CN102736415A - Phtotocuring thermocuring resin composition, dry film and cured resin thereof, and printed circuit board using the same - Google Patents

Abstract

The invention provides a phtotocuring thermocuring resin composition, a dry film and cured resin thereof, and a printed circuit board formed by making the dry film and the cured resin form a cured epitheliuma, such as a solder mask. The phtotocuring thermocuring resin composition is a 1 hydrothermal resin compositon; the dry film is good in storage and stability at room temperature, and is also good at developing performance, resistance to soldering heat performance, insulation reliability, and gold-plating resistance performance; the phtotocuring thermocuring resin composition can be stored at room temperature and comprises carboxyl resin, photopolymerization initiator and plant origin epoxide. Preferably, teh acid value of the carboxyl resin is 30 to 150mgKOH/g, and the preference is given to the photopolymerization group, especially the olefinic unsaturated group; and as the plant origin epoxide, the preference is given to the epoxy soybean oil and the epoxy linseed oil.

Description

Light solidifying/heat solidifying resin composition, its dry film and solidfied material and the printed circuit board (PCB) that uses them

Technical field

The light solidifying/heat solidifying resin composition that the present invention relates to develop through the diluted alkaline property WS, particularly carry out photocuring through ultraviolet exposure or laser explosure solder resist with composition, its dry film and solidfied material and printed circuit board (PCB) with their cured films of forming of use.

Background technology

Because the quick progress of semiconductor device recently, e-machine exists by the tendency of miniaturization and, high performance, multifunction.Follow this tendency, printed circuit board (PCB) is also carrying out the mounted on surfaceization of densification, parts.Usually adopt the photoresistance solder flux in the manufacturing of high-density printed circuit board, and developed dry-film type photoresistance solder flux and aqueous photoresistance solder flux.From considering the angle of environmental problem, use the diluted alkaline property WS to become main flow in the middle of these as the photosensitive composite of the alkali developable of developer solution, several compositional systems (with reference to patent documentation 1) have been proposed in the past.

The photosensitive composite of alkali developable shows alkali-developable through the resin that composition is contained have carboxyl.

Yet the water wettability of carboxyl is big, uses at photonasty insulating material such as solder resists under the situation of the resin with carboxyl, causes the deterioration of insulating reliability easily.

Therefore, from the purpose that improves insulating reliability, anti-sweating heat performance, use glycidyl compound as representative can with the crosslinked Thermocurable composition of carboxyl.

Even because carboxyl and glycidyl also carry out cross-linking reaction in room temperature, thereby the solder resist composition is generally " the 2 liquid type " that is divided into carboxylated compound and glycidyl compound.

Yet the mixed up time (working life) of the solder resist of 2 liquid types is about several hours～1 day, and is very short, must before painting process, mix.And then also exist this mixed processes to need the problem of time.

In order to remedy the defective that 2 such liquid types are had, studied the photosensitive polymer combination of various 1 liquid types.

For example, proposed to replace glycidyl compound use blocked isocyanate compounds and by this blocked isocyanate compounds with contain the photosensitive polymer combination (with reference to patent documentation 2) that carboxy resin, Photoepolymerizationinitiater initiater, thinning agent, tackifiers are formed.In addition, bag glycidyl compound and use (with reference to the patent documentations 3) such as photosensitive polymer combinations that wraps microcapsules in the epoxy resin of carboxylic acid compound and potentialization of reaction of glycidyl compound under the room temperature in also having proposed in the film of heat damage property.

The prior art document

Patent documentation

Patent documentation 1: japanese kokai publication sho 61-243869 number (claims etc.)

Patent documentation 2: TOHKEMY 2001-305726 number (claims etc.)

Patent documentation 3: TOHKEMY 2010-128317 number (claims etc.)

Summary of the invention

Invent problem to be solved

Yet disclosed light solidifying/heat solidifying resin composition exists thermotolerance and the insulating reliability of cured coating film insufficient or worry the such problem of expensiveization in the above-mentioned patent documentation.

Therefore; The objective of the invention is to; The light solidifying/heat solidifying resin composition that is described below is provided, its as 1 liquid type resin combination with and dry film storage stability at room temperature good, and excellence such as development property, anti-sweating heat performance, insulating reliability, anti-gold-plated property.

And then; The present invention also aims to the printed circuit board (PCB) that dry film and the solidfied material through using above-mentioned each excellent that such light solidifying/heat solidifying resin composition obtains is provided and forms cured films such as solder mask by this dry film, solidfied material.

Be used to solve the method for problem

In order to reach aforementioned purpose, according to the present invention, but the light solidifying/heat solidifying resin composition that provides a kind of normal temperature to preserve is characterized in that it contains carboxy resin, Photoepolymerizationinitiater initiater and plant origin epoxy compound.

In preferred embodiment, the aforementioned acid number that contains carboxy resin is preferably 30～150mgKOH/g, preferably has optical polymerism group, particularly an ethylenically unsaturated group in addition.In addition, as aforementioned plant origin epoxy compound, from preferred epoxidised soybean oil of the viewpoint of versatility and epoxidation linseed oil.

In addition, according to the present invention, also provide aforementioned light solidifying/heat solidifying resin composition is applied on the carrier film and makes its dry and dry film photo-curable that obtains; The solidfied material that aforementioned lights hardening resin composition or this dry film is solidified and obtain particularly makes its photocuring on copper and the solidfied material, the photocuring that obtain become pattern-like and the solidfied material that obtains.

And then, according to the present invention, a kind of printed circuit board (PCB) is provided also, it is characterized in that it has the cured film of following acquisition: after making aforementioned light solidifying/heat solidifying resin composition or dry film photocuring become pattern-like, heat curing and obtaining.

The invention effect

According to light solidifying/heat solidifying resin composition of the present invention; Its as 1 liquid type resin combination with and dry film storage stability at room temperature good, and can form the solidfied material of each excellent such as development property, anti-sweating heat performance, insulating reliability, anti-gold-plated property.

Therefore, light solidifying/heat solidifying resin composition of the present invention can favourablely be applicable to the formation of the cured films such as solder mask of printed circuit board (PCB) and flexible print wiring board.

Embodiment

As previously mentioned, light solidifying/heat solidifying resin composition of the present invention is characterised in that, uses the plant origin epoxy compound with containing carboxy resin, Photoepolymerizationinitiater initiater combination.

Research according to inventor etc.; A kind of resin combination is provided; This light solidifying/heat solidifying resin composition excellent storage stability at room temperature; But it is preserved as 1 liquid type resin combination normal temperature, and excellence such as development property, anti-sweating heat performance, insulating reliability, anti-gold-plated property.And then, therefore environment amenable resin combination can also be provided owing to use plant material as the Thermocurable composition.

Below, specify each constituent of light solidifying/heat solidifying resin composition of the present invention.

As the aforementioned carboxy resin that contains,, can use the known in the past various carboxy resins that contain that in molecule, have carboxyl from the purpose of giving cross-linking reaction, adaptation and alkali-developable.Particularly, from the aspect of photo-curable, anti-development property, as carrying out the photosensitive composition that alkali develops, what more preferably have ethylenical unsaturated double bonds in the molecule contains the carboxyl photoresist.And this unsaturated double-bond preferably derives from acrylic or methacrylic acid or their derivant, be preferably have an ethylenically unsaturated group contain carboxyl (methyl) acrylic ester.In addition; Do not have under the situation that contains carboxy resin of ethylenical unsaturated double bonds only using; In order to make composition is photo-curable, need with the required amount of photocuring and with after have the photosensitive compounds (photopolymerization monomer) of a plurality of ethylenically unsaturated groups in the molecule stated.

As the object lesson that contains carboxy resin, the compound of enumerating below preferred (can in oligomer and the polymkeric substance any).

(1) copolymerization that contains the compound of unsaturated group through unsaturated carboxylic acid such as (methyl) acrylic acid and styrene, AMS, low alkyl group (methyl) acrylic ester, isobutylene etc. obtains to contain carboxy resin, and make that the compound reaction of the ethylenically unsaturated group that has in itself and the molecule more than 1 and 1 epoxy radicals forms contain the carboxyl photoresist.

(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 an alkylene oxide addition product glycol; Have phenolic hydroxyl group and alcoholic extract hydroxyl group diol compounds such as compound addition polymerization and obtain contain the carboxyl urethane resin.

(3) through 2 officials such as diisocyanate and bisphenol A type epoxy resin, hydrogenation bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, diformazan phenol-type epoxy resin, bisphenol-type epoxy resin can epoxy resin (methyl) acrylic ester or the anhydride modified thing of its part, contain that the addition polymerization of carboxylic diol compound and diol compound obtains contain carboxyl photonasty urethane resin.

(4) in the resin of aforementioned (2) or (3) synthetic, add the compound that has 1 hydroxyl and (methyl) acryloyl group more than 1 in (methyl) acrylic acid hydroxy alkyl ester equimolecular, and end (methyl) acryloyl groupization contain carboxyl photonasty urethane resin.

(5) in the resin of aforementioned (2) or (3) synthetic, add have the compound of 1 NCO and (methyl) acryloyl group more than 1 in the reaction with same mole thing equimolecular of IPDI and pentaerythritol triacrylate, also end (methyl) acryloyl groupization contains carboxyl photonasty urethane resin.

(6) 2 officials that state after making can or its above multifunctional (Gu shape) epoxy resin and the reaction of (methyl) acrylic acid, and and make that dibasic acid anhydride additions such as hydroxyl that side chain exists and phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride get contain the carboxyl photoresist.

(7) state after making such further with chloropropylene oxide with 2 officials can (Gu shape) epoxy resin hydroxyl carry out epoxidation and polyfunctional epoxy resin and the reaction of (methyl) acrylic acid, and make that the hydroxyl that produced and dibasic acid anhydride carry out that addition gets contain the carboxyl photoresist.

(8) make the so such cyclic carbonate of cyclic ether, propylene glycol carbonate of so multifunctional oxybenzene compound of varnish and oxirane carry out addition; Make the hydroxyl of gained carry out partial esterification with (methyl) acrylic acid, what make that the reaction of multi-anhydrides such as residual hydroxyl and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride forms contains the carboxyl photoresist.

(9) resin that makes above-mentioned (1)～(8) further with (methyl) glycidyl acrylate, Alpha-Methyl diglycidyl (methyl) acrylic ester equimolecular in have 1 epoxy radicals and (methyl) acryloyl group more than 1 the compound addition and contain the carboxyl photoresist.

In addition, in this instructions, (methyl) acrylic ester is meant the term of general designation acrylic ester, methacrylate and their potpourri, and other similarly show too.

In the middle of these, the resin of enumerating in the modifier of (1), (2) and its (4) and (5), (8) can contain the carboxylic acid resin not using so that chloropropylene oxide is synthetic under as the situation of the epoxy compound (resin) of raw material, thereby preferred especially from the viewpoint of halogen.In addition, use the epoxy compound (resin) that does not adopt chloropropylene oxide, also can reach halogen through epoxy compound (resin).

In addition; From stable on heating viewpoint, use among the present invention contain carboxy resin preferably make by as aforementioned (6), (7), (8) in compound and the tetrabydrophthalic anhydride of varnish or the compound deriving that main framings such as bisphenol-A, Bisphenol F have the aromatic series skeleton of record contain the carboxyl photoresist as what the dibasic acid anhydride addition of representative got.But from the viewpoint of storage stability, through the polymerization of the such unsaturated carboxylic acid of (methyl) acrylic acid derive to contain carboxy resin comparatively good.This thinks owing to compare with the carboxyl of being derived by aforesaid acid anhydrides from the carboxyl of the polycarboxylic acid resin of unsaturated carboxylic acid derivative, reactive gentle with epoxy radicals, thereby excellent storage stability.

Above-mentioned that kind contain carboxy resin because the side chain of trunk polymer has a plurality of carboxyls, thereby can develop through the diluted alkaline property WS.

In addition, the above-mentioned acid number that contains carboxy resin is suitably for the scope of 30～200mgKOH/g, more preferably 30～150mgKOH/g, be preferably the scope of 45～120mgKOH/g especially.When containing the acid number deficiency 30mgKOH/g of carboxy resin, alkali develops and becomes difficult, on the other hand; When surpassing 200mgKOH/g; Because developer solution causes the dissolving aggravation of exposure portion, thereby line is thinner than what need, or the portion of exposure according to circumstances and unexposed indistinction ground are peeled off by dissolves; Normal etched pattern describe the difficulty that becomes, so not preferred.

In addition, the above-mentioned weight-average molecular weight that contains carboxy resin is according to resin matrix and difference, is generally 2,000～150,000, further is preferably 5,000～100,000 scope.Weight-average molecular weight less than 2,000 o'clock can make tack-free degradation, the moisture-proof variation of filming after the exposure, and it is residual to produce film during development, and resolution reduces greatly.On the other hand, weight-average molecular weight surpasses at 150,000 o'clock, because the remarkable variation of development property, so not preferred.

Contain the resin that carboxy resin can be not limited to aforementioned list, can use a kind, also can mix more than 2 kinds and use.

In addition, such compounding amount that contains carboxy resin is suitably for below the 60wt% of total composition, is preferably the scope of 10～50wt%.

As the Photoepolymerizationinitiater initiater that uses among 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 at least a kind of Photoepolymerizationinitiater initiater in the group formed of Photoepolymerizationinitiater initiater.

As aforementioned oxime ester is Photoepolymerizationinitiater initiater, can enumerate out N-1919, NCI-831 of C GI-325 as the BASF JAPAN manufactured of commercially available article, Irgacure (registered trademark) OXE01, IrgacureOXE02, ADEKA manufactured etc.In addition, can also preferably use the Photoepolymerizationinitiater initiater that has 2 oxime ester bases in the molecule, specifically, can enumerate out the oxime ester compound of representing in the formula with carbazole structure.

[Chemical formula 1]

(in the formula; X representes alkoxy, phenyl, phenyl (being replaced by alkoxy, the amino of the alkyl of carbon number 1～17, carbon number 1～8, alkylamino or dialkylamino with alkyl of carbon number 1～8), the naphthyl (being replaced by alkoxy, the amino of the alkyl of carbon number 1～17, carbon number 1～8, alkylamino or dialkylamino with alkyl of carbon number 1～8) of alkyl, the carbon number 1～8 of hydrogen atom, carbon number 1～17; Y, Z represent alkoxy, halogen radical, phenyl, phenyl (being replaced by alkoxy, the amino of the alkyl of carbon number 1～17, carbon number 1～8, alkylamino or dialkylamino with alkyl of carbon number 1～8), naphthyl (being replaced by alkoxy, the amino of the alkyl of carbon number 1～17, carbon number 1～8, alkylamino or dialkylamino with alkyl of carbon number 1～8), anthryl, pyridine radicals, benzofuranyl, the benzothienyl of alkyl, the carbon number 1～8 of hydrogen atom, carbon number 1～17 separately; Ar representes alkylidene, ethenylidene, phenylene, diphenylene, inferior pyridine radicals, naphthylene, thienyl, anthrylene, inferior thienyl, the furylidene, 2 of key or carbon number 1～10; 5-pyrroles-two base, 4; 4 '-talan-two base, 4; 2 '-styrene-two base, n are 0 or 1 integer.)

Respectively do for oneself methyl or ethyl of preferred especially X, Y in the above-mentioned general formula, Z is a methyl or phenyl, and n is 0, and Ar is key or phenylene, naphthylene, thienyl or inferior thienyl.

Such oxime ester is 0.02～10wt% that the compounding amount of Photoepolymerizationinitiater initiater is preferably total composition.During not enough 0.02wt%, the photo-curable on copper is not enough, with film peel off in, coating characteristics such as chemical proofing reduce.On the other hand, when surpassing 10wt%, it is fierce that the light absorption of solder resist film coated surface becomes, the tendency that exists the deep curable to reduce.

As aforementioned alpha-aminoacetophenone is Photoepolymerizationinitiater initiater; Can enumerate out 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N specifically, N-dimethylamino benzoylformaldoxime etc.As commercially available article, can enumerate out Irgacure907, Irgacure369, Irgacure379 of BASF JAPAN manufactured etc.

As aforementioned acylphosphine oxide is Photoepolymerizationinitiater initiater, can enumerate out 2,4 specifically; 6-trimethylbenzene formyl diphenyl phosphine oxide, two (2,4,6-trimethylbenzene formyl)-phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide etc.As commercially available article, can enumerate out Lucirin TPO, Irgacure 819 of BASF JAPAN manufactured etc.

These alpha-aminoacetophenones are that Photoepolymerizationinitiater initiater, acylphosphine oxide are 0.5～15wt% that the compounding amount of Photoepolymerizationinitiater initiater is preferably total composition.During deficiency 0.5wt%, can make the photo-curable on the copper not enough equally, film when peeling off, coating characteristics such as chemical proofing reduce.On the other hand, when surpassing 15wt%, the reduction effect that can not get outgasing further makes the light absorption of solder resist film coated surface become fierce, the tendency that exists the deep curable to reduce.

In addition; As being suitable for the Photoepolymerizationinitiater initiater in the light solidifying/heat solidifying resin composition of the present invention, light-initiated auxiliary agent and sensitizer, can enumerate out benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthones compound, ketal compound, benzophenone cpd, tertiary amine compound and xanthone compound etc.

As aforementioned benzoin compound, specifically, can enumerate out for example benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether etc.

As aforementioned acetophenone compound, specifically, can enumerate out for example acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone etc.

As aforementioned anthraquinone compounds, specifically, can enumerate out for example 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone etc.

As aforementioned thioxanthones compound, specifically, for example can enumerate out 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2,4-diisopropyl thioxanthones etc.

As aforementioned ketal compound, specifically, can enumerate out for example acetophenone dimethyl ketal, benzil dimethyl ketal etc.

As aforementioned benzophenone cpd; Specifically, can enumerate out for example benzophenone, 4-benzoyl diphenylsulfide, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4-benzoyl-4 '-ethyl diphenylsulfide, 4-benzoyl-4 '-propyl group diphenylsulfide etc.

As aforementioned tertiary amine compound; Specifically; The compound that can enumerate out ethanolamine compound for example, has dialkyl amido benzene structure; In the for example commercially available article, 4; 4 '-dimethylamino benzophenone (the NISSO CURE MABP that Tso Tat Co., Ltd., Japan makes), 4; 4 '-diethylamino benzophenone dialkyl amido benzophenone such as (EAB that hodogaya chemical Co., Ltd. makes); 7-(diethylamino)-4-methyl-2H-1-chromen-2-one (7-(diethylamino)-4-methylcoumarin) etc. contains the coumarin compound of dialkylamino; 4-dimethylamino ethyl benzoate (Nippon Kayaku K. K make KAYACURE (registered trademark) EPA), 2-dimethylamino ethyl benzoate (the Quantacure DMB that International Biosynthetic Inc. makes), 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (International Biosynthetic Inc. system Quantacure BEA), to dimethylamino benzoic acid isopentyl ethyl ester (the KAYACURE DMBI that Nippon Kayaku K. K makes), 4-dimethylamino benzoic acid 2-Octyl Nitrite (Esolol 507 of VanDyk manufactured), 4,4 '-diethylamino benzophenone (EAB that hodogaya chemical Co., Ltd. makes) etc.

Preferred thioxanthones compound and tertiary amine compound in above-mentioned Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and the sensitizer.Particularly the aspect of curable preferably comprises the thioxanthones compound from the deep.Wherein, preferably comprise 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthones compounds such as 4-diisopropyl thioxanthones.

Compounding amount as such thioxanthones compound is preferably below the 15wt% of total composition.When the compounding amount of thioxanthones compound surpasses 15wt%, when the thick film curable reduces, bring the cost of product to improve.More preferably below the 10wt%.

In addition; As tertiary amine compound; Be preferably the compound with dialkyl amido benzene structure, wherein preferred especially dialkyl amido benzophenone cpd, maximum absorption wavelength are coumarin compound that contains dialkylamino and the cumarin ketone of 350～450nm.

As aforementioned dialkyl amido benzophenone cpd, 4, the toxicity of 4 '-diethylamino benzophenone is low, so preferred.The aforementioned maximum absorption wavelength that contains the coumarin compound of dialkylamino is in 350～410nm and ultraviolet range; Therefore painted few; Water white photosensitive composite certainly is provided, the painted soldering-resistance layer that uses coloring pigment and reflect the coloring pigment intrinsic colour can be provided in addition.Particularly from angle to the excellent sensitization effect of the laser display of wavelength 400～410nm, preferred 7-(diethylamino)-4-methyl-2H-1-chromen-2-one.

As the compounding amount of such tertiary amine compound, be preferably 0.1～15wt% of total composition.During the compounding quantity not sufficient 0.1wt% of tertiary amine compound, existence can not obtain the tendency of sufficient sensitization effect.When surpassing 15wt%, it is fierce that the light absorption that is caused by tertiary amine compound on the surface that dry solder resist is filmed becomes, the tendency that exists the deep curable to reduce.

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

The total amount of such Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer is preferably with respect to contain below 35 mass parts of carboxy resin 100 mass parts.When surpassing 35 mass parts, exist because the tendency that their light absorption causes the deep curable to reduce.

In addition, these Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer be owing to absorb certain wavelengths, thereby light sensitivity step-down according to circumstances, exists as the acting situation of ultraviolet light absorber.Yet these reagent are not the purpose that only is used to improve the light sensitivity of composition.Can make its light that absorbs certain wavelengths as required, improve the photoreactivity on surface, when changing the wire shaped and the opening of resist layer into vertical, cone-shaped, contrary cone-shaped, improve live width and opening machining precision directly.

As aforementioned plant origin epoxy compound, so long as the unsaturated group of vegetable oil is by the then not special qualification of epoxidised material.Wherein from the preferred epoxidised soybean oil of the viewpoint of versatility, epoxidation castor oil.As commercially available article, can enumerate out ADK CIZER D-32, ADK CIZER D-55, ADK CIZER O-130P, ADK CIZER O-180A (being the ADEKA manufactured) etc.

β cracking and α cracking that the reaction of common glycidyl compound and active proton compound is accompanied by glycidyl compound carry out, but its most of β of being ftractures.This thinks to be caused by reactive and sterically hindered.On the other hand, also think, as previously mentioned; The epoxy radicals of the plant origin epoxy compound epoxy construction that two keys are derived of serving as reasons, this structure is the inner loop oxide structure, compares with common glycidyl compound; Reactivity is lower, thereby can obtain excellent storage stability.And then the plant origin epoxy compound is not owing to use the chloropropylene oxide that in common glycidyl compound synthetic, uses, thereby can obtain the result of excellence from the viewpoint of halogen.

The compounding amount of plant origin epoxy compound is preferably with respect to contain the scope of 5～100 mass parts of carboxy resin 100 mass parts, the more preferably scope of 10～50 mass parts.The compounding amount of plant origin epoxy compound is less than under the situation of 5 mass parts, and the reduction of each characteristic such as worry thermotolerance on the other hand, surpasses under the situation of 100 mass parts, and the plant origin epoxy compound is residual, thinks that coating strength reduces, so not preferred.

In order to give thermotolerance, light solidifying/heat solidifying resin composition of the present invention can also contain other Thermocurable compositions except containing aforementioned plant origin epoxy compound.As the Thermocurable composition that uses among the present invention, can use polyimide resins such as melmac, benzoguanamine resin, blocked isocyanate compounds, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxetane compound, episulfide resin, melamine derivant, span to come known habitual heat-curing resins such as acid amides 、 oxazine compound 、 oxazoline compound, carbodiimide compound.Particularly preferably be, have the Thermocurable composition of a plurality of ring-type ethers and/or cyclic thioether base (below, abbreviate " ring-type (sulphur) ether " as) in the molecule.

The Thermocurable composition that has a plurality of ring-types (sulphur) ether in such molecule is any or the compound of 2 kinds of groups that has in the molecule in a plurality of three-membered rings, four-membered ring or pentacyclic ring-type ether or the cyclic thioether base; For example, can enumerate out the compound that has a plurality of epoxy radicals in the molecule is that the compound that has a plurality of oxetanyls in multi-functional epoxy compound, the molecule is that the compound that has a plurality of thioether groups in multifunctional oxetane compound, the molecule is an episulfide resin etc.

As aforementioned multi-functional epoxy compound; Can enumerate out jER (registered trademark) 828, jER834, jER1001, jER1004 that Mitsubishi Chemical Ind makes; The EHPE3150 of Daicel chemical industrial company system; The EPICLON of DIC manufactured (registered trademark) 840, EPICLON 850, EPICLON 1050, EPICLON 2055; EPOTOHTO (registered trademark) YD-011, YD-013, YD-127, YD-128 that chemical company of Nippon Steel makes; The D.E.R.317 of Dow Chemical's system, D.E.R.331, D.E.R.661, D.E.R.664; The ARALDITE 6071 of BASF JAPAN society, ARALDITE 6084, ARALDITE GY250, ARALDITE GY260, SUMI-epoxy ESA-011, ESA-014, ELA-115, ELA-128 that Sumitomo Chemical Co. Ltd. makes, (being trade name) bisphenol A type epoxy resins such as 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; The jERYL903 that Mitsubishi Chemical Ind makes; The EPICLON 152 of DIC manufactured, EPICLON 165; EPOTOHTO YDB-400, YDB-500 that chemical company of Nippon Steel makes, the D.E.R.542 of Dow Chemical's system, the ARALDITE 8011 of BASF JAPAN manufactured; SUMI-epoxy ESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. makes, (being trade name) brominated epoxy resins such as the A.E.R.711 that industrial group of Asahi Chemical Industry makes, A.E.R.714; JER152, jER154 that Mitsubishi Chemical Ind makes; The D.E.N.431 of Dow Chemical's system, D.E.N.438; The EPICLON N-730 of DIC manufactured, EPICLON N-770, EPICLON N-865; EPOTOHTO YDCN-701, YDCN-704 that chemical company of Nippon Steel makes; The ARALDITE ECN1235 of BASF JAPAN manufactured, ARALDITE ECN1273, ARALDITE ECN1299, ARALDITE XPY307; EPPN (registered trademark)-201, EOCN (registered trademark)-1025, EOCN-1020, EOCN-104S, RE-306, the NC-3000 of Japan's chemical drug manufactured, SUMI-epoxy ESCN-195X, ESCN-220 that Sumitomo Chemical Co. Ltd. makes, (being trade name) varnish type epoxy resin such as the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry makes, ECN-299; The EPICLON 830 of DIC manufactured; Mitsubishi Chemical Ind makes jER807; EPOTOHTO YDF-170, YDF-175, YDF-2004 that chemical company of Nippon Steel makes, (being trade name) bisphenol f type epoxy resins such as ARALDITE XPY306 of BASF JAPAN manufactured; EPOTOHTO ST-2004, ST-2007, ST-3000 hydrogenation bisphenol A type epoxy resins such as (trade names) that chemical company of Nippon Steel makes; The jER604 that Mitsubishi Chemical Ind makes; The EPOTOHTO YH-434 that chemical company of Nippon Steel makes; The ARALDITE MY720 of BASF JAPAN manufactured, (being trade name) glycidyl amine type epoxy resins such as SUMI-epoxy ELM-120 that Sumitomo Chemical Co. Ltd. makes; The ARALDITE CY-350 hydantoins type epoxy resin such as (trade names) of BASF JAPAN manufactured; The CELLOXIDE (registered trademark) 2021 of Daicel chemical industrial company system, (being trade name) alicyclic epoxy resins such as the ARALDITE CY175 of BASF JAPAN manufactured, CY179; The YL-933 that Mitsubishi Chemical Ind makes, (being trade name) trihydroxy benzene methylmethane type epoxy resin such as the T.E.N. of Dow Chemical's system, EPPN-501, EPPN-502; YL-6056, YX-4000, YL-6121 diformazan phenol-type epoxy resin or bisphenol-type epoxy resin or their potpourris such as (being trade name) that Mitsubishi Chemical Ind makes; The EBPS-200 of Japan's chemical drug manufactured, ADEKA industrial group makes EPX-30, the EXA-1514 of DIC manufactured bisphenol-s epoxy resins such as (trade names); The jER157S bisphenol-A varnish type epoxy resin such as (trade names) that Mitsubishi Chemical Ind makes; The jERYL-931 that Mitsubishi Chemical Ind makes, ARALDITE 163 grades (being trade name) the four phenol ethane type epoxy resin of BASF JAPAN manufactured; The ARALDITE PT810 (trade name) of BASF JAPAN manufactured, the TEPIC hetero ring type epoxy resin such as (registered trademarks) that daily output chemical industrial company makes; The o-phthalic acid diglycidyl ester resins such as BLEMMER (registered trademark) DGT that Nof Corp. makes; The four glycidyl group xylene phenolic group ethane resin such as ZX-1063 that chemical company of Nippon Steel makes; ESN-190, ESN-360 that chemical company of Nippon Steel makes, the HP-4032 of DIC manufactured, EXA-4750, EXA-4700 etc. contain the epoxy resin of naphthyl; The HP-7200 of DIC manufactured, HP-7200H etc. have the epoxy resin of bicyclopentadiene skeleton; Epihydric alcohol methylpropenoic acid ester copolymerization such as the CP-50S that Nof Corp. makes, CP-50M are epoxy resin; And the copolymerization epoxy resin of cyclohexyl maleimide and GMA; Epoxide modified polybutadiene rubber derivant (for example contest road chemical industrial company makes PB-3600 etc.), CTBN modified epoxy (the for example YR-102 of chemical company of Nippon Steel manufacturing, YR-450 etc.) etc., but be not limited to these epoxy compounds.These epoxy resin can use separately or make up more than 2 kinds and use.In these particularly the epoxide modified compound that obtains through the peracetic acid method such as EHPE3150, PB-3600, CELLOXIDE 2021 (being Daicel chemical industrial company system) owing to do not contain the halogen ion, so preferably as impurity.

As aforementioned multifunctional oxetane compound; Can enumerate out 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, 1 of 4-; The multifunctional oxetanes class of 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 and their oligomer or multipolymer etc.; In addition, oxetanes alcohol and varnish gum, gather the etherate of (para hydroxybenzene ethene), cardo type bisphenols, calixarene kind, resorcinol calixarene kind or silsesquioxane etc. and resin etc. with hydroxyl.In addition, can also enumerate the multipolymer etc. of unsaturated monomer with oxetanes ring and (methyl) alkyl acrylate.

As the compound that has a plurality of cyclic thioether bases in the aforementioned molecule, can enumerate out the bisphenol A-type episulfide resin YL7000 of for example Mitsubishi Chemical Ind's manufacturing etc.In addition, can also use with same synthetic method the oxygen atom of the epoxy radicals of varnish type epoxy resin is replaced into episulfide resin of sulphur atom etc.

It is 0.1～1.5 equivalent that compounding amount when having the Thermocurable composition of a plurality of ring-types (sulphur) ether in the aforementioned molecule of compounding is preferably with respect to 1 equivalent of the carboxyl in the composition, more preferably the scope of 0.2～1.0 equivalent.When the compounding amount that has the Thermocurable composition of a plurality of ring-types (sulphur) ether in the molecule surpasses 2.5 equivalents, because low-molecular-weight ring-type (sulphur) ether remains in the dry coating, reductions such as the intensity of filming, storage stability also worsens in addition, thereby not preferred.

In addition, as other Thermocurable compositions, can add the compound that has a plurality of NCOs or end-blocking NCO in 1 molecule.As the compound that has a plurality of NCOs or end-blocking NCO in the 1 such molecule, can enumerate out the compound that has a plurality of NCOs in 1 molecule and be the compound that has a plurality of end-blocking NCOs in polyisocyanate compounds or 1 molecule is blocked isocyanate compounds etc.

As aforementioned polyisocyanate compounds, can use for example aromatic poly-isocyanate, aliphatic polymeric isocyanate or ester ring type polyisocyanate.Object lesson as aromatic poly-isocyanate; Can enumerate out 4; 4 '-methyl diphenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1; 5-diisocyanate, O-phthalic group diisocyanate, an xylylene diisocyanate and 2,4-toluene dipolymer.Object lesson as aliphatic polymeric isocyanate; Can enumerate out 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 polyisocyanate, can enumerate out the norbornane triisocyanate.And can enumerate the isocyanate compound before enumerated add zoarium, biuret body and isocyanuric acid ester body.

The contained end-blocking NCO of aforementioned blocked isocyanate compounds is that NCO is through being protected and temporary transient deactivated group with the reaction of end-capping reagent (block agent).When being heated to set point of temperature, this end-capping reagent generation NCO that dissociates.

As such blocked isocyanate compounds, can use the addition reaction product of isocyanate compound and isocyanate-terminated dose.As can with the isocyanate compound of end-capping reagent reaction, can enumerate out cyanurate type, biuret type, adduct type etc.As this isocyanate compound, can use for example aromatic poly-isocyanate, aliphatic polymeric isocyanate or ester ring type polyisocyanate.As the object lesson of aromatic poly-isocyanate, aliphatic polymeric isocyanate, ester ring type polyisocyanate, can enumerate out previous illustrative compound.

As aforementioned isocyanate-terminated dose, for example can enumerating out, the phenol of phenol, cresols, xylenol, chlorophenol and ethyl-phenol etc. is end-capping reagent; Lactams such as epsilon-caprolactams, δ-valerolactam, butyrolactam and azetidinone are end-capping reagent; Ethyl acetoacetate and diacetone isoreactivity methylene base system end-capping reagent; 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, benzyl oxide, methyl glycollate, butyl glycolate, DAA, methyl lactate and ethyl lactate are end-capping reagent; Oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, cyclohexane oxime are end-capping reagent; Mercaptan such as butanethiol, hexyl mercaptans, tert-butyl mercaptan, thiophenol, methyl thiophenol, ethylthiophenol are end-capping reagent; Sour acid amides such as acetamide, benzamide is an end-capping reagent; Imide series such as succinimide and maleimide end-capping reagent; Amine such as xylidin, aniline, butylamine, dibutylamine are end-capping reagent; Imidazoles such as imidazoles, 2-ethyl imidazol(e) are end-capping reagent; Imide series end-capping reagents such as methylene acid imide and propylidene acid imide etc.

Aforementioned blocked isocyanate compounds can be commercially available article.For example; Can enumerate out Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (the above Sumitomo of being Bayer Urethane Co., Ltd. system, trade name), Koronate (registered trademark) 2512, Koronate 2513, Koronate 2520 (above is Japanese polyurethane industrial group system, trade name), B-830, B-815, B-846, B-870, B-874, B-882 (the military field of Mitsui chemical company system, trade name), TPA-B80E, 17B-60PX, E402-B80T (chemical company of Asahi Chemical Industry system, trade name) etc.In addition, Sumidur BL-3175, the material of BL-4265 for using first and second oximes to obtain as end-capping reagent.

The compound that has a plurality of NCOs or end-blocking NCO in the 1 above-mentioned molecule can use a kind or make up more than 2 kinds and use separately.

Compounding amount when in such 1 molecule of compounding, having the compound of a plurality of NCOs or end-blocking NCO is suitably for the 1wt%～50wt% of total composition, the ratio of 2～40wt% more preferably.During aforementioned compounding quantity not sufficient 1wt%, so the obdurability that can not get filming fully is not preferred.On the other hand, when surpassing 50wt%, storage stability reduces, so not preferred.

And then, can enumerate out melamine derivant, benzoguanamine derivant etc. as other Thermocurable compositions.Methylol melamine compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound etc. are for example 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 through the methylol with methylol melamine compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound respectively and obtain.Do not limit for the kind of this alkoxy methyl is special, for example can be methoxy, ethoxyl methyl, propoxyl group methyl, butoxymethyl etc.Preferred is the melamine derivant below 0.2% to human body and the useful formalin concentration of environment particularly.

As these commercially available article; Can enumerate out for example CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, CYMEL 370, CYMEL 325, CYMEL327, CYMEL 701, CYMEL 266, CYMEL 267, CYMEL 238, CYMEL 1141, CYMEL 272, CYMEL 202, CYMEL 1156, CYMEL1158, CYMEL 1123, CYMEL 1170, CYMEL 1174, CYMELUFR65, CYMEL 300 (the above Mitsui of being cyanamid manufactured), NIKALAC (registered trademark) Mx-750, NIKALAC Mx-032, NIKALAC Mx-270, NIKALAC Mx-280, NIKALAC Mx-290, NIKALAC Mx-706, NIKALAC Mx-708, NIKALAC Mx-40, NIKALAC Mx-31, NIKALAC Ms-11, NIKALAC Mw-30, NIKALAC Mw-30HM, NIKALAC Mw-390, NIKALAC Mw-100LM, NIKALAC Mw-750LM, (the above SANWA CHEMICAL CO. of being, LTD. makes) etc.Above-mentioned Thermocurable composition can use separately or make up more than 2 kinds and use.

In addition, can contain compound as other Thermocurable compositions with carbodiimide.Through containing the compound with carbodiimide, thereby it is crosslinked that unreacted hydroxyl residual in itself and the solidfied material or unreacted carboxyl are carried out, and can improve coating strength.And then can suppress the deterioration of filming through the hydrolysis of ester bond.

The compound with carbodiimide that uses among the present invention can easily obtain from market.Specifically, can enumerate out the CARBODILITE V-03 that spins the CARBODILITE series that Co., Ltd. makes day clearly, CARBODILITEV-06, CARBODILITE 10M-SP, CARBODILITE 9010 etc.

Compounding amount with compound of carbodiimide is suitably for 0.5～40wt% of total composition, is preferably the scope of 1wt%～30wt%.When the compounding amount with compound of carbodiimide surpassed above-mentioned scope, the intensity of filming reduced, so not preferred.On the other hand, during not enough 0.5wt%, the effect of hydrolytic resistance is impaired, so not preferred.

State in the use under the situation of the Thermocurable composition that has a plurality of ring-types (sulphur) ether in the molecule, preferably contain thermal curing catalyst.As such thermal curing catalyst, can enumerate out 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 dimethyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, amines such as N-dimethyl benzyl amine, hydrazine compounds such as adipic dihydrazide, sebacic dihydrazide; Phosphorus compounds such as triphenyl phasphine etc.In addition; As commercially available article, U-CAT (registered trademark) 3503N of the 2MZ-A that for example has four countries to change into industrial group to make, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound), SAN-APRO manufactured, U-CAT3502T (being the trade name of the blocked isocyanate compounds of dimethyl amine), DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc.Particularly; It is not limited to these compounds; So long as the thermal curing catalyst of epoxy resin or oxetane compound, maybe can promote the material of epoxy radicals and/or oxetanyl and carboxyl reaction to get final product, it 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-s-triazine/Striazine derivatives such as isocyanuric acid addition product preferably uses these compound and combinations of aforementioned hot curing catalysts of also playing the effect of adaptation imparting agent.

The compounding amount of these thermal curing catalysts be common amount ratio promptly fully, for example with respect to Thermocurable composition 100 mass parts that have a plurality of ring-types (sulphur) ether in the molecule, be preferably 0.1～20 mass parts, 0.5～15.0 mass parts more preferably.

For the adaptation that improves interlayer or the adaptation of photo-sensitive resin and base material, in the light solidifying/heat solidifying resin composition of the present invention, can use driving fit promoter.For example can enumerate out benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, morpholinyl methyl isophthalic acid-phenyl-triazole-2-thioketones, 5-amino-morpholinyl methyl-thiazole-2-thioketones, 2-sulfydryl-5-methyl mercapto-thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole specifically, contain amino benzotriazole, vinyl triazole, silane coupling agent etc.

The compound that has a plurality of ethylenically unsaturated groups in can the compounding molecule in the light solidifying/heat solidifying resin composition of the present invention.The compound that has a plurality of ethylenically unsaturated groups in the molecule that uses in the Photocurable resin composition of the present invention; It is for through active energy beam irradiation photocuring, curable resin of the present invention or aforementioned carboxy resin are not dissolved in alkaline aqueous solution or helps its thawless material.As such compound; Can use habitual known polyester (methyl) acrylic ester, polyethers (methyl) acrylic ester, urethane (methyl) acrylic ester, carbonic ester (methyl) acrylic ester, epoxy (methyl) acrylic ester; Specifically, can enumerate out acrylic acid hydroxy alkyl ester classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate; The diacrylate class of glycol such as monoethylene glycol, methoxyl TEG, polyglycol, propylene glycol; N, N-DMAA, N hydroxymethyl acrylamide, N, acrylic amides such as N-dimethylaminopropyl acrylic amide; Acrylic acid N, N-dimethylamino ethyl ester, acrylic acid N, amino alkyl acrylates classes such as N-dimethylamino propyl ester; Polyvalent alcohol or multicomponent methacrylate classes such as their ethylene oxide adduct, propylene oxide adduct or 6-caprolactone addition product such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate; Multicomponent methacrylate classes such as the ethylene oxide adduct of phenoxy group acrylic ester, bisphenol a diacrylate and these phenol or propylene oxide adduct; The multicomponent methacrylate class of glycidol ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; Be not limited to above-claimed cpd, also can enumerate out with direct acroleic acid esterifications of polyvalent alcohol such as polyether glycol, PCDL, C-terminal polybutadiene, polyester polyols or by diisocyanate and carry out urethane acrylateization and the esters of acrylic acid that obtains and melamine acrylic ester and/or each methyl acrylic ester corresponding etc. with the aforesaid propylene acid esters.

And then, can enumerate the Epocryl that the reaction of polyfunctional epoxy resin such as the cresols varnish type epoxy resin of sening as an envoy to and acrylic acid forms; Further make epoxy urethane acrylate compound that the half urethane compound reaction of the diisocyanate such as hydroxy acrylate such as hydroxyl and pentaerythritol triacrylate and isophorone diisocyanate of this Epocryl forms etc.Such epoxy acrylate is that resin can improve photo-curable, and can not reduce dry to touch property.

The compounding amount that has the compound of a plurality of ethylenically unsaturated groups in such molecule be in the solid constituent of composition 1～70wt%, further be preferably 5～60wt%; Contain carboxyl photoresist and time spent with aforementioned, be suitably for respect to contain carboxyl photoresist 100 mass parts and be 5～100 mass parts, the ratio of 5～70 mass parts more preferably.During aforementioned compounding quantity not sufficient 5 mass parts, photo-curable reduces, and is difficult to develop through 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 alkaline aqueous solution, filming becomes fragile, so not preferred.

Hardening resin composition of the present invention can the compounding colorant.As colorant, can use redness, blueness, green, yellow etc. to habitually practise known colorant, can be in pigment, dyestuff, the pigment any.Be to have following colour index (C.I. specifically; The Society of Dyers and Colourists distribution) material of sequence number.But 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, azo lake system, benzimidazolone Xi 、 perylene system, pyrrolopyrrole diketone system, condensation azo system, anthraquinone system, quinacridone etc. are arranged, specifically can enumerate following colorant.

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.

Pyrrolopyrrole diketone 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; The compound that is classified into pigment (Pigment) can be enumerated out by pigment system; Specifically, can enumerate out following compound: 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 the metal replacement or not have substituted phthalocyanine compound.

Green colourant:

As green colourant, phthalocyanine system, anthraquinone Xi 、 perylene system are arranged equally, can use specifically 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 the metal replacement or not have substituted phthalocyanine compound.

Yellow colorants:

As yellow colorants, monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc. are arranged, can enumerate out following colorant specifically.

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.

Remove this,, can add purple, orange, colorant such as dark brown, black in order to adjust tone.

Concrete illustration has pigment violet 19; 23; 29; 32; 36; 38; 42; Solvent violet 13; 36; C.I. pigment orange 1; C.I. pigment orange 5; C.I. pigment orange 13; C.I. pigment orange 14; C.I. pigment orange 16; C.I. pigment orange 17; C.I. pigment orange 24; C.I. pigment orange 34; C.I. pigment orange 36; C.I. pigment orange 38; C.I. pigment orange 40; C.I. pigment orange 43; C.I. pigment orange 46; C.I. pigment orange 49; C.I. pigment orange 51; C.I. pigment orange 61; C.I. pigment orange 63; C.I. pigment orange 64; C.I. pigment orange 71; C.I. pigment orange 73; C.I. pigment brown 23; C.I. pigment brown 25; C.I. pigment black 1; C.I. pigment black 7 etc.

The not special restriction of the compounding ratio of aforementioned colorant, below the 5wt% in the solid constituent of composition, it is sufficient further being preferably 0.1～3wt%.

In order to improve light sensitivity, can use known habitual N-phenylglycine class, phenoxy acetic acids, sulfo-phenoxy acetic acids, thyroidan etc. in the light solidifying/heat solidifying resin composition of the present invention as chain-transferring agent.Enumerate the concrete example of chain-transferring agent, for example mercapto succinic acid, TGA, 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-butane mercaptan, butyl-3-mercaptopropionic acid ester, methyl-3-mercaptopropionic acid ester, 2; 2-(ethylenedioxy) diethyl alkanethiol, ethane mercaptan, 4-methylbenzene mercaptan, lauryl mercaptan, propane mercaptan, butane mercaptan, pentane mercaptan, 1-octane mercaptan, cyclopentane mercaptan, cyclohexane mercaptan, thioglycerol, 4,4-thiobis benzenethiol etc.

And then; 2-sulfydryl-4-butyrolactone (butanolide)), 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 heterogeneous ring compound with sulfydryl of performance chain-transferring agent effect, for example can enumerate sulfydryl-4-butyrolactone (another name:.

Particularly as heterogeneous ring compound chain-transferring agent, that have sulfydryl that does not diminish the development property of light solidifying/heat solidifying resin composition; Preferred mercaptobenzothiazoler, 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 use separately or make up and use more than 2 kinds.

From the purpose that improves insulating reliability, light solidifying/heat solidifying resin composition of the present invention can add hydrotalcite.As the commercially available article of hydrotalcite, can enumerate out ALCAMIZER, DHT-4A, Kyowaad 500, Kyowaad 1000 that Kyowa Chemical Industry Co., Ltd makes, the HT-1 of the STABIACE series that Sakai KCC makes, HT-7, HT-P etc.

Particularly preferably being mean grain size is the synthetic hydrotalcite class below the 2 μ m, and further preferred mean grain size is the synthetic hydrotalcite class below the 1 μ m.In addition, these hydrotalcites can directly use with hydrate, perhaps also can burn till the state use of back with acid anhydrides.

The compounding amount of hydrotalcite is preferably 0.1～30wt% of total composition.Be preferably 0.5～30wt%, the scope of 0.1～25wt% more preferably.When the compounding amount of hydrotalcite surpassed above-mentioned scope, the viscosity of composition and flexibility became too high, and printing reduction or solidfied material become fragile, so not preferred.On the other hand, during not enough 0.1wt%, the effect of electrode corrosion resistance is impaired, so not preferred.

The oxidation Once you begin of most macromolecular material; Oxidative degradation then takes place in succession chainly; Cause the raw-material function of macromolecule to reduce; Therefore, for anti-oxidation, can adding (1) in the light solidifying/heat solidifying resin composition of the present invention, to make the such free radical scavenger (radical scavenger) of the free radical ineffective treatment that produced and/or (2) make the peroxide breakdown that is produced be innoxious substance and the anti-oxidants such as peroxide decomposer that do not produce new free radical.

As the anti-oxidant of performance free radical scavenger effect, can enumerate for example quinhydrones, 4-tert-butyl catechol, 2-tertiary butylated hydroquinone, Hydroquinone monomethylether, 2,6-two-tert-butyl group-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 (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, 1,3; 5-three (3 ', 5 ' two-tertiary butyl-4-hydroxy benzyls)-guanamine, 4,6-(1H; 3H, 5H) quinone based compounds such as phenol system, methylnaphthoquinone (menaquinone), benzoquinones such as triketone, two (2; 2,6,6-tetramethyl-4-piperidyl)-amine compound such as sebacate, phenothiazine etc.

This free radical scavenger can be commercially available product, can enumerate for example ADK STAB (registered trademark) AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (being the ADEKA manufactured), IRGANOX (registered trademark) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (being BASF JAPAN manufactured) etc.

Anti-oxidant as the effect of performance peroxide decomposer; Concrete compound can be enumerated for example phosphorus series compound such as triphenyl phosphite; Pentaerythrite four lauryl thiopropionates, thiodipropionate dilauryl, 3, chalcogenide compounds such as 3 '-distearylthiodi-propionate etc.

This peroxide decomposer can be commercially available product; Can enumerate for example ADK STAB TPP (ADEKA manufactured), Mark AO-412S (Adeka Argus Chemical Co., Ltd. system), Sumilizer (registered trademark) TPS (sumitomo chemical company manufacturing) etc.

Above-mentioned anti-oxidant can use a kind or make up more than 2 kinds and to use separately.

Light solidifying/heat solidifying resin composition of the present invention can also use ultraviolet light absorber except using above-mentioned anti-oxidant.

As such ultraviolet light absorber, can enumerate out benzophenone derivates, benzoate derivatives, benzotriazole derivatives, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivates, Anthranilate derivant, dibenzoylmethane derivative etc.

As benzophenone derivates; Can enumerate out for example 2-hydroxyl-4-methoxyl-benzophenone, 2-hydroxyl-4-methoxy benzophenone, UV-531,2; 2 '-dihydroxy-4-methoxy benzophenone and 2,4 dihydroxyl benzophenone etc.

As benzoate derivatives; Can enumerate out for example salicylic acid 2-Octyl Nitrite, phenyl salicytate, p-t-butylphenyl 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.

As benzotriazole derivatives; Can enumerate out for example 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 '-two-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 pyrrolotriazine derivatives, can enumerate out for example hydroxyphenyltriazinuv, two ethyl hexyl oxy phenol methoxyphenyl triazines etc.

As ultraviolet light absorber; Commercially available article can be used, for example TINUVI PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (being BASF JAPAN manufactured) etc. can be enumerated out.

Aforementioned ultraviolet light absorber can use a kind or make up more than 2 kinds and to use separately, through using with antioxidant combination, and the stabilization of the shaping thing that can realize obtaining through light solidifying/heat solidifying resin composition of the present invention.

In order to improve this physical strength of filming etc., light solidifying/heat solidifying resin composition of the present invention is the compounding filler as required.As such filler, can use by known habitual inorganic filler and organic filler, particularly can preferably use barium sulphate, spherical silicon dioxide, Nuo Yibao (Neuburg) tripoli particle and talcum.And then, can use metal hydroxides such as titanium dioxide, metal oxide, hydrate of aluminium as the extender pigment filler in order to obtain the outward appearance and the anti-flammability of white.The compounding amount of filler is preferably below the 75wt% of total composition, more preferably the ratio of 0.1～60wt%.When the compounding amount of filler surpassed the 75wt% of total composition, the viscosity of insulation compsn uprised, and coating, formability reduce, and perhaps solidfied material becomes fragile, so not preferred.

And then for the modulation of the aforementioned synthetic and composition that contains the carboxyl photoresist or be used to be applied to the adjusting of the viscosity of substrate or carrier film, light solidifying/heat solidifying resin composition of the present invention can be with an organic solvent.

As such organic solvent, can enumerate out ketone, aromatic hydrocarbon based, gylcol ether, glycol ether acetate class, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.The ketone that MEK, cyclohexanone etc. more particularly, are arranged; Toluene, xylene, tetramethylbenzene etc. aromatic hydrocarbon based; Glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, BC, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, DPG Anaesthetie Ether, triethylene glycol list ethylether; Ester classes such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol butyl ether acetic acid esters, 2-hydroxy-methyl isobutyl acid; Alcohols such as ethanol, propyl alcohol, monoethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, petroleum naphtha, hydrotreated petroleum naphtha, solvent naphtha etc.Such organic solvent can use separately or use as the potpourri more than 2 kinds.

Light solidifying/heat solidifying resin composition of the present invention can be as required the further known habitual hot polymerization inhibitor of compounding; Known habitual tackifier such as fine particle silica, organobentonite, polynite; The foam-breaking agent and/or the levelling agent of silicone-based, fluorine system, macromolecular etc.; The silane coupling agent of imidazoles system, thiazole system, triazole system etc., anti-oxidant, the known habitual additive kind that rust preventive etc. are such.

For thermal polymerization or the polymerization by the time that prevents polymerizable compound, can use hot polymerization inhibitor.As hot polymerization inhibitor; For example can enumerate 4-metoxyphenol, quinhydrones, with the substituted quinhydrones of alkyl or aryl, tert-butyl catechol, pyrogallol, 2-dihydroxy benaophenonel, 4-methoxyl-2-dihydroxy benaophenonel, stannous chloride, phenothiazine, tetrachloroquinone, naphthylamines, betanaphthol, 2; 6-di-t-butyl-4-cresols, 2, the chelate of reactant, gaultherolin and phenothiazine, nitroso compound, nitroso compound and the A1 of 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), pyridine, nitrobenzene, dinitro benzene, picric acid, 4-toluidine, methylene blue, copper and organic sequestering agent etc.

Light solidifying/heat solidifying resin composition of the present invention is for example adjusted to the viscosity that is suitable for coating process with aforementioned organic solvent; The methods such as method, silk screen print method, curtain Tu Fa that are coated with through dip coating, flow coat method, rolling method, rod are applied on the base material; And under about 60～100 ℃ temperature, make organic solvent volatile dry contained in the composition (temporary transient dry), can form tack-free filming thus.In addition, after above-mentioned composition is applied on the carrier film and makes it dry state with film and reel, fit on the base material, thereby can form resin insulating barrier.Thereafter; Through contact (or noncontact mode); Utilize active energy beam optionally to make public across forming figuratum photomask; Perhaps carry out direct pattern exposure, use dilute alkaline aqueous solution (for example 0.3～3wt% aqueous sodium carbonate) that unexposed portion is developed, form corrosion-resisting pattern thus through the direct exposure machine of laser.And then; Make its heat curing through being heated to for example about 140～180 ℃ temperature; Make the aforementioned epoxy radicals that contains the carboxyl and the epoxidized vegetable oil of carboxy resin (perhaps under the situation that contains other Thermocurable compositions; Ring-type (sulphur) ether that also comprises other Thermocurable compositions) reaction, thus the cured coating film of each excellent such as thermotolerance, chemical proofing, anti-hydroscopicity, adaptation, electrical characteristics can be formed.

As above-mentioned base material; Except that the printed circuit board (PCB) that is pre-formed circuit, the flexible print wiring board; Can also use paper-phenolics, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth/nonwoven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthon-epoxy resin, use the copper clad laminate of all grades (FR-4 etc.) of fluorine resin/tygon/compound substances such as PPO/ cyanate, and Kapton, PET film, glass substrate, ceramic substrate, wafer board etc.

Be coated with the volatile dry that carries out after the light solidifying/heat solidifying resin composition of the present invention, can have used heated air circulation type drying oven, IR stove, heating plate, convection furnace etc. (use has the device that carries out the thermal source of air heat mode with steam to be made the method for the hot air convection contact in the dryer and blow to the mode on the support from nozzle) and carry out.

Behind such as previously discussed coating light solidifying/heat solidifying resin composition of the present invention and the volatile dry, make public (irradiation of active energy beam) that gained is filmed.The exposure portion of filming (through the part of active energy beam irradiation) solidifies.

Exposure machine as being used for the irradiation of above-mentioned active energy beam, can use direct drawing apparatus (for example directly using the direct drawing apparatus of laser of laser rendering image) through the cad data of computing machine, be equipped with metal halide lamp exposure machine, be equipped with (surpassing) high-pressure sodium lamp exposure machine, the exposure machine of mercury short-arc lamp is installed or has used the direct drawing apparatus of UV-lamps such as (surpassing) high-pressure sodium lamp.In addition, as active energy beam, be the laser of the scope of 350～410nm as long as use maximum wavelength, then gas laser, Solid State Laser all can.In addition, this exposure generally can be 5～800mJ/cm because of differences such as thickness ², be preferably 5～500mJ/cm ²Scope in.As above-mentioned direct drawing apparatus, can use for example Orbotech Japan Co., the device that Ltd. makes, the device of PENTAX manufactured etc. are as long as be that the device of the laser generation of 350～410nm then can use arbitrary device for making maximum wavelength.

As aforementioned developing method, can utilize infusion process, spray process, spray-on process, brushing method etc., as developer solution, can use alkaline aqueous solutions such as potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammoniacal liquor, amine.

Light solidifying/heat solidifying resin composition of the present invention is except with the aqueous method that is coated directly onto base material, can also solder resist be applied on the film of polyethylene terephthalate etc. and the form of the dry film of the dry and solder mask that forms is used to have in advance.Below illustrate the situation of light solidifying/heat solidifying resin composition of the present invention as dry film.

Dry film has the structure that the order lamination according to carrier film, solder mask and the strippable cover film that uses as required forms.Solder mask for for example the Photocurable resin composition of alkali-developable is applied on carrier film or the cover film and dry get layer.As long as after forming solder mask on the carrier film, cover film is laminated on it, perhaps, can obtain dry film forming solder mask on the cover film and this layered product being laminated on the carrier film.

As carrier film, use the thermoplastic films such as mylar of thick 2～150 μ m.

Solder mask forms as follows: through knife type coater, lip formula coating machine, comma coating machine, film coated machine etc., with the thickness of alkali-developable Photocurable resin composition with 10～150 μ m, evenly be applied on carrier film or the cover film and dry and form.

As cover film, can use polyethylene film, polypropylene film etc., preferable with the cover film that the bonding force of solder mask is littler than carrier film.

In order to use dry film on printed circuit board (PCB), to make diaphragm (permanent diaphragm), peel off cover film, overlapping solder mask and the base material that is formed with circuit use laminating machine that it is fitted, and form solder mask being formed with on the base material of circuit.Solder mask to forming likewise makes public, develops, is heating and curing with aforementioned, then can form cured coating film.Carrier film is peeled off before exposure or after the exposure and is got final product.

Embodiment

Below embodiment is shown and comparative example specifies the present invention, the present invention does not receive the qualification of following embodiment certainly.In addition, below, " part " and " % " all is quality criteria not having under the situation about specifying.

< containing the synthetic example 1 of carboxyl photoresist >

In TC acetic acid esters 600g, add orthoresol varnish type epoxy resin (big Japanese ink chemical industry strain formula meeting manufactured, EPICLONN-695,95 ℃ of softening points, epoxide equivalent 214, average sense radix 7.6) 1070g (diglycidyl radix (aromatic rings sum): 5.0 moles), acrylic acid 360g (5.0 moles) and quinhydrones 1.5g; Be heated to 100 ℃ and stirring, uniform dissolution.Then, add triphenylphosphine 4.3g, be heated to 110 ℃, react after 2 hours, be warming up to 120 ℃, further carry out reaction in 12 hours.In the reactant liquor of gained, add fragrant family hydrocarbon (Solvesso150) 415g, tetrabydrophthalic anhydride 456.0g (3.0 moles); Under 110 ℃, carry out reaction in 4 hours; After the cooling, obtain the resin solution of solid constituent acid number 89mgKOH/g, solid constituent 65%.This resin solution is called A-1.

< containing the synthetic example 2 of carboxyl photoresist >

In the beaker that possesses thermometer, stirring machine, tap funnel and reflux condenser; Add methyl methacrylate, Jia Jibingxisuanyizhi and methacrylic acid according to 1: 1: 2 ratio of molar ratio computing; And add dipropylene glycol monomethyl ether as solvent, as the AIBN of catalyzer; Stirring is 4 hours under nitrogen atmosphere, under 80 ℃, obtains resin solution.Cool off this resin solution; Use is as the methylnaphthohydroquinone of polymerization inhibitor, as the tetrabutyl phosphonium bromide phosphine of catalyzer; To the GMA of 20 moles of % of carboxyl addition reaction of above-mentioned resin, take out the cooling back under 95～105 ℃ of following conditions of 16 hours.The involatile composition that has the photoresist of ethylenic unsaturated bond and carboxyl when obtaining like this is 65%, the acid number of solid constituent is that 120mgKOH/g, Mw are about 20,000.Below, this resin solution is called A-2.

Embodiment 1～4 and comparative example 1～3

Various compositions shown in the below table 1 are carried out compounding according to the ratio shown in the table 1 (mass parts), and after the stirring machine ready-mixed, it is mixing to use three roller roller mills to carry out, and the modulation solder resist is used photosensitive polymer combination.

Table 1

Performance evaluation:

< storage stabilities under 20 ℃ >

The embodiment 1～4 of table 1, the resin combination of comparative example 1～3 were taken care of 3 months 20 ℃ dark place, measured the tackify rate after 3 months.Metewand is described below.

Zero: tackify rate 0%～100%.

△: tackify rate 100～200%.

*: the tackify rate is more than 200% or gelation.

< storage stabilities under 50 ℃ >

The embodiment 1～4 of table 1, the resin combination of comparative example 1～3 are taken care of 50 ℃ dark place, measured tackify rate through at present.The tackify rate surpasses at 200% o'clock and is judged as and can not uses, and measures the time in the time can not using.

< the righttest exposure >

After the circuit pattern substrate polishing grinding to the thick 35 μ m of copper, washing, drying, then, through the light solidifying/heat solidifying resin composition of silk screen print method whole coating previous embodiment and comparative example, drying is 60 minutes in 80 ℃ heated air circulation type drying oven.After the drying, use to carry the exposure device of high-pressure sodium lamp (short-arc lamp), (Kodak No.2) makes public through stage metraster, and (30 ℃, 0.2MPa, 1wt%Na will develop ₂CO ₃Be made as the righttest exposure when the pattern of residual stage metraster is 7 sections in the time of the WS) 60 seconds.

< development property >

Through silk screen print method, the light solidifying/heat solidifying resin composition of previous embodiment and comparative example is applied on the copper-clad base plate so that dried thickness is about 25 μ m, in 80 ℃ heated air circulation type drying oven, make its dry 30 minutes.After the drying, through 1wt%Na ₂CO ₃The WS develops, and measures up to the removed time of dry coating through stopwatch.

< dry to touch property >

The light solidifying/heat solidifying resin composition of previous embodiment and comparative example is applied on the figuratum copper clad laminate of formation through the whole face of serigraphy respectively, in 80 ℃ heated air circulation type drying oven, makes its dry 30 minutes, place cool to room temperature.The PET film is pressed on this substrate, then, estimates the subsides of film when peeling off the minus film and pay state.Determinating reference is described below.

Zero: during stripping film, do not have resistance fully, have vestige slightly but film.

△: during stripping film, resistance is arranged slightly, filming has vestige slightly.

*: during stripping film, resistance is arranged, filming has sharp trace.

< resolution >

After the circuit pattern substrate polishing grinding with live width/interval 300/300 μ m, the thick 35 μ m of copper; Washing, drying, then; Through the light solidifying/heat solidifying resin composition of silk screen print method coating previous embodiment and comparative example, in 80 ℃ heated air circulation type drying oven, make its dry 30 minutes.After the drying, use the exposure device that is equipped with high-pressure sodium lamp to make public.Exposing patterns uses spacer portion to describe the negative film of the line of 20/30/40/50/60/70/80/90/100 μ m.According to exposure is the righttest exposure irradiation active energy beam of photosensitive polymer combination.After the exposure, under the condition of expulsion pressure 0.2MPa with 30 ℃ 1wt%Na ₂CO ₃The WS carried out for 60 seconds and develops, through under 150 ℃, carrying out 60 minutes heat curing, the acquisition cured coating film.Use is adjusted into 200 times optical microscope and obtains the minimum residual wires of the solder resist of gained with the cured coating film of photosensitive polymer combination, with it as resolution.

Attribute testing:

Be applied on the figuratum copper clad laminate of formation through the whole face of composition of serigraphy with aforementioned each embodiment and comparative example, drying is 30 minutes under 80 ℃, places cool to room temperature.The exposure device that use is equipped with high-pressure sodium lamp (short-arc lamp) with the righttest exposure to this base plate exposure soldering-resistant pattern, under the condition of expulsion pressure 0.2MPa with 30 ℃ 1wt%Na ₂CO ₃The WS carried out for 60 seconds and develops, and obtained corrosion-resisting pattern.Use the UV furnace conveyor at accumulated exposure amount 1000mJ/cm ²Condition under this substrate carried out ultraviolet ray irradiation after, 150 ℃ of heating 60 minutes and solidifying down.Printed base plate (evaluation substrate) to gained is estimated characteristic as follows.

< anti-sweating heat performance >

The evaluation substrate that is coated with the rosin series solder flux is impregnated in the solder bath that is redefined for 260 ℃, behind modification alcohol washing solder flux, the expansion of visual valuation resist layer, peels off.Determinating reference is following.

Zero: though repeatedly more than 3 times 10 seconds dippings also unconfirmed to peeling off.

△: peel off slightly when flood 10 seconds more than 3 times repeatedly.

*: when flooding with interior 10 seconds for 3 times, resist layer has expansion, peels off.

< the gold-plated property of chemically-resistant >

Use electroless nickel bath and the chemical gilding of commercially available article to bathe, under the condition of nickel 0.5 μ m, golden 0.03 μ m, carry out plating, peel off through band and estimate resist layer and have or not to peel off and have or not infiltration, peel off through band then and estimate resist layer and have or not and peel off with plating.Determinating reference is following.

Zero: do not find to infiltrate, peel off.

△: confirm infiltration a little behind the plating, but band is not stripped from after peeling off.

*: find to have slightly infiltration behind the plating, also find after band is peeled off to peel off.

< alkali resistance >

At room temperature will estimate substrate and in the 10wt%NaOH WS, flood 30 minutes, the stripping of confirm infiltrating, filming and peel off through what band was peeled off.Determinating reference is described below.

Zero: no infiltration, stripping, peel off.

△: confirming has infiltration, stripping slightly or peels off.

*: confirm to more infiltration, stripping or peel off.

< electrode corrosion resistance (insulating reliability) >

The Alloy instead of Copper foil substrate uses the comb-type electrode pattern of μ m of live width/at interval=100/100; Make under these conditions and estimate substrate; This comb-type electrode is applied the bias voltage of DC30V under 85 ℃, the heating and moistening condition of 85%R.H., a situation arises to estimate dendrite after 500 hours.Determinating reference is described below.

Zero: the generation of dendrite is few.

*: the generation of dendrite is many.

< dry film making >

With the solder resist of embodiment 1,2 and comparative example 1 with photosensitive polymer combination respectively with MEK suitably after the dilution; Use applicator to be applied on the PET film (eastern Cao makes FB-50:16 μ m); So that dried thickness is 30 μ m, under 40～100 ℃, make its drying, obtain dry film.

<substrate manufacture >

After will being formed with the substrate polishing grinding of circuit; The dry film that uses vacuum laminator (name mechanism is made made MVLP-500) under pressurization degree: 0.8MPa, 70 ℃, 1 minute, the condition of vacuum tightness: 133.3Pa, said method to be made carries out heated lamination, and acquisition has the substrate (unexposed substrate) of unexposed solder mask.To the substrate of gained, likewise carry out the righttest exposure, development property, resolution, anti-sweating heat performance, anti-gold-plated property, alkali-proof each test with aforementioned evaluation method.

Evaluation result is shown in table 2.

Table 2

Result by shown in the above-mentioned table 2 can know, the excellent storage stability of 1 liquid type resin combination of the present invention, and anti-sweating heat performance, anti-gold-plated property, alkali resistance, electrode excellent corrosion resistance are useful as solder resist.With respect to this, do not use under the situation of comparative example 1 of Thermocurable composition, storage stability is no problem, but can not satisfy each characteristic.On the other hand, not that each characteristic is no problem under the situation of comparative example 2,3 of universal epoxy resin of plant origin epoxy compound using as the Thermocurable composition, but the remarkable variation of storage stability.

Claims (7)

1. a light solidifying/heat solidifying resin composition is characterized in that, it contains carboxy resin, Photoepolymerizationinitiater initiater and plant origin epoxy compound.

2. light solidifying/heat solidifying resin composition according to claim 1 is characterized in that, the aforementioned carboxy resin that contains is the carboxy resin that contains with photonasty group.

3. light solidifying/heat solidifying resin composition according to claim 1 is characterized in that, aforementioned plant origin epoxy compound is by any the constituting more than a kind or 2 kinds in epoxidised soybean oil, the epoxidation linseed oil.

4. according to each described light solidifying/heat solidifying resin composition in the claim 1 to 3, it is characterized in that it is can be through the solder resist of diluted alkaline property WS development.

5. the dry film of a photo-curable, it is applied to film and dry and obtain with each described light solidifying/heat solidifying resin composition in the aforementioned claim 1 to 3.

6. solidfied material, it obtains through following: make that each described light solidifying/heat solidifying resin composition photocuring obtains in the aforementioned claim 1 to 3; Perhaps this light solidifying/heat solidifying resin composition is applied to film and dry and obtain dry film, make this dry film photocuring and obtain.

7. printed circuit board (PCB), it has the cured film of following acquisition: make after each described light solidifying/heat solidifying resin composition photocuring becomes pattern-like in the aforementioned claim 1 to 3 heat curing and obtaining; Perhaps this light solidifying/heat solidifying resin composition is applied to film and dry and after obtaining dry film, making this dry film photocuring become pattern-like, heat curing and obtaining.