solid constituent that contains carboxy resin that obtains is 50mgKOH/g.

Synthesis example 3

(A-3) be equivalent to the synthetic of the aforementioned resin that contains carboxy resin (4):

In removable flask, add RE310S (the 2 officials energy bisphenol A type epoxy resin that 368.0g makes as the Japanese chemical drug (strain) of bisphenol type epoxy compound, the 184g/ equivalent), 142.7g acrylic acid (molecular weight: 72.06), 2.94g is as 2 of hot polymerization inhibitor epoxide equivalent:, 6-di-t-butyl-paracresol and 1.53g are as the triphenylphosphine of catalysts, the acid number that reacts until reactant liquor under 98 ℃ temperature is below the 0.5mgKOH/g, obtains epoxy carbonate (a) (theoretical molecular: 510.7).Then, in this reactant liquor, add carbitol acetic acid esters, 105.5g dihydromethyl propionic acid (the b) (molecular weight: 134.16), make it be warmed up to 45 ℃ of 588.2g as reaction dissolvent.In this solution, slowly splash into 264.7g isophorone diisocyanate (c) (molecular weight: 222.28), make temperature of reaction be no more than 65 ℃.After dripping end, temperature is increased to 80 ℃, makes its reaction 6 hours, until recording 2250cm by the infrared absorption spectrum determination method ^-1Near absorption disappears, and then reaction is 2 hours under 98 ℃ temperature, obtains comprising the resin solution of 60 weight % aqueous alkaline solution-soluble urethane resins.Measure acid number, be 28.9mgKOH/g (solid constituent acid number: 48.1mgKOH/g).

(A-4) be equivalent to the aforementioned resin that contains carboxy resin (7):

Use with aforementioned contain carboxy resin (7) suitable, contain the photonasty group and used the multi-functional epoxy's of xenol Novolac structure photonasty to contain carboxy resin [ZCR-1601H (solid constituent 65%, the acid number of resin are 98mgKOH/g) that Japanese chemical drug corporate system is made].

The preparation of aluminium hydroxide slurry:

700g aluminium hydroxide (HIGILITE42M that clear and electrician's (strain) makes), 280g are mixed stirring as carbitol acetic acid esters, the 20g BYK-110 of solvent, use the zirconium oxide bead of 0.5 μ m to carry out dispersion treatment by ball mill.After repeating this operation 3 times,, make aluminium hydroxide slurry (C-1) by the filtrator of 3 μ m.

Embodiment 1～14, comparative example 1～3

Use the resin solution of aforementioned each synthesis example, cooperate, carry out premixed, carry out mixingly then with 3 roll-type roller mills, prepare the solder resist photosensitive polymer combination by stirring machine according to the ratio (mass parts) shown in various compositions shown in the table 1 and the table 1.At this, measure granularity with the particle size analyzer that ERICHSEN company makes, estimate the dispersion degree of the photosensitive polymer combination that obtains, be 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 Thermocurable Photocurable resin composition of silk screen print method whole coating previous embodiment 2～14 and comparative example 2,3, drying is 30 minutes in 80 ℃ heated air circulation type drying oven.After the drying, use the exposure device (HMW-680-GW20 that ORC MANUFACTURING Co.Ltd makes) that is equipped with metal halide lamp to expose by stage metraster (KodakNo.2), will develop (30 ℃, 0.2MPa, 1wt%Na ₂CO ₃Exposure when aqueous solution) pattern of residual stage metraster is 6 sections during 90 seconds is as optimum exposure.

Attribute testing:

The composition of the various embodiments described above 1～14 and comparative example 1～3 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.For the hot curing resin composition of embodiment 1 and comparative example 1, the substrate that obtains is heating and curing under 150 ℃ made its curing in 60 minutes.For the Photocurable resin composition of embodiment 2～14 and comparative example 2,3, use the exposure device (HMW-680-GW20) that is equipped with metal halide lamp the soldering-resistant pattern on the substrate that obtains to be exposed, with 30 ℃ 1wt%Na with optimum exposure ₂CO ₃Aqueous solution was developed for 90 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.The printed base plate (evaluation substrate) that obtains is carried out following evaluating characteristics.

The circuit covering power

The above-mentioned substrate that obtains was like that heated under 140 ℃ 1 hour again.Confirm heating, had or not variable color by the color of the copper circuit of solder resist cover part by 140 ℃, 1 hour.

Zero: copper circuit does not have variable color

*: can see the copper circuit variable color

Solder heat resistance

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

Zero: carry out flooding 1 time 10 second, can't see and peel off.

△: carry out flooding 1 time 5 second, can't see and peel off.

*: carry out flooding 1 time 5 second, resist layer has expansion, peels off.

Low warpage properties

To go up the cured film of making at Kapton 100H (DU PONT-TORAY CO., Kapton, thickness that LTD. makes are 25 μ m) and be cut into 50 * 50mm size, measure the warpage at 4 angles, obtain its mean value, estimate according to following benchmark.

Zero: the not enough 1mm of warpage

△: warpage is the above and not enough 4mm of 1mm

*: warpage is more than the 4mm

Resolution

The photosensitive polymer combination of embodiment 2～14 and comparative example 2,3 is applied on the full copper base by the whole face of serigraphy, and drying is 30 minutes under 80 ℃.Use the negative film of L/S (line/space)=100/500 μ m to expose, develop under these conditions with optimum exposure.After the development, confirm to have or not the line of 100 μ m residual.

Zero: the residual line that 100 μ m are arranged on the full copper base.

*: the line that does not have residual 100 μ m on the full copper base.

Anti-flammability

By serigraphy the whole face of the composition of each embodiment and comparative example is applied to 12.5 μ m or thick Kapton (the DU PONT-TORAY CO. of 25 μ m, LTD. make Kapton 50H, 100H), after under 80 ℃ dry 20 minutes, naturally cool 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.For the hot curing resin composition of embodiment 1 and comparative example 1, the two sided coatings substrate heating under 150 ℃ that obtains was made its curing in 60 minutes.Photocurable resin composition for embodiment 2～14 and comparative example 2,3, use the exposure device (HMW-680-GW20) that is equipped with metal halide lamp to carry out whole exposure the two sided coatings substrate that obtains, with 30 ℃ 1wt%Na with the optimum exposure solder resist ₂CO ₃Aqueous solution was developed for 90 seconds under the condition of spray pressure 0.2MPa, 150 ℃ of following heat curings 60 minutes, obtained assess sample.This anti-flammability evaluation is carried out thin material testing vertical flammability based on the UL94 specification with sample.Be shown VTM-0 or VTM-1 based on the UL94 specification table during evaluation.

Aforementioned each evaluation test the results are summarized in table 2, table 3.

[table 2]

[table 3]

Embodiment 15,16

Mismatch the silicone-based defoamer, other is according to the preparation of compositions hardening resin composition shown in the embodiment shown in the table 13,14, dilute with MEK, be applied on the carrier film, heat drying, forming thickness is the photosensitive polymer combination layer of 20 μ m, and the coverlay of fitting thereon obtains dry film.Afterwards, peel off coverlay, the use laminating machine to forming on the figuratum copper clad laminate, is made the test substrate with film adhered.With aforesaid test method and evaluation method similarly, carry out the evaluation test of each characteristic.The result is as shown in table 4.

[table 4]

Claims (12)

1. a hardening resin composition is characterized in that, it contains (A) and contains carboxy resin, (B) titanium dioxide and (C) aluminium hydroxide.

2. hardening resin composition according to claim 1 is characterized in that, it further contains the Thermocurable composition that has 2 above ring-type ethers and/or cyclic thioether base in (D) molecule.

3. hardening resin composition according to claim 1 is characterized in that, it further contains (E) phosphorus-containing compound.

4. hardening resin composition according to claim 1 is characterized in that, it further contains (F) Photoepolymerizationinitiater initiater and (G) photopolymerization monomer.

5. hardening resin composition according to claim 1 is characterized in that, it contains described titanium dioxide (B) colorant (H) in addition.

6. hardening resin composition according to claim 1 is characterized in that, the described carboxy resin (A) that contains is the carboxy resin that contains with carbamate skeleton.

7. hardening resin composition according to claim 1 is characterized in that, the described carboxy resin (A) that contains has xenol Novolac structure and olefinic unsaturated group.

8. hardening resin composition according to claim 2 is characterized in that, the Thermocurable composition (D) that has 2 above ring-type ethers and/or cyclic thioether base in the described molecule is the epoxy resin with xenol Novolac skeleton.

9. according to each described hardening resin composition of claim 1～8, it is characterized in that it is a solder resist.

10. dry film, it is applied on the film by each the described hardening resin composition with claim 1～8 and drying forms.

11. a solidfied material, it carries out heat curing by the dry coating that each the described hardening resin composition with claim 1～8 is applied on the base material and drying obtains and/or photocuring obtains; Perhaps, by the dry coating that described hardening resin composition is applied on the film and the dry dry film lamination that forms obtains to the base material being carried out heat curing and/or photocuring obtains.

12. a printed circuit board (PCB), it has the described solidfied material of aforementioned claim 11.