CN1680470A - Curable resin comosition and coating film thereof - Google Patents

Abstract

The present invention provides a cured resin composition having low hydrolyzability and halogen-free stable flame-resistance, excellent in solder heat-resistance, chemical resistance, adhesiveness, electric insulation and the like. The invention further provides a cured resin composition and a cured film thereof for a carrier tape and a flexible print circuit board, excellent in flexing resistance and causing little warpage after curing. The photosetting /thermosetting resin composition and the thermosetting composition are useful for a solder resist for print circuit boards, which are characterized in: containing a phosphate acidamine compound. Further, a cured film having the resin composition is also provided.

Description

Curable resin composition and cured coating film thereof

Technical field

The present invention relates to as the welding resistance printing ink of the manufacturing that is used for the encapsulation of the manufacturing of printed-wiring board (PWB) and tape carrier and useful not halogen-containing, curable resin composition with flame retardant resistance.In more detail, relate to as the welding resistance printing ink that is used for printed-wiring board (PWB), perhaps (belt engages automatically: Tape AutomatedBonding) as being used for TAB, CSP (chip size packages: Chip Size Package), Chip on Film) etc. (tape carrier encapsulation: semi-conductor carrier band that uses Tape Carrier Package) and COF (cover brilliant film: the welding resistance printing ink in and useful curable resin composition and cured coating film thereof to TCP, this resin combination is water-disintegrable low, at solder heat resistance, chemical resistance, sticking power, aspects such as electrical insulating property are good, and not halogen-containing, has stable flame retardant resistance.

Background technology

Usually, solder resist as printed-wiring board (PWB), from high precision, highdensity viewpoint, be extensive use of following solder resist: form image by developing after the uviolizing, the aqueous developable solder flux of after fixing (self solidifies) with the light and heat irradiation.Particularly, consider, use dilute alkaline aqueous solution just becoming main flow as the aqueous solder resist of the alkali developable of developing solution from the environmental problem aspect.

As this alkali developable solder resist, the solder resist composition for example be made up of photoresist, Photoepolymerizationinitiater initiater, thinner and epoxy compounds has been proposed, wherein photoresist is in the reaction product of phenolic epoxy compound and unsaturated monocarboxylic acid, the saturated or unsaturated multi-anhydride of addition and form (with reference to patent documentation 1).

The method of giving this solder resist composition flame retardant resistance generally has: the method for adding bromine compounds, adding phosphoric acid ester are as the method for fire retardant and the method for adding red phosphorus etc.But present situation is that in above-mentioned composition, even use brominated epoxy resin in the epoxy compounds that adds as the Thermocurable composition, the content of bromine is also lower, can not obtain sufficient flame retardant resistance.In addition, in the raw material of above-mentioned photoresist, use the method for the phenol aldehyde type epoxy resin of brominated phenols also to be considered, but have the problem that can not adapt with halogenization.

In addition, add the method for phosphoric acid ester, in alkali development treatment when printed-wiring board (PWB) is made and the electroplating processes etc., have the phosphoric acid ester hydrolysis, the problem that coating characteristics such as electrical insulating property and electrocorrosion are reduced.In addition, add the method for red phosphorus, have the bad order of the painted grade that red phosphorus causes and the problem that sensitivity reduces occurs, and the problem that when storage solder resist composition, is subjected to the restriction of fire service law etc.

In addition, when above-mentioned composition is used for tape carrier (tape carrier) and flexibility printed circuit board purposes, because flexibility is relatively poor, and the torsion resistance after solidifying is bigger, the problem that the reliability when appearance slight crack when existence causes being out of shape easily and component packages worsens.At these, the solder resist composition that proposition is made up of photoresist, described photoresist is in the reaction product of Bisphenol F (or A) type multi-group epoxy compound and unsaturated monocarboxylic acid, the addition acid anhydrides forms (with reference to patent documentation 2).

Thus, by choosing straight catenate polyfunctional epoxy resin as raw material, the torsion resistance after can improving flexibility and solidifying.In addition, also propose with the epoxy compounds that in main framing, contains bromine as the raw material combination thing.But present situation is that brominated amount is low, can not obtain sufficient flame retardant resistance.In addition, this flame-retardant composition exist can not with the non-halogen problem that adapts.

In addition, as light solidified/heat-curable composition not halogen-containing, that have flame retardant resistance, proposed to contain the composition of following resin compound: with the multi-group epoxy compound, after reacting with the such phosphorus compound of unsaturated monocarboxylic acid and diphenyl phosphonic acid, addition polyprotonic acid acid anhydrides forms resin compound (with reference to patent documentation 3).

But, multi-group epoxy compound and phosphorus compound are reacted formed resin, because the problems such as molecular weight of the phosphorus compound of introducing are difficult to make phosphorus content to uprise, existence can not obtain the problem of sufficient flame retardant resistance and have water-disintegrable problem.

In addition, Tape Automated Bonding) etc. (belt engages automatically: in the manufacturing of tape carrier (tape carrier) and flexibility printed circuit board at TAB, the spool of employing is arranged to the situation of spool (roller is to roller) as mode of movement, the mode of noncontact exposure is used in the irradiation of activation evergy line mostly under this situation.Therefore, the inhibition of the free radical reaction that oxygen causes the time can take place in exposure, particularly, the phenomenon that can cause the solidified nature reduction on easy affected solder resist surface, the result is, because this surface cure reduction causes anti-plating and chemical resistance to reduce, and then, become also that soldering-resistance layer breaks away from so bad reason after the electroplating processes.Therefore, use the thermohardening type solder resist.

As this thermohardening type welding resistance printing ink, have with Resins, epoxy and diprotic acid acid anhydrides epoxy resin solder mask ink composition (with reference to patent documentation 4) as essential composition, but adjusted to film when giving flexibility to formed, and the sticking power variation between the polyimide of base material has the problem of anti-plating, PCT (pressurecooker test steam pressure pot) patience and solder heat resistance reduction.In addition, also has the problem that is difficult to give the such flame retardant resistance of polyimide.

Patent documentation 1: the spy opens clear 61-243869 communique (claim)

Patent documentation 2: the spy opens flat 5-32746 communique (claim)

Patent documentation 3: the spy opens 2000-327742 communique (claim)

Patent documentation 4: special fair 5-75032 communique (claim)

Summary of the invention

Therefore, in order to solve the above-mentioned problems in the prior art, the present invention aims to provide a kind of water-disintegrable low, good at aspects such as solder heat resistance, chemical resistance, sticking power, electrical insulating properties, and not halogen-containing, as to have stable flame retardant resistance curable resin composition, further, provide a kind of be suitable for tape carrier (tapecarrier) and flexibility printed circuit board, flexibility excellence and solidify the less curable resin composition of back distortion.

In addition, another purpose of the present invention provides a kind of by with activation evergy line irradiation and/or heat above-mentioned curable resin composition, or only by heating, the cured coating film that makes its curing and obtain, this films water-disintegrable low, good at aspects such as solder heat resistance, chemical resistance, sticking power, electrical insulating properties, and not halogen-containing, have stable flame retardant resistance.

The present inventor has carried out conscientious research to achieve these goals, found that, its grown form is the curable resin composition that uses as the solder resist that printed-wiring board (PWB) is used, be the curable resin composition that contains the phosphoamide compound shown in the following general formula (I), it is water-disintegrable low, and is good at aspects such as solder heat resistance, chemical resistance, sticking power, electrical insulating properties, and it is not halogen-containing, have stable flame retardant resistance, so far, finish the present invention.

In the formula, R ¹, R ²Can be identical or different, the alkyl of expression hydrogen atom or carbonatoms 1～4.

As its a kind of concrete mode, aforementioned curable resin composition is the light solidified/hot curing resin composition that can develop by alkali aqueous solution, and this curable resin composition comprises:

(A) in a molecule, contain the carboxylic resin of the carboxyl more than 1,

(B) in a molecule, have the compound of the vinyl unsaturated link(age) more than 2,

(C) Photoepolymerizationinitiater initiater and

(D) in a molecule, have the oxyethane ring more than 1 and/or the compound of trimethylene oxide ring.

In addition, as other concrete mode, aforementioned curable resin composition is to contain

(A-2) have carboxyl more than 2 in 1 molecule, acid value is 20～120mgKOH/g, and second-order transition temperature is-60～40 ℃, and weight-average molecular weight is 5,000～100,000 carboxylic resin,

(D-1) in 1 molecule, have the oxyethane ring more than 2 multi-functional epoxy compounds and

(E) organic solvent

Heat-curing resin.

Just, find can make it water-disintegrable low by in these curable resin compositions, adding the phosphoamide compound shown in the above-mentioned general formula (I), good at aspects such as solder heat resistance, chemical resistance, sticking power, electrical insulating properties, and not halogen-containing, and give stable flame retardant resistance.Phosphoamide compound shown in the above-mentioned general formula (I) is compared with phosphoric acid ester etc., water-disintegrable remarkable reduction, and fusing point is higher, thus can not melt in the heat treated when printed-wiring board (PWB) is made, not halogen-containing, can give stable flame retardant resistance.

In addition, as alternate manner, can provide a kind of by with activation evergy line irradiation and/or heat above-mentioned curable resin composition, or only by heating, the cured coating film that makes its curing and obtain, this films water-disintegrable low, and is good at aspects such as solder heat resistance, chemical resistance, sticking power, electrical insulating properties, and not halogen-containing, have stable flame retardant resistance.

The curable resin composition of the application of the invention, the material that do not produce dioxin etc. and destroy environment, water-disintegrable low can be provided, good at aspects such as solder heat resistance, chemical resistance, sticking power, electrical insulating properties, and printed-wiring board (PWB) not halogen-containing, that have stable flame retardant resistance.Particularly, can provide have PCT patience, flexibility is good, the flexibility printed circuit board of the high reliability of the less cured article (filming) of distortion, be suitable in the flexible printed-wiring board (PWB)s such as the semi-conductor carrier band that in TAB, CSP, TCP, uses and COF.

Embodiment

Basic mode of the present invention is the curable resin composition that uses as the solder resist that printed-wiring board (PWB) is used, and is the curable resin composition that contains the phosphoamide compound shown in the following general formula (I).

In the formula, R ¹, R ²Can be identical or different, the alkyl of expression hydrogen atom or carbonatoms 1～4.

First mode as its curable resin composition is a kind of curable resin composition, it is characterized in that, this curable resin composition is the light solidified/hot curing resin composition that can develop by alkali aqueous solution, and this curable resin composition comprises:

(A) in a molecule, contain the carboxylic resin of the carboxyl more than 1,

(B) in a molecule, have the compound of the vinyl unsaturated link(age) more than 2,

(C) Photoepolymerizationinitiater initiater and

(D) in a molecule, have the oxyethane ring more than 1 and/or the compound of trimethylene oxide ring.

In addition, be a kind of curable resin composition as second mode of curable resin composition, it is characterized in that: this curable resin composition is to contain

(A-2) have carboxyl more than 2 in 1 molecule, acid value is 20～120mgKOH/g, and second-order transition temperature is-60～40 ℃, and weight-average molecular weight is 5,000～100,000 carboxylic resin,

(D-1) in 1 molecule, have the oxyethane ring more than 2 multi-functional epoxy compounds and

(E) organic solvent

Hot curing resin composition.

Below, each moiety of the curable resin composition that the solder resist used as printed-wiring board (PWB) of the present invention is used is described in detail.

At first; can pass through diphenylphosphine acyl chloride, diphenylphosphine acyl group bromide, two-3 as the phosphoamide compound shown in the following general formula (I) of feature of the present invention; 5-xylyl phosphoryl muriate etc. has the diaryl phosphoryl halogenide class of the alkyl of hydrogen atom or carbon atom 1～4, preferred diphenylphosphine acyl chloride; after dissolving in water-insoluble organic solvents such as ethylene dichloride with piperazine, add basic catalyst such as triethylamine and synthesize.For example, by diphenylphosphine acyl chloride and piperazine derivatives and the R of the above-mentioned general formula (I) that comes ¹And R ²Be the N of hydrogen atom, N '-two (two phenoxy group phosphoryls) piperazine contains the phosphorus atom of about 11 weight %, contains the nitrogen-atoms of the 5 weight % that have an appointment, and fusing point is about 186.7 ℃.There are four countries to change into the SP-703 that industrial makes as commercially available product.

R in the formula ¹, R ²Can be identical or different, the alkyl of expression hydrogen atom or carbonatoms 1～4.

Phosphoamide compound shown in the above-mentioned general formula (I) that so obtains is compared with phosphoric acid ester, have water-disintegrable extremely low, and the high feature of fusing point.In addition,, when burning, can form phosphine nitrile etc., compare, also have the feature that can further improve the flame retardant resistance effect with phosphoric acid ester owing to contain nitrogen in the molecule.

This phosphoamide compound is because water-disintegrable extremely low, so can not reduce the desired electrical insulating property of welding resistance printing ink that uses in the manufacturing of the manufacturing of printed-wiring board (PWB) and tape carrier encapsulation.In addition, this phosphoamide melting point compound is higher and be insoluble, can play the effect of organic filler so conclude it, and can not reduce flexibility.

In curable resin composition of the present invention, the addition of the phosphoamide compound shown in the above-mentioned general formula (I) is 5～50 weight %, is preferably 10～40 weight %, more preferably 20～40 weight %.During the addition less than 5 weight % of phosphoamide compound, the content of phosphorus atom is lower, though with other fire retardant coupling, can not obtain enough flame retardant resistances, so bad.On the other hand, when the addition of phosphoamide compound surpassed 50 weight %, coating strength reduced, so also not preferred.

Then, the curable resin to using in the curable resin composition of the present invention is described in detail.

First mode of curable resin composition of the present invention is the curable resin composition of the light solidified/Thermocurable that can develop by alkali aqueous solution, and this curable resin composition comprises:

(A) in a molecule, contain the carboxy resin that contains of carboxyl more than 1,

(B) in a molecule, have the compound of the vinyl unsaturated link(age) more than 2,

(C) Photoepolymerizationinitiater initiater and

(D) in a molecule, have the oxyethane ring more than 1 and/or the compound of trimethylene oxide ring.

As preferred mode is that the aforementioned resin (A) that contains carboxyl further contains the carboxyl photoresist for what have vinyl unsaturated link(age) more than 2 in (A-1) 1 molecule.

Contain carboxy resin (A) as what in above-mentioned a part, contain carboxyl more than 1, can use resin with carboxyl, can be itself to have the carboxylic photoresist (A-1) of vinyl unsaturated double-bond and do not contain any in the carboxylic resin (A) of vinyl unsaturated double-bond particularly, be not limited to specific material, but the resin of enumerating below preferred especially use the (in oligopolymer and the polymkeric substance any all can).

Can enumerate:

(1) by unsaturated carboxylic acid with have a carboxy resin that contains that the compound copolymerization of unsaturated double-bond obtains;

(2) in unsaturated carboxylic acid and the multipolymer of compound with unsaturated double-bond, what make that the vinyl unsaturated group obtains as the side chain addition contains the carboxyl photoresist;

(3) in the multipolymer of the compound that in a part, has epoxy group(ing) and a unsaturated double-bond and compound with unsaturated double-bond, make the reaction of itself and unsaturated monocarboxylic acid, the carboxylic photoresist that the anhydride reaction of the secondary hydroxyl of generation and saturated or unsaturated polyprotonic acid is obtained;

(4) in the multipolymer of acid anhydrides with unsaturated double-bond and other compound with unsaturated double-bond, the carboxylic photoresist that it is obtained with the compound reaction that has hydroxyl and unsaturated double-bond in a part;

(5) make the reaction of multi-group epoxy compound and unsaturated monocarboxylic acid, make the anhydride reaction of the hydroxyl of generation and saturated or unsaturated polyprotonic acid and the carboxylic photoresist that obtains;

(6) saturated or unsaturated multi-anhydride is reacted in containing the polymkeric substance of hydroxyl after, have the compound reaction of epoxy group(ing) and unsaturated double-bond in the carboxylic acid of generation and a part and the photoresist that contains hydroxyl and carboxyl that obtains;

(7) the multi-group epoxy compound, unsaturated monocarboxylic acid, and in a part, have at least can with the reaction product of the compound of 1 reactive group beyond the alcohols hydroxyl of 1 alcohols hydroxyl and epoxy reaction in, itself and saturated or unsaturated multi-anhydride are reacted and the carboxylic photoresist that obtains; And

(8) make the polyfunctional group oxetane compound reaction that has 2 trimethylene oxide rings in unsaturated monocarboxylic acid and a part at least, the primary hydroxyl in the modification oxetane resin that obtains reacts with saturated or unsaturated multi-anhydride and the carboxylic photoresist that obtains etc.

What wherein, preferably have 2 above photosensitivity unsaturated double-bonds in a part contains carboxyl photoresist, the carboxylic photoresist (A-1) of especially preferably aforementioned (5).

Further, in containing in the unsaturated photoresist of carboxyl of aforementioned (5), following resin can provide flexible printed-wiring board (PWB)s such as being suitable for the semi-conductor carrier band that uses and COF in TAB, CSP, TCP, and PCT patience, flexibility is good, solidify the less cured article of back distortion.

Just, the at least a kind of multi-group epoxy compound (a) in being selected from the compound shown in following general formula (II), following general formula (III) and the following logical formula V and the reactant of unsaturated monocarboxylic acid (b), make the reaction of itself and saturated and/or unsaturated multi-anhydride (c) and obtain contain carboxyl photoresist (A-1).

In the formula, R ³, R ⁴Expression hydrogen atom or methyl, R ⁵Expression hydrogen atom or glycidyl, n represents 1～50 value.

In the formula, M represents the group shown in the following general formula (IV), R ⁶The residue of expression aliphatics or aromatic series polyfunctional group carboxylic acid, m represents 1～50 value.

In the formula, R ⁷, R ⁸Expression divalent cyclohexane ring and/or phenyl ring, R ⁹, R ¹⁰Expression hydrogen atom or methyl, R ¹¹Expression hydrogen atom or glycidyl, k represents 0～25 value.

In the formula, X represents different divalent aromatic ring mutually with Y, and G represents glycidyl and/or hydrogen atom, and p represents 1～20 integer.

As above-mentioned unsaturated monocarboxylic acid (b), except vinylformic acid, methacrylic acid, TRANSCINNAMIC ACID, Ba Dousuan, Sorbic Acid, the alpha-cyano TRANSCINNAMIC ACID, beyond β-styrene acrylic etc., can also enumerate (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, (methyl) vinylformic acid phenyl glycidyl ester, the unsaturated dicarboxylic acid anhydride affixture of hydroxy acryl acid esters such as (methyl) vinylformic acid caprolactone affixture etc.In unsaturated monocarboxylic acid (b), particularly preferably be vinylformic acid and methacrylic acid.These unsaturated monocarboxylic acids can individually or make up more than 2 kinds and use.

In addition, at this moment said " (methyl) acrylate " is the term of the general name of expression acrylate and methacrylic ester, and other similar phraseology also is same.

With respect to the aforementioned multi-group epoxy compounds' of per 1.0 equivalents (a) epoxy group(ing), the addition amount of these unsaturated monocarboxylic acids (b) is 0.8～1.3 equivalent, is preferably 0.95～1.05 equivalent.When addition quantity not sufficient 0.8 equivalent of unsaturated monocarboxylic acid (b), unreacted epoxy groups and the carboxyl reaction that comes from the saturated and/or unsaturated multi-anhydride (c) of addition after this, storage stability is reduced, become the reason that causes gelation, therefore not preferred.On the other hand, when the addition amount surpassed 1.3 equivalents, the stink that is caused by unsaturated monocarboxylic acid smartened, and excessive unsaturated monocarboxylic acid gasifies when thermofixation, and corrosion Copper Foil etc. are therefore not preferred.

In addition, as aforementioned saturated and/or unsaturated multi-anhydride (c), can enumerate methyltetrahydro Tetra hydro Phthalic anhydride, tetrahydronaphthalic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, norbornene dicarboxylic anhydride, 3, ester ring type dibasic acid anhydrides such as 6-nadic anhydride, methyl nadic anhydride, tetrabromophthalic anhydride; Aliphatics or aromatic acid or tricarboxylic anhydrides such as succinyl oxide, maleic anhydride, itaconic anhydride, octenyl succinic acid anhydride, five (dodecenyl succinic) succinyl oxide, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride; Perhaps aliphatics or aromatic tetracarboxylic acid's dianhydrides such as biphenyl tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, fourth tetracarboxylic dianhydride, pentamethylene tetracarboxylic dianhydride, pyromellitic acid acid anhydride, benzophenone tetracarboxylic dianhydride, it can individually or make up more than 2 kinds and use.Wherein preferred especially ester ring type dibasic acid anhydride.

The acid value that the consumption of these saturated and/or unsaturated multi-anhydrides (c) preferably can make the carboxylic photoresist (A-1) that obtains is at 50～200mgKOH/g, preferably in the scope at 50～120mgKOH/g.When the not enough 50mgKOH/g of the acid value of carboxylic photoresist (A-1), the solvability variation in alkali aqueous solution, filming of formation is difficult to develop.On the other hand, when surpassing 200mgKOH/g,, all will expose to the surface of exposure portion regardless of conditions of exposure always, therefore not preferred.

Multi-group epoxy compound (a) as the raw material of above-mentioned carboxylic photoresist (A-1) is described.

Epoxy compounds shown in the aforementioned formula (II) is a kind of with the R in the general formula (II) ⁵To be 1～50 Bisphenol F type or bisphenol A-type 2 functional group's epoxy compoundss after the dissolving, react and the bis-phenol skeleton resin of polyfunctional groupization by making itself and epoxyhalopropane described later and alkali metal hydroxide in non-proton property polar solvents such as methyl-sulphoxide etc. the value that all is hydrogen atom, n.

When the n value less than 1 in the general formula (II), film-forming properties when touch dry, dry film and anti-crackle reduction, therefore not preferred.On the other hand, when n surpassed 50, the development reduction can not get resolving power, and is therefore also not preferred.

As aforementioned epoxyhalopropane, for example can use epoxy chloropropane, epoxy bromopropane, epoxy iodopropane, β-Jia Jihuanyanglvbingwan, Beta-methyl epoxy bromopropane, Beta-methyl epoxy iodopropane etc.In addition, the addition amount of epoxyhalopropane is preferably on average more than 50%, more preferably more than 80%.When the addition quantity not sufficient 50% of epoxyhalopropane, then when sensitization, be difficult to obtain anti-development, and water resisting property reduces also, therefore not preferred.

In addition,, can use caustic soda, Ke Xingjia, lithium hydroxide, calcium hydroxide etc., preferred especially caustic soda as alkali metal hydroxide.Wish epoxidised alcohols hydroxyl in the linear epoxy compounds with respect to the aforementioned terminal epoxy groups of 1mol, the consumption of this alkali metal hydroxide is preferably 0.5～2mol.

The temperature of the addition reaction of above-mentioned epoxyhalopropane is preferably 20～100 ℃.If the temperature deficiency of addition reaction then reacts slack-off for 20 ℃, the reaction needed long period, on the other hand,, temperature of reaction then causes more side reaction if surpassing 100 ℃, therefore not preferred.

Multi-group epoxy compound shown in the aforementioned formula (III) be by, with bisphenol A-type and/or Bisphenol F type 2 functional group's epoxy compoundss with (d) have the compound of at least 2 carboxyls as raw material in a part, use known as described later esterifying catalyst, make its alternately polymerization and obtain the linear epoxy compounds of terminal epoxy groups, make the multi-group epoxy compound (a) shown in itself and the aforementioned formula (II) similarly, be dissolved in the non-proton property polar solvent such as methyl-sulphoxide, with epoxyhalopropane and alkali metal hydroxide reaction and polyfunctional groupization.

During the value less than 1 of the m of general formula (III), film-forming properties when touch dry, dry film and anti-crackle reduction, therefore not preferred.On the other hand, when m surpassed 50, the development reduction can not get resolving power, and is therefore also not preferred.In addition, the addition amount of epoxyhalopropane is preferably on average more than 50%, more preferably more than 80%.When the addition quantity not sufficient 50% of epoxyhalopropane, then when sensitization, be difficult to obtain anti-development, and water resisting property reduces also, therefore not preferred.

As the above-mentioned compound (d) that in a part, has at least 2 carboxyls, for example can enumerate, 1, the 4-cyclohexyl dicarboxylic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, the hexahydro-m-phthalic acid, hexahydroterephthalic acid, phthalic acid, m-phthalic acid, terephthalic acid, succsinic acid, hexanodioic acid, muconic acid, suberic acid, sebacic acid, the adduct of 2-hydroxy-2-methyl succsinic acid and Tetra hydro Phthalic anhydride etc., from ultraviolet perviousness and the angle of paying flexibility, preferred especially 1, the 4-cyclohexyl dicarboxylic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, the hexahydro-m-phthalic acid, hexahydroterephthalic acid, hexanodioic acid, muconic acid, suberic acid, the dicarboxylic acid compound of aliphatics such as sebacic acid or ester ring type.It can individually or make up more than 2 kinds and use.

In addition, as aforementioned esterifying catalyst, can enumerate the phosphine class that can make epoxy group(ing) and carboxyl quantitative reaction, alkali metal compound, amine etc.Specifically can enumerate the phosphine classes such as salt of trialkyls such as tributylphosphine, triphenylphosphine or triaryl phosphine or itself and oxide compound; Alkali-metal oxyhydroxide such as sodium, lithium, potassium, halogenide, alkoxide, acid amides etc.; Trolamine, N, aliphatics such as N-lupetazin, triethylamine, three n-propyl amine, vulkacit H, pyridine, tetramethylammonium bromide or aromatic primary, second month in a season, uncle, quaternary ammonium etc., it can individually or make up more than 2 kinds and use.

With respect to the epoxy group(ing) of 1mol (1 equivalent) bisphenol A-type and/or Bisphenol F type 2 functional group's epoxy compoundss, these catalyst consumption are preferably the ratio of 0.1～25mol%, further the ratio of preferred 0.5～20mol%, the more preferably ratio of 1～15mol%.Reason is, when catalyst consumption is less than 0.1mol%, needs the certain reaction time, and is therefore uneconomical, on the other hand, when surpassing 25mol%, is difficult to control because reaction is too fast on the contrary, so not preferred.

Epoxy compounds shown in the aforementioned formula (V) be by, to have two functional group's phenolic compound of 2 phenols hydroxyls as raw material in the aromatic epoxy compound (hereinafter referred to as two functional group's aromatic epoxy compounds) that has 2 glycidyls in a part and a part, use known as described later catalyst for etherification, in solvent or in the presence of solvent-free, make its alternately polymerization and obtain the linear epoxy compounds of terminal epoxy groups, make the multi-group epoxy compound (a) shown in itself and the aforementioned formula (II) similarly, be dissolved in the non-proton property polar solvent such as methyl-sulphoxide, with epoxyhalopropane and alkali metal hydroxide reaction and polyfunctional groupization.

As two functional group's aromatic epoxy compounds of the raw material of aforementioned formula (V), can use in xenol type diglycidylether shown in following formula (VI)～(IX), di-cresylol type diglycidylether, bisphenol type diglycidylether, naphthalene type diglycidylether etc. two functional group's aromatic epoxy compounds of at least a kind with aromatic ring.By with this two functional group's aromatic epoxy compounds as with the alternating copolymer of two functional group's aromatic alcohols in a side monomer component, can obtain the good epoxy compounds in aspect such as intensity, thermotolerance, electrical insulating property at cured article.

In the formula, R ¹², R ¹³, R ¹⁴, R ¹⁵Can be identical or different, expression hydrogen atom or carbonatoms are 1～4 alkyl, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹Can be identical or different, the alkyl or the halogen atom of expression hydrogen atom, carbonatoms 1～4, R ²⁰, R ²¹Can be identical or different, expression hydrogen atom, methyl or halogenated methyl.

As aforementioned xenol type, di-cresylol type, bisphenol type or naphthalene type diglycidylether, for example can use, by the product that diphenol compound, di-cresylol compound, bisphenol cpd or dihydroxy naphthlene and epichlorohydrin reaction are made.In addition, also can use commercially available epoxy compounds,, can enumerate Yuka Sell Epoxy Co., the trade(brand)name " EPIKOTE YL-6056 " that Ltd. (oiling シ エ Le エ Port キ シ (strain)) makes etc. for example as xenol type diglycidylether; As di-cresylol type diglycidylether, can enumerate Yuka Sell EpoxyCo., the trade(brand)name " EPIKOTE YX-4000 " that Ltd. makes etc.; As the bisphenol type diglycidylether, can enumerate bisphenol type epoxy compounds such as trade(brand)name " ARALDITE# 260 " that Asahi-Ciba Limited makes, " ARALDITE# 6071 ", or the trade(brand)name Bisphenol F type epoxy compoundss such as " EPICLON 830S " of Dainippon Ink. ﹠ Chemicals Inc's manufacturing, or the trade(brand)name bisphenol S type epoxy compoundss such as " EPICLON EXA1514 " of Dainippon Ink. ﹠ Chemicals Inc's manufacturing; As naphthalene type diglycidylether, can enumerate the trade(brand)name " EPICLON HP-4032 (D) " of Dainippon Ink. ﹠ Chemicals Inc's manufacturing etc., it can individually or make up more than 2 kinds and use.

As two functional group's phenolic compound of the raw material of aforementioned formula (V), it has feature in configuration aspects, in order to improve thermotolerance, can use the material that contains aromatic nucleus, has symmetrical structure or rigid structure.As this compound, for example can enumerate 1,4-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, 2,7-dihydroxy naphthlene, 2, dihydroxy naphthlene derivatives such as 8-dihydroxy naphthlene, 2,2 '-biphenol derivatives such as di-cresylol, xenol, dihydroxyphenyl propane, Bisphenol F, bisphenol S, alkyl replace bisphenol derivatives such as bis-phenol, hydroquinone derivatives such as quinhydrones, toluhydroquinone, Trimethylhydroquinone etc., it can individually or make up more than 2 kinds and use.

As the catalyst for etherification that in the reaction of two functional group's aromatic epoxy compounds and two functional group's phenolic compound, uses, preferred phosphine class, alkali metal compound, the amine that can make glycidyl and phenolic hydroxyl group quantitative reaction that use either alone or in combination.Catalyzer beyond these is because its gelation with the alcohols hydroxyl reaction that generates in the reaction of glycidyl and phenolic hydroxyl group is therefore not preferred.As the phosphine class, can enumerate salt of trialkyls such as tributylphosphine, triphenylphosphine or triaryl phosphine or itself and oxide compound etc.As alkali metal compound, can enumerate alkali-metal oxyhydroxide such as sodium, lithium, potassium, halogenide, alkoxide, acid amides etc., it can individually or make up more than 2 kinds and use.As amine, can enumerate aliphatics or aromatic primary, second month in a season, uncle, quaternary ammonium etc., it can individually or make up more than 2 kinds and use.As the concrete example of amine, can enumerate trolamine, N, N-lupetazin, triethylamine, three n-propyl amine, vulkacit H, pyridine, tetramethylammonium bromide etc.

With respect to add-on is two functional group's aromatic epoxy compounds and two functional group's phenolic compound of 100 weight parts, and these catalyst for etherification are at 0.001～1 weight part, preferably use in the scope of 0.01～1 weight part.Reason is, when catalyst consumption is less than 0.001 weight part, needs the certain reaction time, and is therefore uneconomical, on the other hand, when surpassing 1 weight part, is difficult to control because reaction is too fast on the contrary, so not preferred.In the presence of this catalyzer, the reaction of two functional group's aromatic epoxy resin compounds and two functional group's phenolic compound preferably in inert gas or in the air, in the presence of aforementioned catalyzer, makes its reaction in about 130～180 ℃ temperature range.

As the compound (B) that in first mode of aforementioned curable resin composition, uses, in a part, have the vinyl unsaturated link(age) more than 2, can enumerate the esters of acrylic acid that for example 2-hydroxy ethyl methacrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate etc. contain hydroxyl; Water miscible esters of acrylic acid such as polyethyleneglycol diacrylate, polypropyleneglycol diacrylate; Multi-group alcohols' such as Viscoat 295, tetramethylol methane tetraacrylate, dipentaerythritol acrylate polyfunctional group polyester acrylate class; The ethylene oxide adduct of multi-group alcohol such as TriMethylolPropane(TMP), Hydrogenated Bisphenol A or polyfunctional group phenol such as dihydroxyphenyl propane, xenol, the esters of acrylic acid of propylene oxide adduct; Polyfunctional group or simple function group urethane acrylate as the isocyanate-modified thing of the above-mentioned acrylate that contains hydroxyl; Epoxy acrylate class as the vinylformic acid affixture of bisphenol A diglycidyl ether, Hydrogenated Bisphenol A diglycidylether or phenol type novolac epoxy, and with the corresponding methyl acrylic ester of aforesaid propylene esters of gallic acid, they can individually or will be used in combination more than 2 kinds.Wherein, polyfunctional group (methyl) acrylic compound that preferably in 1 molecule, has (methyl) acryloxy more than 2.

As the Photoepolymerizationinitiater initiater (C) that in first mode of aforementioned curable resin composition, uses, can enumerate for example st-yrax and st-yrax alkyl ethers such as st-yrax, st-yrax methyl ether, st-yrax ethyl ether, benzoin isobutyl propyl group ether; Methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1, acetophenones such as 1-dichloroacetophenone; 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl-third-1-ketone, 2-benzyl-2-dimethylin-1-(4-morpholinyl phenyl)-Ding-1-ketone, N, amido acetophenones such as N dimethylamine benzoylformaldoxime; Anthraquinone classes such as 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthene ketones such as 4-di-isopropyl thioxanthone; Ketal classes such as methyl phenyl ketone dimethyl ketal, benzyl dimethyl ketal; Benzophenone, 4, benzophenone or xanthone classes such as 4 '-two (diethylin) benzophenone; 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.

These known Photoepolymerizationinitiater initiaters (C) commonly used can use or use the above mixture of 2 classes separately, in addition, can also add N, N dimethylamine yl benzoic acid ethyl ester, N, light-initiated auxiliary agents such as tertiary amines such as N dimethylamine yl benzoic acid isopentyl ester, amyl group-4-dimethylin benzoic ether, triethylamine, trolamine.

In addition, in order to promote photoresponse, can also be added on the visible light zone has CGI-784 cyclopentadiene titanium compounds such as (Ciba Specialty Chemicals Ltd. manufacturings) of absorption etc.

Wherein, particularly preferred Photoepolymerizationinitiater initiater (C) is 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl-third-1-ketone, 2-benzyl-2-dimethylin-1-(4-morpholinyl phenyl)-Ding-1-ketone etc.; but be not particularly limited in these compounds; so long as make the material of unsaturated group radical polymerization such as (methyl) acryl in UV-light or visible light zone absorb light; just be not limited to Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, they can individually or make up multiple use.

With respect to total amount is that 100 weight parts are (as solid state component, down with) aforementioned carboxylic resin (A) and/or carboxylic photoresist (A-1) and the aforementioned compound (B) that in a part, has 2 above vinyl unsaturated link(age)s, the consumption of aforementioned lights polymerization starter (C) when auxiliary agent (use light-initiated be their total amount) preferably 0.1～25 weight part, be preferably the ratio of 0.5～20 weight part.The addition of Photoepolymerizationinitiater initiater (C) even the irradiation of activation evergy line can not be solidified, perhaps must increase irradiation time, thereby be difficult to obtain the suitable rerum natura of filming during less than above-mentioned scope.On the other hand, even add the above Photoepolymerizationinitiater initiater (C) of above-mentioned scope, light solidified can not change yet, and is not preferred at economic aspect.

As the compound (D) that in first mode of aforementioned curable resin composition, uses, in a part, have 1 above oxyethane ring and/or trimethylene oxide ring, can be set forth in the multi-group epoxy compound (D-1) who has 2 above oxyethane rings in a part, in a part, have the multi-group epoxy compound (D-2) of the trimethylene oxide ring more than 2 and in a part, have the oxyethane ring and each compound (D-3) more than 1 of trimethylene oxide ring.

As multi-group epoxy compound (D-1), (for example for example enumerate phenol aldehyde type epoxy resin, under acid catalyst, make phenols such as phenol, cresols, halogenated phenol, alkylphenol and formaldehyde reaction obtain the resol class, make the reaction of this resol class and epoxy chloropropane and/or methyl epichlorohydrin and the product that obtains, EOCN-103, the EOCN-104S, EOCN-1020, EOCN-1027, EPPN-201, the BREN-S that have Nippon Kayaku K. K to make as commercially available product; DEN-431, DEN-438 that Dow Chemical makes; N-730, the N-770 that Dainippon Ink. ﹠ Chemicals Inc makes, N-865, N-665, N-673, N-695, VH-4150 etc.), bisphenol A type epoxy resin (for example, the product that the reaction of bisphenols such as dihydroxyphenyl propane, tetrabromo-bisphenol and epoxy chloropropane and/or methyl epichlorohydrin is obtained, as commercially available product Yuka Sell Epoxy Co. is arranged, EPIKOTE 1004, EPIKOTE 1002 that Ltd. makes; The DER-330 that Dow Chemical makes, DER-337 etc.), tris-phenol type Resins, epoxy (for example, make tris-phenol, three cresols methane etc. react the product that obtains with epoxy chloropropane and/or methyl epichlorohydrin, the EPPN-501 that Nippon Kayaku K. K's manufacturing is arranged as commercially available product, EPPN-502 etc.), three (2, the 3-epoxypropyl) chlorinated isocyanurates, the biphenol diglycidylether, and other alicyclic epoxy resins, contain amino Resins, epoxy, copoly type Resins, epoxy, Cardo type Resins, epoxy, known Resins, epoxy commonly used such as calixarene (calyx arene) type Resins, epoxy, they can individually or make up more than 2 kinds and use.

The polyfunctional group oxetane compound (D-2) that uses in first mode of aforementioned curable resin composition for example, can be a raw material with 3-ethyl-trimethylene oxide alcohols such as 3-methylol trimethylene oxide, obtains by etherificate, esterification.Particularly, can enumerate 1,4-two { [(3-ethyl-3-oxetanyl) methoxyl group] methyl } benzene, (Toagosei Co., Ltd makes 3-ethyl-3-methylol trimethylene oxide, trade(brand)name OXT-101), (Toagosei Co., Ltd makes 3-ethyl-3-(phenoxymethyl) trimethylene oxide, trade(brand)name OXT-211), (Toagosei Co., Ltd makes 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide, trade(brand)name OXT-212), 1, (Toagosei Co., Ltd makes 4-two { [(3-ethyl-3-oxetanyl) methoxyl group] methyl } benzene, trade(brand)name OXT-121), two (3-ethyl-3-trimethylene oxide ylmethyl) ether (Toagosei Co., Ltd makes, trade(brand)name OXT-221) etc.In addition, can also enumerate phenol phenol aldehyde type oxetane compound etc.

These polyfunctional group oxetane compounds (D-2) can individually or make up more than 2 kinds and use.

As in first mode of aforementioned curable resin composition, use, in a part, have each compound (D-3) more than 1 of oxyethane ring and trimethylene oxide ring, for example, can enumerate the compound that etherificates such as trimethylene oxide alcohols such as 3-ethyl-3-methylol trimethylene oxide and Racemic glycidol are formed, and these compounds are further added compound that polycarboxylic acid, esterification form etc.

Carboxyl with respect to the aforementioned carboxylic resin of 1 equivalent (A), these additions that have the compound (D) of 1 above oxyethane ring and/or trimethylene oxide ring in a part are 0.6～2.0 equivalent, and properties such as this anti-plating at cured coating film, solder heat resistance are preferred.When above-mentioned addition less than 0.6 equivalent, so the alkali resistance of cured article and anti-plating reduction be not preferred.On the other hand, when surpassing 2.0 equivalents, have the oxyethane ring more than 1 and/or the compound (D) of trimethylene oxide ring as unreacted reactant in residual aforementioned a part and can cause reductions such as thermotolerance, so not preferred.

Below, second mode of curable resin composition of the present invention is to contain:

(A-2) to have carboxyl, acid value more than 2 in a part be 20～120mgKOH/g, second-order transition temperature for-60～40 ℃ and weight-average molecular weight are 5,000～100,000 carboxylic resin,

(D-1) in a part, have the oxyethane ring more than 2 the multi-group epoxy compound and

(E) organic solvent

The curable resin composition of Thermocurable, be the curable resin that further contains (F) sulfhydryl compound as preferred mode.

Above-mentioned carboxyl, the acid value that in a part, has more than 2 be 20～120mgKOH/g, second-order transition temperature for-60～40 ℃ and weight-average molecular weight be 5,000～100,000 carboxylic resin (A-2), as long as its acid value, second-order transition temperature and weight-average molecular weight just can be used known carboxylic resin commonly used in above-mentioned scope.Have as particularly preferred, with the compound that in a part, contains 1 polymerizability unsaturated link(age) and 1 carboxyl copolymer resins as essential monomer component.Can enumerate vinylformic acid as the above-mentioned compound that in a part, has 1 polymerizability unsaturated link(age) and 1 carboxyl, methacrylic acid and list (the 2-acryloxy ethyl) succsinic acid that the addition multi-anhydride forms in containing (methyl) acrylate of hydroxyl, single (2-acryloxy ethyl) phthalic acid, single (2-acryloxy ethyl) hexahydrophthalic acid, single (2-acryloxy propyl group) succsinic acid, single (2-acryloxy propyl group) phthalic acid, single (2-acryloxy propyl group) hexahydrophthalic acid, single (2-methacryloxyethyl) succsinic acid, single (2-methacryloxyethyl) phthalic acid, single (2-methacryloxyethyl) hexahydrophthalic acid, single (2-methacryloxypropyl) succsinic acid, single (2-methacryloxypropyl) phthalic acid, single (2-methacryloxypropyl) hexahydrophthalic acid etc.Wherein, water-disintegrable low because acrylic or methacrylic is sour, thermostability is also excellent, so preferred especially.These compounds can individually or make up to mix more than 2 kinds and use.In addition, with (methyl) described later acrylic ester copolymer the time, these compounds that have 1 polymerizability unsaturated link(age) and 1 carboxyl in 1 molecule are containing ratio in the resin of carboxyl, and must to make acid value be 20～120mgKOH/g.When acid value deficiency 20mgKOH/g, cross-linking density step-down, reductions such as thermotolerance, solvent resistance.Otherwise when acid value surpassed 120mgKOH/g, the warpage that the cure shrinkage in the time of can producing thermofixation causes increased, and the problems such as reactive force grow when crooked.

In addition, as with the aforementioned polymerizable monomer that in a part, has the compound copolymerization of 1 polymerizability unsaturated link(age) and 1 carboxyl, can use known polymerizable monomer commonly used, but from glass transition point that reduces copolymer resins and the purpose that improves anti-plating, preferred (methyl) acrylate of alkyl with carbonatoms 6～21, aryl or aralkyl that adds is as the comonomer composition.As concrete example, can enumerate the just own ester of vinylformic acid, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, the different boryl ester of vinylformic acid, isodecyl acrylate, vinylformic acid dodecyl ester, vinylformic acid Octadecane base ester and their methacrylic ester etc.Wherein, from the hydrophobic property aspect, preferred especially 2-ethylhexyl acrylate, 2-ethylhexyl methacrylic ester, vinylformic acid dodecyl ester, methacrylic acid dodecyl ester, by using these materials can be prevented electroplate liquid the overlay film that forms is soaked into, prevents the effect that hot water floats, peels off when cleaning, improve anti-plating.In addition, also can use the methyl acrylate that when high temperature such as electric welding, is difficult to discharge thermolysis gas or methyl methacrylate as the 3rd comonomer composition as required.In addition, (methyl) acrylate with alkyl of carbonatoms 2～5 is understood thermolysis and is produced (methyl) vinylformic acid and olefin gas, and becomes the expansible reason, so not preferred as comonomer.

With (methyl) acrylate of the aforementioned alkyl that in a part, has the compound of 1 polymerizability unsaturated link(age) and 1 carboxyl and have carbonatoms 6～21, aryl or aralkyl glass transition point (Tg) as the copolymer resins (carboxylic resin) of essential composition, can form the Tg of polymkeric substance and the part by weight of each composition according to the independent polymerization of each monomer, try to achieve by following formula (1) is approximate.Determine that the monomer composition so that Tg is-60～40 ℃, is preferably-40～20 ℃ especially.

1/Tg＝W ₁/Tg ₁+W ₂/Tg ₂+...+W _n/Tg _n???...(1)

In the formula, Tg represents the glass transition point (K) of multipolymer, Tg ₁, Tg ₂..., Tg _nThe glass transition point (K) of representing the polymkeric substance that each composition forms separately.In addition, W ₁, W ₂..., W _nWeight fraction (the W that represents each composition ₁+ W ₂+ ...+W _n=1).

The glass transition point of the carboxylic resin (A-2) that so obtains, when surpassing 40 ℃, the distortion during the thermofixation postcooling increases, and on the other hand, when being lower than-60 ℃, the hardness of filming after the thermofixation reduces, so not preferred.

In addition, the weight-average molecular weight of aforementioned carboxylic resin (A-2) is preferably 5,000～100, in 000 the scope.When weight-average molecular weight less than 5,000 o'clock, be difficult to make copolymer resins, stabilized resins can not be provided.In addition, because the carboxyl number of per molecule reduces, can not obtain good coating property after the thermofixation.On the other hand,, when being printed onto resin combination on the base material, can producing seepage and peel off with version when surpassing at 100,000 o'clock, the transfer printing variation, the coating property after operability and the thermofixation also reduces.

As the multi-group epoxy compound (D-1) who in second mode of aforementioned curable resin composition, uses, in a part, have the oxyethane ring more than 2, can use the identical material of polyfunctional compound (D-1) shown in first mode with aforementioned curable resin composition.

Particularly, can be with the Racemic glycidol ethers of the phenol aldehyde type of bisphenol A-type, Hydrogenated Bisphenol A type, Bisphenol F type, bisphenol S type, phenol phenol aldehyde type, cresols phenol aldehyde type, dihydroxyphenyl propane, biphenol type, bis-xylene phenol type, tris-phenol type etc.; Glycidyl esters classes such as diglycidyl phthalate; Glycidyl amines such as triglycidyl group chlorinated isocyanurates and four glycidyl group MXDP; 3,4-oxirane ring hexenyl methyl-3 ', alicyclic epoxy resin classes such as 4 '-oxirane ring hexene carboxylicesters; Known Resins, epoxy commonly used such as epoxidized polybutadiene uses more than 2 kinds alone or in combination.

Contain the carboxyl of carboxy resin with respect to 1 equivalent aforementioned (A-2), these multi-group epoxy compounds' (D-1) adding proportion is 0.6～2.0 equivalent, is preferred in properties such as the anti-plating of cured coating film, PCT patience, solder heat resistances.

The organic solvent (E) that uses in second mode as aforementioned curable resin composition, can enumerate ketone, cellosolve class, Trivalin SF class, cellosolve acetate esters, Trivalin SF acetate esters, propylene glycol ethers, dipropylene glycol ethers, propylene glycol acetate esters, dipropylene glycol acetate esters, aromatic hydrocarbon based etc., they can use more than 2 kinds alone or in combination.In addition, when considering the printing of composition, the boiling point of these organic solvents is preferred at 140～180 ℃, can not produce during silk screen printing and ooze out.

There is no particular limitation for the addition of these organic solvents (E), and in order to ensure the thickness of coating and cured coating film, its ratio is preferably below the 30 weight % for being below the 50 weight % in composition.

In addition, in first mode of curable resin composition of the present invention, also can add organic solvent (E) to regulate the viscosity of composition.

As the sulfhydryl compound (F) that in second mode of aforementioned curable resin composition, uses, can use known sulfhydryl compound commonly used, as particularly preferred, can enumerate 2 mercaptopropionic acid, trimethylolpropane tris (2-thiopropionate), 2 mercapto ethanol, the amino thiophenol of 2-, 3-sulfydryl-1,2,4-triazole, 3-sulfydryl-propyl trimethoxy silicane etc. contains the silane coupling agent of sulfydryl etc.They can use separately separately, also can will be used in combination more than 2 kinds.With respect to the aforementioned carboxylic resins of per 100 weight parts (A-2), the addition of sulfhydryl compound is advisable with the scope of 1～10 weight part.The addition of sulfhydryl compound (F) is during less than above-mentioned scope, may can not get the sticking power with polyimide base material, so not preferred.Otherwise, when surpassing above-mentioned scope, can consume the epoxy group(ing) (with epoxy reaction) of necessary aforementioned epoxy resins in the crosslinking reaction, cross-linking density reduces, so not preferred.

In order to promote the curing reaction with multi-group epoxy compound or polyfunctional group oxetane compound, in curable resin composition of the present invention, can also add known, commonly used curing catalyst as required, for example, can enumerate imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-imidazole derivatives such as 2-ethyl-4-methylimidazole; Acetylguanamine, benzene are for guanamines classes such as guanamines; Benzyldimethylamine, 4-(dimethylamino)-N, N-dimethyl benzylamine, 4-methoxyl group-N, N-dimethyl benzylamine, 4-methyl-N, aminated compoundss such as N-dimethyl benzylamine, Dyhard RU 100, trimeric cyanamide.As commercially available having, for example four countries change into U-CAT3503N, the U-CAT3502T (all being the trade(brand)name with the block isocyanate compound of dimethylamine block) etc. that 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4HMHZ (being the trade(brand)name of glyoxaline compound), San-Apro Ltd. that industrial (four countries Cheng Gong Ye (strain)) makes make.

This nitrogenous compound has the effect of the flame retardant effect of the phosphoamide compound shown in the raising aforementioned formula (I), particularly by Dyhard RU 100 and trimeric cyanamide are used simultaneously, can improve flame retardant resistance.

In addition, in curable resin composition of the present invention, further as required, following substances can also be added more than 2 kinds alone or in combination: known mineral fillers commonly used such as barium sulfate, barium titanate, silicon oxide powder, micro mist shape silicon oxide, soft silica, crystallinity silicon-dioxide, fused silica, spherical silicon dioxide, talcum, clay, magnesiumcarbonate, lime carbonate, aluminum oxide, aluminium hydroxide, mica.They can be used to the cure shrinkage that suppresses to film, improve character such as sticking power, hardness.With respect to the aforementioned carboxylic resin of per 100 weight parts, the addition of mineral filler preferably is advisable with 10～100 weight parts with 5～300 weight parts.In addition, when being used for flexibility printed circuit board,, be preferably the ratio of 5～65 weight parts to be advisable below 100 weight parts.If the addition of mineral filler surpasses aforementioned proportion, then the flexibility of cured coating film and folding resistance reduce, so not preferred.

In addition, curable resin composition of the present invention can also be used dyeing such as mineral dye, pigment dyestuff, organic dye, but causes light sensitivity to reduce because organic dye becomes, so preferably use mineral dye or pigment dyestuff.Particularly, can enumerate that phthalocyanine blue, phthalocyanine green, iodine are green, dual-azo yellow, Viola crystallina, titanium oxide, carbon black, naphthalene are black etc.In addition, from environmental problem etc., preferably especially use non-halogen pigment dyestuff.

In addition, not bringing in the scope of bad influence, can also add known thermal polymerization inhibitors commonly used such as quinhydrones, Hydroquinone monomethylether, tert-butyl catechol, pyrogallol, thiodiphenylamine to filming; Known tackifier commonly used such as fine particle silica, organobentonite, montmorillonite; The defrother and/or the levelling agent of silicone, fluorine class, high score subclass etc.; Known various additives commonly used such as sticking power imparting agent such as imidazoles, thiazoles, triazole species, silane coupling agent.

In addition, in order further to improve flame retardant resistance, can also add water-disintegrable few P contained compounds such as phosphazene compound.

Curable resin composition as light solidified/Thermocurable first mode of curable resin composition of the present invention, that can develop with alkali aqueous solution, can be applied on the printed-wiring board (PWB) that is formed with circuit by methods such as silk screen print method, curtain coating method, spraying method, rolling methods, for example the organic solvent volatile dry (interim dry) that contains in the composition can form the touch dry excellence, long the filming of life-span of developing by making under 60～100 ℃ temperature.Afterwards, can make unexposed development can form corrosion-resisting pattern with dilute alkaline aqueous solution optionally with the active ray exposure by forming figuratum photomask; Further, for example make its thermofixation, thereby can form the insulating coating film of sticking power, hardness, solder heat resistance, chemical resistance, solvent resistance, electrical insulating property, electric erosion resistance excellence by the temperature that is heated to 140～180 ℃.

Can use dilute alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, yellow soda ash, salt of wormwood, sodium phosphate, water glass, ammonia, amine as above-mentioned dilute alkaline aqueous solution.

In addition, as the radiation source that makes photocuring suitable be low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp etc.In addition, can also use laser beam etc. as the exposure active ray.

In addition; curable resin composition second mode, Thermocurable as curable resin composition of the present invention; can be applied in flexibility printed circuit board, tape carrier encapsulation or the electroluminescent cell that is formed with circuit by silk screen print method; for example; make its thermofixation by the temperature that is heated to 120～180 ℃; can shrink and produce distortion owing to cure shrinkage and cooling thereby form, and to excellent soldering-resistance layer and protective membranes such as the sticking power of base material, flexibility, folding resistance, flexibility, anti-plating, PCT patience, solder heat resistance, electrical insulating properties.

Embodiment

Enumerate embodiment below and comparative example specifically describes the present invention, the present invention is not limited to following embodiment certainly.In addition, following " part " and " % " is to be benchmark with weight not having under the situation about specifying all.

1. as the synthesis example of light solidified/hot curing resin composition first mode of curable resin composition of the present invention, that can develop with alkali aqueous solution

Synthesis example 1Synthesizing of carboxylic photoresist (A-1)

Measure 210 parts of cresols phenol aldehyde type epoxy resin (EPICLON N-680, Dainippon Ink. ﹠ Chemicals Inc makes, epoxy equivalent (weight)=210) and 109.7 parts of Trivalin SF acetic ester, heating for dissolving in the flask that thermometer, agitator, dropping funnel and reflux exchanger are housed.Then, add 0.1 part of quinhydrones and 2.0 parts of triphenylphosphines as catalysts as polymerization retarder.With this mixture heating up to 95～105 ℃, slowly drip 72 parts of vinylformic acid, reacted about 16 hours, be below the 3.0mgKOH/g up to acid value.Reaction product is cooled to 80～90 ℃, adds 76.1 parts of tetrahydronaphthalic anhydrides, reacted about 6 hours, until the absorption peak (1780cm that determines acid anhydrides with infrared absorption spectrophotometry ^-1) till the disappearance.In this reaction solution, add the aromatic solvent IPSOL#150 dilution back taking-up that 109.7 parts of Idemitsu Petrochemical Co., Ltd. make.The non-volatility composition of carboxylic photoresist (A-1) paint that so obtains is 62%, and the solid acid value is 78mgKOH/g.Below, this reaction soln is called the A-1-1 paint.

Synthesis example 2Synthesizing of carboxylic photoresist (A-1)

In the flask that whipping appts, prolong and thermometer are housed, 380 parts of bisphenol f type epoxy resin (epoxy equivalent (weight)=950 of packing into, 85 ℃ of softening temperatures, mean polymerisation degree n=6.2) and 925 parts of epoxy chloropropane, after it is dissolved in 462.5 parts of methyl-sulphoxides, under agitation in 70 ℃ of sodium hydroxide that add 60.9 parts of (1.5mol) purity 98.5%, 100 minutes times spent.Further reacted 3 hours after the interpolation at 70 ℃.Reaction adds 250 parts of water and washes after finishing.After the oily water separation, under reduced pressure more than half methyl-sulphoxide and excessive unreacted epoxy chloropropane are reclaimed in distillation from oil reservoir, to contain the remaining by-product salt and the reaction product of methyl-sulphoxide dissolves in 750 parts of methyl iso-butyl ketone (MIBK), further add 10 part of 30% aqueous sodium hydroxide solution, reacted 1 hour down at 70 ℃.After reaction finishes, carry out 2 washings with 200 parts of water.After the oily water separation, reclaim methyl iso-butyl ketone (MIBK), obtain epoxy equivalent (weight)=310, the Resins, epoxy that softening temperature is 69 ℃ (a) from the oil reservoir distillation.The multi-group epoxy compound (a) by aforementioned formula (II) expression who obtains if calculate from epoxy equivalent (weight), has 5 by epoxidation in 6.2 alcohols hydroxyls of aforementioned initial substance bisphenol f type epoxy resin approximately.310 parts of these multi-group epoxy compounds (a) and 313.2 parts of Trivalin SF acetic ester are put into the four-hole boiling flask that stirrer and reflux exchanger are housed, 90 ℃ of heated and stirred, dissolving.The solution that obtains is disposable to be cooled to 60 ℃, adds 72 parts of vinylformic acid, 0.5 part of quinhydrones, 2 parts of triphenylphosphines, is heated to 100 ℃, reacts about 60 hours, obtains the reaction product that acid value is 0.2mgKOH/g.It is added 140 parts of tetrahydronaphthalic anhydrides, be heated to 90 ℃, react, reach 100mgKOH/g, obtain containing the solution of 62.5% carboxylic photoresist (A-1) until the solid state component acid value.Below this solution is called the A-1-2 paint.

Embodiment 1,2 and comparative example 1,2

Use each paint that obtains in the aforementioned synthesis example, as shown in table 1 with after each mixing element pre-mixing, mixing with 3 roll-type mixing rolls, obtain light solidified/hot curing resin composition.The evaluation result of each light solidified/hot curing resin composition is as shown in table 2.

Table 1

		Embodiment		Comparative example
						1	?2	?1	?2
		The A-1-1 paint		161.3	?48.4					?161.3	?161.3
The A-1-2 paint						-	?112.0	?-	?-
		?Irg-907 *1		14.0	?14.0					?14.0	?14.0
?DETX *2						2.0	?2.0	?2.0	?2.0
		Dyhard RU 100		0.5	?0.5					?0.5	?0.5
?KS-66 *3						2.0	?2.0	?2.0	?2.0
		Phthalocyanine blue		1.5	?1.5					?1.5	?1.5
?SP-703 *4						80.0	?80.0	?-	?-
		?TPP *5		-	?-					?-	?90.0
Barium sulfate						40.0	?40.0	?120.0	?30.0
		?DPM *6		50.0	?50.0					?50.0	?50.0
?N-680CA75 *7						15.0	?15.0	?15.0	?15.0
		?YX-4000 *8		35.0	?30.0					?35.0	?35.0
?PB3600 *9						-	?12.0	?-	?-
		?DPHA *10		15.0	?15.0					?15.0	?15.0
Remarks	*The Photoepolymerizationinitiater initiater that 1:Ciba Specialty Chemicals Ltd. makes, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl-third-1-ketone *2: the Photoepolymerizationinitiater initiater of Nippon Kayaku K. K, 2, the 4-diethyl sulfide is for xanthone *3: the silicone antifoam agent that KCC of SHIN-ETSU HANTOTAI makes *4: the phosphoamide based flame retardant shown in the general formula (I) that Shikoku Chem makes *5: triphenylphosphate (general phosphoric acid ester fire retardant) *6: DPGME *7: the cresols phenol aldehyde type epoxy resin that Dainippon Ink. ﹠ Chemicals Inc is made is dissolved in the paint (nonvolatile component 75%) that the Trivalin SF acetic ester forms *8:Japan Epoxy Resins Co., the di-toluene phenol-type epoxy resin that Ltd. makes *9: Daisel chemical industry Co., Ltd (DAICEL CHEMICAL INDUSTRIES, LTD.) epoxidized polybutadiene of Zhi Zaoing *10: dipentaerythritol acrylate

Table 2

	Embodiment		Comparative example
					1	?2	?1	?2
	(1) flame retardant resistance	○	?○	?×					?○
(2) solder heat resistance					○	?○	?○	?○
	(3) acid resistance	○	?○	?○					?△
(4) alkali resistance					○	?○	?○	?×

In addition, the method for the performance test in the above-mentioned table 2 is as follows.

Performance evaluation:

(1) flame retardant resistance

Change on the flame retardant resistance substrate RO-67G (0.2mm t material) of the halogen of manufacturing in Hitachi respectively by silk screen printing, be coated with above-mentioned light solidified/hot curing resin composition comprehensively, make dry coating be about 20 μ m, after under 80 ℃ dry 15 minutes, the back side is coated with similarly comprehensively, after under 80 ℃ dry 20 minutes, at exposure 300mJ/cm ²Condition under blanket exposure is carried out on the two sides simultaneously, under the condition of spray pressure 0.2MPa, with 30 ℃, 1% Na ₂CO ₃The aqueous solution developed 60 seconds.This substrate 150 ℃ of thermofixations 60 minutes, is made and estimated substrate.

According to the UL94 flammability test, this test film is carried out the mensuration of combustion time.

Zero: be equivalent to UL V-0

(5 test films burn total combustion time 2 times the time respectively below 50 seconds)

△: be equivalent to UL V-1

(be 50～250 seconds total combustion time that 5 test films burn respectively 2 times the time)

*: there is not self fire extinguishing property

(5 test films burn total combustion time 2 times the time respectively more than 250 seconds)

(2) solder heat resistance

On the printed-wiring board (PWB) that has formed circuit, be coated with above-mentioned each light solidified/compositions of thermosetting resin by silk screen printing comprehensively, make dry coating be about 20 μ m, after under 80 ℃ dry 15 minutes, at exposure 300mJ/cm ²Condition under carry out the cloth exposure map, under the condition of spray pressure 0.2MPa, with 30 ℃, 1% Na ₂CO ₃The aqueous solution developed 60 seconds.Coating rosin based solder flux on the cured coating film that obtains, dipping is 10 seconds in 260 ℃ solder bath, according to the state of following benchmark evaluation cured coating film.

Zero: on cured coating film, do not expand, peel off, variable color

△: a little expansion is arranged on cured coating film, peel off, variable color

*: on cured coating film, exist expand, peel off, variable color

(3) acid resistance

According to the substrate that obtains with above-mentioned same method, dipping is 30 minutes in the aqueous sulfuric acid of 50 ℃ 10vol%, after the washing, carries out stripping test by the glassine paper adhesive tape, and the peeling off of resist, variable color are estimated.

Zero: do not find fully to change

△: small variation only occurs

*: on filming, produce and peel off

(4) alkali resistance

With above-mentioned acid resistance similarly, the substrate that obtains was flooded 30 minutes in the sodium hydroxide solution of 50 ℃ 10 weight %, after the washing, carry out stripping test by the glassine paper adhesive tape, the peeling off of resist, variable color are estimated.

Zero: do not find fully to change

△: small variation only occurs

*: on filming, produce and peel off

From the result shown in the table 2 as can be seen, the cured coating film that is made by light solidified/compositions of thermosetting resin of the present invention has following characteristic: not halogen-containing, have flame retardant resistance, excellence aspect chemical resistances such as acid resistance, alkali resistance.On the other side, the comparative example 1 that does not add the phosphoamide compound shown in the general formula (I) does not have flame retardant resistance, on the other hand, though the comparative example 2 that has added as the triphenylphosphate of general phosphoric acid ester fire retardant demonstrates flame retardant resistance, acid resistance, alkali resistance are relatively poor.

2. as the embodiment of the hot curing resin composition of curable resin composition second mode of the present invention

Synthesis example 3Resin (A-2) synthetic that contains carboxyl

In the flask that thermometer, agitator, dropping funnel and reflux exchanger are housed, add 333.3 parts of Trivalin SF acetic ester, 24.0 parts of Diisopropyl azodicarboxylates, under nitrogen atmosphere, be heated to 70 ℃.To the mix monomer that wherein drips 18.0 parts of vinylformic acid, 162.5 parts of Propenoic acid, 2-methyl, isobutyl esters and 319.5 parts of 2-ethylhexyl methacrylic esters, 3 hours times spent.Afterwards, further stir, reaction 4 hours, obtain the carboxylic resin solution of calculated value=9.7 ℃ of nonvolatile component 60%, solid state component acid value 28.1mgKOH/g, weight-average molecular weight 16,000, Tg.Below, should be called the A-2-1 paint by carboxylic resin solution.

Synthesis example 4Resin (A-2) synthetic that contains carboxyl

In the flask that thermometer, agitator, dropping funnel and reflux exchanger are housed, add 333.3 parts of dipropylene glycol monomethyl ether, 20.0 parts of Diisopropyl azodicarboxylates, under nitrogen atmosphere, be heated to 70 ℃.To the mix monomer that wherein drips 36.0 parts of vinylformic acid, 189.0 parts of methyl methacrylates and 275.0 parts of methacrylic acid dodecyl esters, 3 hours times spent.Afterwards, further stir, reaction 4 hours, obtain the carboxylic resin solution of calculated value=-12.2 ℃ of nonvolatile component 60%, solid state component acid value 56.1mgKOH/g, weight-average molecular weight 25,000, Tg.Below, should be called the A-2-2 paint by carboxylic resin solution.

Compare synthesis example 1Synthesizing of the comparison resin of carboxylic resin (A-2)

In the flask that thermometer, agitator, dropping funnel and reflux exchanger are housed, add 466.7 parts of dipropylene glycol monomethyl ether, 12.0 parts of Diisopropyl azodicarboxylates, under nitrogen atmosphere, be heated to 70 ℃.To the mix monomer that wherein drips 72.0 parts of vinylformic acid, 428.0 parts of Propenoic acid, 2-methyl, isobutyl esters and 200.0 parts of 2-hydroxyethyl meth acrylates, 3 hours times spent.Afterwards, further stir, reaction 4 hours, obtain the carboxylic resin solution of calculated value=55.2 ℃ of nonvolatile component 60%, solid state component acid value 80.1mgKOH/g, weight-average molecular weight 45,000, Tg.Below, should be called the A-2-R paint by carboxylic resin solution.

Embodiment 3,4 and comparative example 3～5

Use is by synthesis example 3,4 and compare each paint that synthesis example 1 obtains carboxylic resin, and is mixing with 3 roll-type mixing rolls after the blending ratio pre-mixing shown in the following table 3, obtains hot curing resin composition.

Table 3

		Embodiment		Comparative example
							3	4	3	4	5
		The A-2-1 paint		100	-	-						100	100
The A-2-2 paint							-	100	-	-	-
		The A-2-R paint		-	-	100						-	-
?TEPIC-H *1							10	10	10	10	10
		?SP-703 *2		28	28	-						-	-
?TPP *3							-	-	-	-	34
		?PnB *4		10	10	10						10	10
?A-189 *5							-	3	-	-	-
		Phthalocyanine blue		2	2	2						2	2
?2PHZ *6							1	1	1	1	1
		Barium sulfate		12	12	40						40	6
?KS-66 *7							1	1	1	1	1
		Remarks	*1: the triglycidyl group chlorinated isocyanurates of the high melting temperature type that Nissan Chemical Ind Ltd makes *2: the phosphoamide based flame retardant shown in the general formula (I) that Shikoku Chem makes *3: as the Triphenyl phosphate of general fire retardant *4: the propylene glycol single-butyl ether *3-sulfydryl-propyl trimethoxy silicane that 5:nihonunica dipropylene glycol makes *6: four countries change into the imidazolium compounds that industrial makes *7: the silicone defoamer that KCC of SHIN-ETSU HANTOTAI makes

Performance evaluation:

(1) flame retardant resistance

Change in Hitachi on the flame retardant resistance substrate RO-67G (0.2mmt material) of halogen of manufacturing, be coated with each hot curing resin composition of the Thermocurable of the foregoing description 3,4 and comparative example 3～5 by silk screen printing comprehensively, making on each face is 20 μ m, with the thermofixation in 150 ℃, 30 minutes of heated air circulation type drying oven.According to the UL94 flammability test, this test film is carried out the mensuration of combustion time.

Zero: be equivalent to UL V-0

(5 test films burn total combustion time 2 times the time respectively below 50 seconds)

△: be equivalent to UL V-1

(be 50～250 seconds total combustion time that 5 test films burn respectively 2 times the time)

*: there is not self fire extinguishing property

(5 test films burn total combustion time 2 times the time respectively more than 250 seconds)

(2) folding resistance

Be printed on respectively on each kapton material (kapton) (thick 25 μ m) by silk screen printing each curable resin composition comprehensively, in 30 minutes, solidifying (dry film thickness 20 μ m) under 150 ℃ the Thermocurable of the foregoing description 3,4 and comparative example 3～5.The cured film that obtains is bent 180 °, according to following benchmark evaluation.

Zero: do not have crackle on the cured film

△: a small amount of crackle is arranged on the cured film

*: crackle is arranged on the cured film

(3) distortion

Be printed on each kapton material (150 * 110mm, thick 25 μ m) by silk screen printing each curable resin composition comprehensively, in 30 minutes, solidifying (dry film thickness 20 μ m) under 150 ℃ the Thermocurable of the foregoing description 2～4.After the cooling, the distortion of the cured coating film that obtains according to following benchmark evaluation.

Zero: not distortion fully

△: a small amount of warpage occurs

*: distortion appears

(4) alkali resistance

With above-mentioned acid resistance similarly, the substrate that obtains was flooded 30 minutes in the sodium hydroxide solution of 50 ℃ 10 weight %, after the washing, carry out stripping test by the glassine paper adhesive tape, the peeling off of resist, variable color are estimated.

Zero: do not find fully to change

△: small variation occurs

*: on filming, produce and peel off

(5) solder heat resistance

On tellite (thickness 1.6mm), each curable resin composition of the Thermocurable of Butut printing the foregoing description 3,4 and comparative example 3～5 solidifies in 150 ℃, 30 minutes (dry film thickness 20 μ m) respectively.Coating rosin based solder flux on the cured coating film that obtains, dipping is 10 seconds in 260 ℃ solder bath, according to the state of following benchmark evaluation cured coating film.

Zero: on cured coating film, do not expand, peel off, variable color

△: a little expansion is arranged on cured coating film, peel off, variable color

*: on cured coating film, exist expand, peel off, variable color

Above evaluation result is as shown in table 4.

Table 4

	Embodiment		Comparative example
						3	?4	3	4	?5
	(1) flame retardant resistance	○	?○	×	×						?○
(2) folding resistance						○	?○	△	○	?○
	(3) distortion	○	?○	×	○						?○
(4) alkali resistance						△	?○	○	○	?×
	(5) solder heat resistance	○	?○	○	○						?△

From the result shown in the table 4 as can be seen, the embodiment 3,4 that adds the phosphoamide based flame retardant is not halogen-containing, demonstrates flame retardant resistance, the characteristic good at aspects such as folding resistance, distortion, alkali resistances.On the other hand, the Tg of the carboxylic resin of comparative example 3 is higher, and it is big that the distortion that cure shrinkage produces becomes, though comparative example 5 has used general phosphoric acid ester fire retardant, obtains flame retardant resistance, and alkali resistance is relatively poor.

Claims (11)

1. One kind as printed-wiring board (PWB) with the curable resin composition that solder resist uses, it is characterized in that: contain the phosphoamide compound shown in the following general formula (I), in the formula (I), R ¹, R ²Can be identical or different, the alkyl of expression hydrogen atom or carbonatoms 1～4.

   
2. 2. curable resin composition according to claim 1 is characterized in that: described curable resin composition is the light solidified/hot curing resin composition that can develop with alkali aqueous solution, contains following composition:

   (A) in a part, contain the carboxylic resin of 1 above carboxyl,

   (B) in a part, contain the compound of the vinyl unsaturated link(age) more than 2,

   (C) Photoepolymerizationinitiater initiater and

   (D) in a part, have the oxyethane ring more than 1 and/or the compound of trimethylene oxide ring.
3. 3. curable resin composition according to claim 2 is characterized in that: described carboxylic resin (A) further has the carboxylic photoresist of the vinyl unsaturated link(age) more than 2 in a part for (A-1).
4. 4. curable resin composition according to claim 3, it is characterized in that: the described carboxyl photoresist (A-1) that contains is to be selected from least a kind of multi-group epoxy compound (a) in the compound shown in following general formula (II), following general formula (III) and the following logical formula V and the reactant of unsaturated monocarboxylic acid (b), obtain resin with saturated and/or unsaturated multi-anhydride (c) reaction

   R in the formula (II) ³, R ⁴Expression hydrogen atom or methyl, R ⁵Expression hydrogen atom or glycidyl, n represents 1～50 value,

   M represents the group shown in the following general formula (IV), R in the formula (III) ⁶The residue of expression aliphatics or aromatic series polyfunctional group carboxylic acid, m represents 1～50 value,

   R in the formula (IV) ⁷, R ⁸Expression divalent cyclohexane ring and/or phenyl ring, R ⁹, R ¹⁰Expression hydrogen atom or methyl, R ¹¹Expression hydrogen atom or glycidyl, k represents 0～25 value,

   X represents different divalent aromatic ring mutually with Y in the formula V, and G represents glycidyl and/or hydrogen atom, and p represents 1～20 integer.
5. 5. curable resin composition according to claim 1 is characterized in that, described curable resin composition is the hot curing resin composition that contains following composition:

   (A-2) have 2 above carboxyls in a part, acid value is 20～120mgKOH/g, and second-order transition temperature is-60～40 ℃, and weight-average molecular weight is 5,000～100,000 carboxylic resin,

   (D-1) in 1 molecule, have the oxyethane ring more than 2 the multi-group epoxy compound and

   (E) organic solvent.
6. 6. curable resin composition according to claim 5 is characterized in that: further contain (F) sulfhydryl compound.
7. 7. curable resin composition according to claim 6 is characterized in that: described (F) sulfhydryl compound is 3-sulfydryl-propyl trimethoxy silicane.
8. 8. according to the curable resin composition of claim 1 to 7 described in each, it is characterized in that: described phosphoamide compound content in composition is 5～50 weight %.
9. 9. cured coating film is characterized in that: the curable resin composition that aforementioned claim 1 to 4 is put down in writing in each by irradiation of activation evergy line and/or heating solidifies and obtains.
10. 10. cured coating film is characterized in that: the curable resin composition that aforementioned claim 5 to 7 is put down in writing in each by heating solidifies and obtains.
11. 11. a cured coating film is characterized in that: by heating the curable resin composition of record in the aforementioned claim 8 is solidified and obtain.