CN100379780C - Curable resins and curable resin compositions containing the same - Google Patents

Abstract

There is provided a curable resin having an unsaturated group and a carboxyl group at the terminals of its side chains, such as a curable resin obtained by reacting an unsaturated group-containing monocarboxylic acid (d) with a reaction product (c) of a compound having three or more phenolic hydroxyl groups in its molecule (a) and an alkylene oxide (b) and further reacting a polybasic acid anhydride (f) with the resultant reaction product (e). By compounding such a curable resin with a photopolymerization initiator, a photosensitive (meth)acrylate compound, an epoxy compound, a diluent solvent, another curable resin which has a carboxyl group and an unsaturated group in its molecule and which is in the state of solid at room temperature, a flame-retardant, etc., there is obtained a photocurable and thermosetting resin composition which is useful for the formation of a solder resist of a printed circuit board, an interlaminar insulating layer of a multi-layer circuit board, or the like.

Description

Curable resin and contain the curable resin composition of this curable resin

Technical field

The present invention relates to a kind ofly have the curable resin of unsaturated group and carboxyl and contain the curable resin composition of this curable resin in side chain terminal.More particularly, the present invention relates to a kind ofly have outside good scolding tin thermotolerance, anti-PCT (autoclave test) property, also have the curable resin of curing tunicles such as good adhesion, resistance to chemical reagents, anti-electroless gold plating, electrical insulating property, anti-water absorbability and contain the curable resin composition of this curable resin.

The invention still further relates to a kind of solder resist that is applicable to printed circuit board (PCB), and can provide after predrying and have good touch dry, development, and light solidified and heat-curing resin with cured articles such as good adhesion, scolding tin thermotolerance, resistance to chemical reagents, anti-water absorbability, anti-electroless gold plating, PCT patience, electrical insulating property, flame retardant resistances, the particularly light solidified of flame retardant resistance and hot curing resin composition.

Background technology

At present, as etch-resistant coatings such as printed circuit board (PCB) (supercoat; Resist) light solidified of Shi Yonging and hot curing resin composition are because of being subjected to having doubt such as environmental problem, so many to use the diluted alkaline aqueous solution to be main flow as the photocuring-hot curing resin composition of the alkali developable of developing solution.

As light solidified and the hot curing resin composition of the aforementioned use diluted alkaline aqueous solution as the alkali developable of developing solution; can list: for example the phenolic varnish type epoxy compounds with contain the curable resin of the monocarboxylic reaction product of unsaturated group through acid anhydrides addition gained; Photoepolymerizationinitiater initiater; the anticorrosion protection ink composite of photo polymerization monomer and epoxy compounds gained (spy opens clear 61-243869 number); having the alcohol dihydroxyl that has the aromatic alcohols resin reaction gained of 2 phenolic hydroxyls in the aromatic epoxy resin of 2 glycidyls and 1 molecule in 1 molecule reacts with epihalohydrins again; the gained reaction product again with the monocarboxylic acid reaction that contains unsaturated group, make the anticorrosion protection ink composite (spy opens flat 5-32746 number) that contains curable resin etc. subsequently behind the addition acid anhydrides.

At present, use the curable resin composition (spy open clear 61-243869 number) of cresols phenolic resin varnish type epoxy resin as the starting raw material gained, it solidifies tunicle and has characteristics such as good scolding tin thermotolerance, resistance to chemical reagents, electrical insulating property, so wide technical such as electronic material such as employed permanent cover sheet when the utmost point is suitable for making solder resist that tellite uses or thin-film package manufacturing.

But along with the development of nearest electrical equipment industry, semiconductor industry, the utmost point need be developed has better characteristic, for example can satisfy to have better thermotolerance and the desired various curable resins of PCT patience.

As aforementioned curable resin composition with excellent heat resistance and PCT patience, can list: for example contain cresols phenolic resin varnish type epoxy resin and dimethylol propionic acid and acrylic acid reactant, composition (spy opens flat 6-324490 number) with the curable resin of tetrahydronaphthalic anhydride reaction gained, contain the reactant of cresols phenolic resin varnish type epoxy resin and vinylformic acid and p-leptodactyline alcohol and the composition (spy opens flat 11-288091 number) that Tetra Hydro Phthalic Anhydride reacts the curable resin of gained, the resin and (methyl) vinylformic acid that contain the pendant hydroxyl group part epoxidation gained of bisphenol-type epoxy resin, the various compositions that contain the curable resin of alkali-soluble subsequently with the composition (spy opens flat 9-54434 number, and the spy opens the 2001-13684 communique) of the curable resin of multi-anhydride reaction gained etc.

But, aforementioned curable resin composition, it solidifies tunicle, does not satisfy excellent heat resistance and PCT patience yet fully simultaneously.

Such as mentioned above, as the motion of existing several compositional systems of curable resin composition, now be used in widely in the manufacturing of actual printed circuit board (PCB) so far.But, because of making printed circuit board (PCB), compactization along with electronics also form densification in recent years, do not reach high performance yet but solidify tunicle, therefore, need ask operability in the manufacturing processed for making this tunicle.

That is, use the printed circuit board (PCB) of the anticorrosion protection of curable resin composition formation in the past coating, not good as the PCT patience of long-term reliability test, in the PCT test, can produce peeling off of etch-resistant coating film.The problem of aforementioned long-term reliability is not limited in the etch-resistant coating on the printed circuit board (PCB), also comes across on the goods of other purposes such as interlayer insulating film of piling up multilayer circuit boards such as (built up) substrate, and is preferably or not.Again, with regard to improving the operability aspect, popularizing of automatic exposure machine also can produce the problem of predrying back touch dry.

Again, the curing tunicle of aforementioned curable resin composition so require in the purposes of flame retardant resistance in brute force, still is subjected to the restriction of use range because of as easy as rolling off a log burning on safety.Give the method for curable resin composition flame retardant resistance, for example adding fire retardant is general known method, but when using this composition, will produce problems such as thermotolerance or wet fastness reduction, and extremely difficulty reaches practicability.

Summary of the invention

In view of foregoing problems, the purpose of this invention is to provide a kind ofly, and can form the alkali-soluble curable resin that base material is had the cured article of various characteristicses such as good adhesion or hardness, resistance to chemical reagents, anti-water absorbability with high level equilibrated thermotolerance and PCT patience.

Another object of the present invention provides a kind of by using aforementioned curable resin, and make the good curing tunicle of various characteristicses such as the desired scolding tin thermotolerances such as solder resist that fully satisfy printed circuit board (PCB), PCT patience, adhesivity, resistance to chemical reagents, electroless gold plating patience, electrical insulating property, anti-moisture absorption with base material, with the curable resin composition with good touch dry, development, particularly light solidified and hot curing resin composition.

Another purpose of the present invention provides a kind of aforementioned scolding tin thermotolerance, resistance to chemical reagents, anti-water absorbability, adhesivity, PCT patience, electroless gold plating patience of not undermining, various advantages such as electrical insulating property, and light solidified and hot curing resin composition with excellent flame retardancy.

For realizing aforementioned purpose, according to the present invention, provide the curable resin that a kind of side chain terminal has unsaturated group and carboxyl, the one embodiment is, by the compound (not comprising the phenolic varnish type phenolic resin) that has 3 or above phenolic hydroxyl in 1 molecule (a) with the reaction product (c) of oxirane (b) gained, with the monocarboxylic acid that contains unsaturated group (d) reaction, the reaction product of gained (e) is reacted the curable resin of gained again with multi-anhydride (f).

Again, another embodiment of curable resin of the present invention is, for example provides a kind of side chain to have the following formula (I) and (II) curable resin of represented group.

In the formula, R ¹, R ²Represent hydrogen atom, methyl or ethyl independently of one another, R ³, R ⁴With R ⁵Represent that independently of one another hydrogen atom, carbon number are 1 to 6 alkyl, aryl, aralkyl, cyano group, fluorine atom or furyl, Z is the multi-anhydride residue, and n is 0.5 to 10 value.

According to preferable embodiment more specifically, the compound (a) that has 3 or above phenolic hydroxyl in aforementioned 1 molecule is phenol shown in the following formula (III) and the condenses with aromatic series aldehydes gained of phenolic hydroxyl, and the monocarboxylic acid (d) that contains unsaturated group is vinylformic acid and/or methacrylic acid, and multi-anhydride (f) is an ester ring type dibasic acid anhydride etc.

In the formula, R is that hydrogen atom or carbon number are 1 to 18 alkyl, and X is hydrogen atom or halogen atom, and Y is that carbon number is 1 to 18 alkyl or alkoxyl group, and k is 0,1 or 2 integer, and m is 0 or above integer.

Curable resin of the present invention, because of side chain terminal has unsaturated group and carboxyl, so have good reactivity, and the amount of the hydrophilic alcoholic hydroxyl of low reactivity seldom or not exists, so can obtain the thermotolerance of high level and the balance of PCT patience, and can form the cured article that has various characteristicses such as good adhesion or hardness, resistance to chemical reagents, anti-water absorbability for substrate.Therefore contain this curable resin simultaneously, curable resin composition with Photoepolymerizationinitiater initiater, photosensitivity acrylate or methacrylate compound, epoxy compounds and diluting solvent etc., except that showing good alkali-developable, also can provide a kind of cured article with excellent heat resistance, PCT patience, adhesivity, resistance to chemical reagents, electroless gold plating patience, electrical insulating property, anti-water absorbability etc.

Therefore, according to a further aspect in the invention, the present invention provides a kind of curable resin composition that contains above-mentioned curable resin.

According to preferable embodiment of the present invention, provide a kind of light solidified and hot curing resin composition, it contains (A) described curable resin, (B) Photoepolymerizationinitiater initiater, (C) photosensitivity acrylate or methacrylate compound, (D) Resins, epoxy, reach (E) diluting solvent, wherein said curable resin is by having 3 or the compound (a) of above phenolic hydroxyl and the reaction product (c) of oxirane (b) gained in 1 molecule, react with the monocarboxylic acid that contains unsaturated group (d), the reaction product of gained (e) again with the curable resin of multi-anhydride (f) reaction gained, or side chain has the aforementioned formula (I) and (II) curable resin of represented group.

According to better concrete scheme of the present invention, provide a kind of light solidified and hot curing resin composition, it also contains and has carboxyl and unsaturated group in the molecule and at room temperature be solid curable resin (F) except that containing aforementioned each composition.

In better embodiment, preferably also contain curing catalysts (G) in light solidified and the hot curing resin composition.

In addition, according to other preferred embodiments more specifically of the present invention, provide the flame retardant photocurable and the hot curing resin composition that also contain fire retardant (H).Fire retardant (H) is preferred for example use from halogenated epoxy resin, halogenated aromatic compound, halo alicyclic compound, phosphoric acid ester flame retardant, with the weisspiessglanz flame retardant selected at least a kind.

Description of drawings

Fig. 1 is the infrared absorption spectrum for synthesis example 1 prepared curable resin.

Embodiment

Present inventors, for solving foregoing problems through further investigation, found that, use by the compound (a) that has 3 or above phenolic hydroxyl in 1 molecule through with the reaction product (c) of oxirane (b) addition gained, react with the monocarboxylic acid that contains unsaturated group (d) again, (wherein particularly following curable resin: the monocarboxylic acid that contains unsaturated group is vinylformic acid and/or methacrylic acid to the reaction product of gained (e) with the curable resin of multi-anhydride (f) reaction gained again, and multi-anhydride (f) is the ester ring type dibasic acid anhydride), or side chain is when having the curable resin of aforementioned formula (I) and (II) represented group, can make with excellent heat resistance, PCT patience, various base materials had good adhesion, resistance to chemical reagents, electroless gold plating patience, electrical insulating property, the cured article of anti-water absorbability etc., thereby finish the present invention.

Promptly, the present invention is by having 3 or the compound (a) of above phenolic hydroxyl and the addition reaction of oxirane (b) in 1 molecule, make chain extension and form good pliability, stretchiness, and terminal hydroxyl through being produced with the oxirane addition reaction, contain monocarboxylic acid (d) addition reaction of unsaturated group and the addition reaction of multi-anhydride (f) again, unsaturated group or carboxyl are not present on the same side chain, and, because of it lays respectively at the end of each side chain, so have good reactivity, again, because of having, so have good alkali-developable apart from main chain terminal carboxyl(group) far away.In addition, this resin is not because of having or only have a little in the past by the such lower hydrophilic alcoholic hydroxyl of reactivity of the acid anhydrides institute resin of epoxy acrylate, so have splendid anti-water absorbability.

Therefore, the organic solvent, Photoepolymerizationinitiater initiater, photosensitivity acrylate or the curable resin compositions such as methacrylate compound, Resins, epoxy that contain above-mentioned curable resin simultaneously, except that having good alkali-developable, light solidified and Thermocurable, after the selectivity exposure of filming, development and processing solidification treatment, can provide a kind of cured article with good scolding tin thermotolerance, PCT patience, adhesivity, resistance to chemical reagents, electroless gold plating patience, electrical insulating property, anti-water absorbability etc.

But the aforementioned composition that does not contain the curable resin of alcoholic hydroxyl is because of its touch dry extreme difference, so with regard to the aspect of operability, also use to good with other resins.In the time of can obtaining referring to the property touched for all characteristics are reduced, serve as to use under the room temperature that has carboxyl and unsaturated group in the molecule to get final product as the solid resin to merge a curable resin that uses.

Therefore, aforementioned photocuring-the hot curing resin composition of the present invention that contains organic solvent, Photoepolymerizationinitiater initiater, photosensitivity acrylate or methacrylate compound, the epoxy compounds etc. of 2 kinds curable resin simultaneously, except that showing splendid touch dry and alkali-developable, after its selectivity of filming exposure, development and processing solidification treatment, can provide a kind of curing tunicle with good adhesion, good scolding tin thermotolerance, resistance to chemical reagents, electroless gold plating patience, PCT patience, electrical insulating property.

In addition, above-mentioned curable resin composition is by cooperating fire retardant, and the result can obtain good flame retardant resistance, and in adding the characteristic that also can not reduce tunicles such as anti-water absorbability or thermotolerance under the fire retardant.

Below, will elaborate to curable resin of the present invention and the curable resin composition that contains it.

At first, curable resin of the present invention (A) as previously mentioned, it is the curable resin that has the represented group of aforementioned formula (I) and formula (II) on side chain, or by the compound that has 3 or above phenolic hydroxyl in 1 molecule (below, be called for short the compound contain multifunctional phenolic hydroxyl) (a) with the reaction product (c) of oxirane (b), react with the monocarboxylic acid that contains unsaturated group (d) again, gained reaction product (e) is reacted the curable resin of gained again with multi-anhydride (f), catalyzer is as described later used in each reaction, and can easily carry out in solvent.

Distinctness is elaborated to previous reaction.At first, the reaction of compound of multifunctional phenolic hydroxyl (a) and oxirane (b) when for example using poly(4-hydroxystyrene) and propylene oxide, can be carried out according to following mode.In the following reaction formula, formula (1) is phenolic hydroxyl 1 equivalent with respect to the compound that contains multifunctional phenolic hydroxyl (a), propylene oxide (b) is that less than 1 normal ratio is when reacting with the epoxy group(ing), formula (2) for propylene oxide (b) be 1 normal ratio when reacting with epoxy group(ing), formula (3) for propylene oxide (b) be 1 equivalent or the above ratio sketch chart when reacting with epoxy group(ing).

Secondly, to the reaction that contains unsaturated group monocarboxylic acid (d) of the reaction product (c) of aforementioned formula (1), (2) or (3), when for example using vinylformic acid, be to carry out as following mode.Promptly, the compound that contain multifunctional phenolic hydroxyl (a) such to aforementioned formula (1), if the addition of propylene oxide (b) is a part when carrying out, addition to the monocarboxylic acid that contains unsaturated group (d) of this addition reaction (c), be such shown in following formula (4), will preferentially produce the hydroxyl that compound (a) addition that contains multifunctional phenolic hydroxyl has propylene oxide (b).To the addition of the monocarboxylic acid that contains unsaturated group (d) of the reactant (c) of formula (2), be that the mode according to following formula (5) produces again.To the addition of the monocarboxylic acid that contains unsaturated group (d) of the reactant (c) of formula (3), be that the mode according to following formula (6) produces again.

At last, to the reaction of the multi-anhydride (f) of the reactant of aforementioned formula (4), (5) or (6), when for example using Tetra Hydro Phthalic Anhydride, be to carry out according to following mode.The addition of multi-anhydride is preferably to produce alcoholic hydroxyl, and as the mode of following formula (7), (8) or (9) carry out, can produce various variations according to the difference of its markup percentage.

As the compound that contains multi-functional hydroxyl (a), can list: for example phenol with have the condenses of the aromatic series aldehydes of phenolic hydroxyl, poly(4-hydroxystyrene), 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 2,3-, 2, aldehydes condenses, list or the dihydroxy naphthlene of the condenses of 6-or 2,7 dihydroxy naphthalene and aldehydes, single naphthols and above-mentioned dihydroxy naphthlene and condenses, list or the dihydroxy naphthlene of xylylene-glycol class and the affixture of diolefin etc., but not only be defined in this.

The compound that contains multifunctional phenolic hydroxyl as described above, it has on the aromatic nucleus of phenolic hydroxyl or has on phenolic hydroxyl and the hydrocarbon skeleton aromatic nucleus bond, can have functional groups such as the halogen atom of comprising, oxygen, nitrogen, sulphur, for example also comprise the compound of heteroaromatic bases such as halogen radical, ether, ester group, carbonyl, hydroxyl, aldehyde radical, amino, amido, itrile group, nitro, thiol group, thioether group, other pyridyl or imidazolyl.

In the aforementioned compound that contains multifunctional phenolic hydroxyl, phenol shown in the preferred following formula (III) and condenses with aromatic series aldehydes of phenolic hydroxyl.

In the formula, the meaning of R, X, Y, k, m is identical with aforementioned content.

For example can use the compound shown in the following formula (IV) as phenol, can list for example phenol, ortho-cresol, meta-cresol, p-cresol, o-brominated cresols, a position bromo cresols, para-brominated cresols, ethylphenol, propylphenol, butylphenol, hexylphenol, octyl phenol, nonylphenol etc.In addition, also can use for example phenylphenol, cumylphenol etc.

In the formula, R is that hydrogen atom or carbon number are that 1 to 18 alkyl, X are hydrogen atom or halogen atom.

As aromatic aldehyde, can list: the compound shown in the following formula V, for example hydroxyl benzaldehyde, methoxyl group hydroxyl benzaldehyde, dimethoxy hydroxyl benzaldehyde, salicylic aldehyde etc. with phenolic hydroxyl.

In the formula, Y is that carbon number is 1 to 18 alkyl or alkoxyl group, and k is 0,1 or 2.

Above-mentioned phenol and above-mentioned condenses with aromatic series aldehydes of phenolic hydroxyl, for the former 1 mole, the latter is to use 0.1 to 3.0 mole, be preferably 0.3 to 1.5 mole ratio, and under the existence of an acidic catalyst (other organic acid salts etc. are general as generating phenolic varnish catalyzer user for inorganic acids such as hydrochloric acid, sulfuric acid, organic acids such as oxalic acid, toluenesulphonic acids), in 80 to 250 ℃, be preferably the reaction gained that carried out under 100 to 180 ℃ the temperature 1 to 6 hour.

Proportional to adding of the oxirane (b) of the above-mentioned compound (a) that contains multifunctional phenolic hydroxyl, with to above-mentioned phenolic hydroxyl 1 equivalent that contains the compound (a) of multifunctional phenolic hydroxyl, be preferably 0.5 to 10.0 mole, more preferably 1.0 to 6.0 moles.Be lower than 0.5 mole with the occasion that is higher than 10.0 moles, have the doubt that lacks light solidified and Thermocurable during as carboxylic curable resin (A).When curable resin composition adds fire retardant (H), have the doubt of thermotolerance, the reduction of anti-water absorbability again.

Addition reaction to the oxirane (b) of the above-mentioned compound (a) that contains multifunctional phenolic hydroxyl, for example under the existence of the mixture of level Four basic salt compounds such as alkali metal compounds such as sodium hydroxide, potassium hydroxide or tri methyl benzyl ammonium oxyhydroxide, tetramethyl-ammonium oxyhydroxide, tetraethyl ammonium oxyhydroxide or alkali metal compound and level Four basic salt compound, for example use ketones such as methyl ethyl ketone, pimelinketone, mibk, toluene, dimethylbenzene, tetramethyl-benzene etc. are aromatic hydrocarbon based, or its mixed solvent, in 80 to 180 ℃, normal pressure is to 10kg/cm ²Under carry out.

As oxirane (b), can list for example oxyethane, propylene oxide, butylene oxide ring, epoxy Trimethylmethane, trimethylene oxide, tetrahydrofuran (THF), tetrahydropyrans etc.With regard to aspects such as reactivity, be good with oxyethane, propylene oxide, butylene oxide ring, epoxy Trimethylmethane etc. again wherein.

Temperature of reaction in the esterification of the reaction product (c) of the above-mentioned same oxirane of compound (a) (b) that contains multifunctional phenolic hydroxyl and the monocarboxylic acid (d) that contains unsaturated group, with about 50 to 150 ℃ be good, in decompression down, under the normal pressure, add and depress all and can react.In the aforementioned esterification, contain unsaturated group-first carboxylic acid (d), be that 300 to 700 addition amount is good to have two key equivalents that can make curable resin of the present invention.Again, for example can to use aromatic hydrocarbonss such as toluene, dimethylbenzene, tetramethyl-benzene be good to reaction solvent.Aforementioned solvents can use separately or mix use 2 kinds or more than.Esterifying catalyst for example can use sulfuric acid, hydrochloric acid, phosphoric acid, boron trifluoride acid, methylsulfonic acid, Phenylsulfonic acid, p-toluenesulphonic acids, Zeo-karb etc.Esterification is for example carried out under the existence of polymerization retarder to good, and polymerization retarder for example can use quinhydrones, toluhydroquinone, Hydroquinone monomethylether, pyrocatechol, pyrogallol etc.

As the aforementioned representation compound that contains the monocarboxylic acid (d) of unsaturated group, can list for example vinylformic acid, methacrylic acid, Ba Dousuan, TRANSCINNAMIC ACID, alpha-cyano TRANSCINNAMIC ACID, β-styrene acrylic, β-furfuryl group vinylformic acid etc., be good wherein to use vinylformic acid and/or methacrylic acid with regard to the rerum natura of photoreactivity and cured article, particularly thermotolerance, electrical insulating property and anti-hygroscopic influence.The aforementioned monocarboxylic acid that contains unsaturated group can use separately or mix use 2 kinds or more than.

Previous reaction product (c) and the reaction product (e) that contains the monocarboxylic acid (d) of unsaturated group, through making curable resin of the present invention (A) with multi-anhydride (f) reaction, in this reaction, the usage quantity of multi-anhydride (f) is to make the addition amount be preferably 30 to 150mgKOH/g with the acid number that can make the curable resin that is generated, and more preferably 30 to 120mgKOH/g.When the acid number of curable resin was lower than 30mgKOH/g, to the solvability variation of alkali aqueous solution, it is difficult that the development of filming of formation becomes.On the other hand, when the acid number of curable resin is higher than 150mgKOH/g, under the condition that need not expose, also can make the surface development of exposure portion, so not preferred.

Reaction is under the existence of aftermentioned organic solvent and under the existence of polymerization retarders such as quinhydrones or oxygen, generally carries out under 50 to 150 ℃.At this moment, as required, phosphides such as imidazolium compoundss such as quarternary ammonium salt, 2-ethyl-4-methylimidazole, triphenylphosphine such as tertiary amines such as triethylamine, triethyl benzyl ammonium muriate can be added as catalyzer.

As above-mentioned multi-anhydride (f), can list for example methyl tetrahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, polymeric amide acid anhydrides (Na ジ _ッThe Network acid anhydrides), 3, ester ring type dibasic acid anhydrides such as 6-endo-methylene group-Tetra Hydro Phthalic Anhydride, methyl-carbic anhydride, tetrabromophthalic anhydride; Aliphatics or aromatic binary or tricarboxylic anhydrides such as succinyl oxide, maleic anhydride, itaconic anhydride, octene succinyl oxide, five dodecenyl succinic anhydrides, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, or aliphatics such as biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic acid dianhydride, ring penta tetracarboxylic dianhydride, pyromellitic acid acid anhydride, benzophenone tetracarboxylic dianhydride or aromatic series tetraprotic acid dianhydride etc., it can use more than a kind or 2 kinds.Wherein preferred especially ester ring type dibasic acid anhydride.

Aforementioned curable resin of the present invention can cooperate with Photoepolymerizationinitiater initiater (B) with the formation Photocurable resin composition, and produces photocuring via the irradiation of active energy ray.As the radiation source of photocuring, can use Cooper-Hewitt lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, xenon lamp, metal halides lamp etc.Other for example laser beam etc. also can be used as active energy ray and use.

As Photoepolymerizationinitiater initiater (B), can list as benzoin and benzoin alkane ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ethers; Phenyl methyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, phenyl methyl ketone classes such as 1-two ring phenyl methyl ketones; 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-2-morpholinyl-aminoacetone-1,2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone, N, aminoacenaphthene classes such as N-dimethylamino acetyl benzene; Anthraquinone classes such as 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloro anthraquinone; 2,4-dimethyl thioxanthone, 2-clopenthixal ketone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 2, thioxanthene ketones such as 4-di-isopropyl thioxanthone; Ketal classes such as phenyl methyl ketone dimethyl ketal, benzyl dimethyl ketal; 2,4, mercaptan compounds such as 5-triarylimidazoles dimer, hibon, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4, organic halogens such as 6-three-s-triazine, tribromo-ethanol, trisbromomethyl phenyl sulfone; Benzophenone, 4,4 '-benzophenone or thioxanthene ketones such as two diethylamino benzophenone; 2,4,6-Three methyl Benzene accidental cause diphenyl phosphine oxide etc.Aforementioned known habitual Photoepolymerizationinitiater initiater, can be separately or with 2 kinds or abovely use as mixture, in addition, can add N again, N-dimethylaminobenzoic acid ethyl ester, N, Photoepolymerizationinitiater initiaters such as tertiary amines such as N-dimethylaminobenzoic acid isopentyl ester, amyl group-4-dimethylaminobenzoic acid ester, triethylamine, trolamine.Again, the compounds for promoting that photoresponse is added such as two cyclopentadiene titanium compounds that have (the Ciba corporate systems) such as CGI-784 of absorption in visible domain.Be not particularly limited in this; so long as can be in UV-light or visible region absorb light; and can make compound that unsaturated group such as (methyl) acryl produces radical polymerization just, then be not limited to Photoepolymerizationinitiater initiater, light-initiated auxiliary agent etc., and can be separately or with multiple merging use.

Preferably be combined as 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-2-morpholinyl-aminoacetone-1 and 2,4-diethyl thioxanthone or 2-di-isopropyl thioxanthone, 4-benzoin-4 '-combinations such as methyldiphenyl base sulfide.

The use level of aforementioned lights polymerization starter (B) (being its total amount when using light-initiated auxiliary agent), in with respect to curable resin (A or contain F again) 100 mass parts (with the solid composition, below identical) be 0.1 to 30 mass parts, be preferably the ratio of 0.5 to 20 mass parts.When the addition of Photoepolymerizationinitiater initiater (B) is lower than above-mentioned scope,, maybe must increase irradiation time even also can not produce curing down via the active energy ray irradiation, otherwise be difficult to obtain suitable to membrane property.On the other hand, if the addition of Photoepolymerizationinitiater initiater can't change to light solidified when surpassing aforementioned range, so do not have an economy.

Other curable resin compositions of the present invention except that aforementioned curable resin (A), Photoepolymerizationinitiater initiater (B), also can add other photosensitivity acrylate or methacrylate compound (C) to improve light solidified.

As photosensitivity acrylate or methacrylate compound (C), can use to have 1 or above (methyl) acryl in 1 molecule, and be liquid, semisolid or solid photosensitivity acrylate or methacrylate compound under room temperature.The application target of these photosensitivity acrylate or methylacrylic acid ester cpds is outside the photoreactive purpose for light solidified that promotes flame retardant resistance and hot curing resin composition, the light solidified and the hot curing resin composition that also have flame retardant resistance are adjusted to the viscosity that various coating process suits, and increase the solvability effect to alkali aqueous solution.But, when using under the room temperature in a large number, fail the touch dry that obtains filming, and the characteristic of filming also has the tendency of deterioration, so and be not suitable for a large amount of uses to aqueous photosensitivity acrylate or methacrylate compound (C).The addition of photosensitivity acrylate or methacrylate compound (C) with respect to curable resin (A or contain F again) 100 mass parts, is 10 to 60 mass parts, is preferably the ratio of 15 to 50 mass parts.When addition surpasses aforementioned range, will make the touch dry deterioration of filming, so for not good.

As photosensitivity acrylate or methacrylate compound (C), can list for example esters of acrylic acid of hydroxyls such as 2-hydroxy ethyl methacrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, Dipentaerythritol five acrylate; Water-soluble acrylic ester such as polyethyleneglycol diacrylate, polypropyleneglycol diacrylate class; The multifunctional polyester esters of acrylic acid of polyvalent alcohols such as Viscoat 295, tetramethylol methane tetraacrylate, dipentaerythritol acrylate; The ethylene oxide adduct of polyfunctional alcohol such as TriMethylolPropane(TMP), Hydrogenated Bisphenol A or multi-phenols such as dihydroxyphenyl propane, biphenol and/or the esters of acrylic acid of propylene oxide adduct; Multifunctional or the simple function of the isocyanate addition product of the acrylate of above-mentioned hydroxyl gathers urethane acrylate; The epoxy acrylate class of (methyl) vinylformic acid affixture of bisphenol A diglycidyl ether, Hydrogenated Bisphenol A diglycidylether or phenol phenolic resin varnish, with above-mentioned methyl acrylic ester corresponding to esters of acrylic acid etc., it can be separately or with 2 kinds or above being used in combination.Be preferable with polyfunctional acrylic ester or the methacrylate compound that has 2 or above (methyl) acryl in 1 molecule again wherein.

Again, curable resin of the present invention (A) or other curable resins (F) that illustrate subsequently, can be separately or add free-radical polymerised linking agent such as vinylbenzene or merge and use with other photosensitivity acrylate or methacrylate compound, the heated polymerizable method that can be undertaken by organo-peroxide or azo-compound is solidified by the polymerized at normal temperature method that organo-peroxide and promotor are carried out.

As organo-peroxide, can list for example tert butyl peroxy benzoate, t-butyl peroxy-2-Ethylhexyl Alcohol ester, benzoyl peroxide, cyclohexanone peroxide, methylethyl ketone peroxide, two-4-butyl cyclohexyl peroxycarbonates etc., as azo-compound, can list for example azobis isobutyronitrile etc.Aforementioned known organo-peroxide or azo-compound, its can be used singly or in combination 2 kinds or more than, it uses the ratio with general quantity to get final product, generally speaking, being the ratio of 0.1 to 10 mass parts to curable resin (A or contain F again) 100 mass parts.

As promotor, for example can use the polyvalent metal salt such as sad, naphthenate of cobalt, iron, manganese etc., known compound such as organic amine such as xylidine, Diethyl Aniline, p-Tolylamine, thanomin, and can be separately or with 2 kinds or above being used in combination.

For with constituting curable resin composition, or when improving characteristic such as the scolding tin thermotolerance of solidifying tunicle, PCT patience, can cooperate epoxy compounds (D) again with curable resin of the present invention (A).

Use level as the epoxy compounds (D) of Thermocurable composition can suit according to concrete purposes to set, in general, and being that the ratio of 5～100 mass parts suits with respect to described curable resin (A) 100 mass parts.

Epoxy compounds (D) is japan epoxy resin corporate system エ ピ キ ュ ア 1 for example, エ ピ キ ュ ア 1, エ ピ キ ュ ア 1, エ ピ キ ュ ア 1, the system エ of Dainippon Ink. ﹠ Chemicals Inc Port ュ one ト 840, エ Port ュ one ト 850, エ Port コ one ト 1050, エ Port コ one ト 2055, the system エ of Toto Kasei KK Port ト one ト YD-011, YD-013, YD-127, YD-128, the system ス ミ one エ Port キ シ ESA-011 of Sumitomo Chemical Company Ltd, ESA-014, ELA-115, ELA-128 bisphenol A type epoxy resins such as (being all trade(brand)name); Japan epoxy resin corporate system エ ピ キ ュ ア one YL903, the エ of Dainippon Ink. ﹠ Chemicals Inc Port ュ one ト 152, エ Port ュ one ト 165, the system エ of Toto Kasei KK Port ト one ト YDB-400, YDB-500, Sumitomo Chemical Company Ltd's system 2 ス ミ one エ Port キ シ ESB-400, ESB-700 brominated epoxy resins such as (being all trade(brand)name); Japan epoxy resin corporate system エ ピ キ ュ ア 1, エ ピ キ ュ ア 1, the system エ of Dainippon Ink. ﹠ Chemicals Inc Port ュ one ト N-730, エ Port コ one ト N-770, エ Port コ one ト N-865, the system エ of Toto Kasei KK Port ト one ト YDCN-701, YDCN-704, Japan chemical drug corporate system EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the system ス ミ one エ Port キ シ ESCN-195X of Sumitomo Chemical Company Ltd, ESCN-220 phenolic resin varnish type epoxy resins such as (being all trade(brand)name); The system エ of Dainippon Ink. ﹠ Chemicals Inc Port コ one ト 830, japan epoxy resin corporate system エ ピ キ エ ア 1, the system エ of Toto Kasei KK Port ト one ト YDF-170, YDF-175, YDF-2004 bisphenol f type epoxy resins such as (being all trade(brand)name); The system エ of Toto Kasei KK Port ト one ト ST-2004, ST-2007, ST3000 bisphenol-A epoxy resins such as (being all trade(brand)name); Japan epoxy resin corporate system エ ピ キ ュ ア 1, the system エ of Toto Kasei KK Port ト one ト YH-434, the system ス ミ of Sumitomo Chemical Company Ltd one エ Port キ シ ELM-120 glycidyl group amine type Resins, epoxy such as (being all trade(brand)name); ダ イ セ Le chemical industry Co., Ltd. is to セ ロ キ サ イ De 2021 alicyclic epoxy resins such as (trade(brand)names); Japan epoxy resin corporate system YL-933, Japanese chemical drug corporate system EPPN-501, EPPN-502 trihydroxybenzene methylmethane type Resins, epoxy such as (being all trade(brand)name); Japan epoxy resin corporate system YL-6056, YX-4000, YL-6121 di-cresylol type or united phenol-type epoxy resin or its mixtures such as (being all trade(brand)name); Japan chemical drug corporate system EBPS-200, Asahi Electro-Chemical Co. Ltd are to EPX-30, the system EXA 1 of Dainippon Ink. ﹠ Chemicals Inc bisphenol-s epoxy resins such as (being all trade(brand)name); Japan epoxy resin corporate system エ ピ キ ュ ア one 157S bisphenol-A phenolic varnish type Resins, epoxy such as (trade(brand)names); Japan epoxy resin corporate system エ ピ キ ュ ア one YL-931 four penylene ethane type Resins, epoxy such as (trade(brand)names); The system TEPIC of daily output chemical company hetero ring type Resins, epoxy such as (trade(brand)names); The system Block レ of NOF Corp Application マ one DGT diglycidyl phthalate resins such as (trade(brand)names); The system ZX-1063 of Toto Kasei KK four glycidyl group quinolyl ethane resin such as (trade(brand)names); Chemical company of Nippon Steel system ESN-190, ESN-360, Dainippon Ink. ﹠ Chemicals Inc system HP-4032, EXA-4750, EXA-4700 (being all trade(brand)name) etc. contain naphthyl Resins, epoxy; Dainippon Ink. ﹠ Chemicals Inc system HP-7200, HP7200H (being all trade(brand)name) etc. have the Resins, epoxy of Dicyclopentadiene (DCPD) skeleton; The copoly type Resins, epoxy of NOF Corp system CP-50S, CP-50M glycidyl methacrylates such as (being all trade(brand)name); Also list the copolymerization Resins, epoxy of cyclohexyl maleimide and methacrylic ester etc.But be not limited in this.Aforementioned epoxy resins be used singly or in combination 2 kinds or more than.

Diluting soln (E) is used for aforementioned curable resin and epoxy compounds dissolving, or composition is adjusted to the viscosity that is applicable to described coating process, its use level to be being the scope of 1 to 300 mass parts with respect to curable resin (A or contain F again) 100 mass parts, and can set aptly according to selected cooperation coating process.

As diluting soln (E), can list for example ketone such as ethyl methyl ketone, pimelinketone; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; Gylcol ethers such as methylcyclohexane, ethylene glycol butyl ether, methyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ethyl ether, dipropylene glycol Anaesthetie Ether, triethylene glycol list ethyl ether; Ester classes such as ethyl acetate, butylacetate, butyl cellosolve acetate, Trivalin SF acetic ester; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrogenation naphtha, solvent naphtha etc., it can use separately or with 2 kinds or above mixing.

Again, in light solidified of the present invention and hot curing resin composition, preferred other curable resins (F) that use, as described above, as long as have carboxyl and unsaturated group in the molecule and at room temperature be the solid resin.As such curable resin, can list phenolic varnish type epoxy compounds for example and the monocarboxylic reaction product that the contains unsaturated group curable resin of addition acid anhydrides gained again, phenolic resin varnish type epoxy resin and dimethylol propionic acid and acrylic acid reaction product are reacted the curable resin (spy opens flat 6-324490 communique) of gained again with Tetra Hydro Phthalic Anhydride, the curable resin (spy opens flat 11-288091 communique) of the reaction product of phenolic resin varnish type epoxy resin and vinylformic acid and p-leptodactyline alcohol and Tetra Hydro Phthalic Anhydride reaction gained, the alcohol secondary hydroxyl and the epihalohydrins reaction that have the aromatic alcohols resin reaction gained that has 2 phenolic hydroxyls in the aromatic epoxy resin of 2 glycidyls and 1 molecule in 1 molecule, the reaction product of gained again with the monocarboxylic acid that contains unsaturated group, the curable resin of addition acid anhydrides and then, the vinyl of methacrylic acid and methyl methacrylate and interior ester modified 2-hydroxyethyl meth acrylate (for example ダ イ セ Le chemical industry Co., Ltd. system プ ラ Network セ Le FM1) is thing altogether, with the acrylate of the epoxy-cyclohexane methyl alcohol (ethylenic copolymer (spy opens flat 8-41150 communique) of サ イ Network ロ マ one-A200) the reaction gained of ダ イ セ Le chemical industry Co., Ltd. for example, the ethylenic copolymer (spy opens flat 8-259624 communique) of the ethylenic copolymer of methacrylic acid and succsinic acid modification 6-caprolactone modification 2-hydroxyethyl meth acrylate (for example プ ラ Network セ Le FM1A of ダ イ セ Le chemical industry Co., Ltd.) and epoxy group(ing) cyclohexyl methyl acrylate (for example サ イ Network ロ マ one A200 of ダ イ セ Le chemical industry Co., Ltd.) reaction gained etc., but not only be defined in this.

In the preferred version of light solidified of the present invention and hot curing resin composition, aforementioned curable resin (A) can be done suitable adjustment according to purpose with the ratio that cooperates of (F), with respect to aforementioned curable resin (A), (F) adding proportion was generally 70: 30 to 30: 70, and acid number is 30 to 150mgKOH/g, is preferably 40 to 110mgKOH/g scope.When the acid number after the cooperating of curable resin (A) and (F) is lower than 30mgKOH/g, will reduce solvability to alkali aqueous solution, make formed film to be difficult to produce develop.And when surpassing 150mgKOH/g, no matter conditions of exposure develops as what all forming in exposure portion surface, so for not good.

For promoting the reaction of curable resin and epoxy compounds, can use curing catalysts (G) again.Curing catalysts (G) is a catalyzer that the various characteristics of solder resists such as scolding tin thermotolerance, adhesivity, electroless gold plating patience is particularly more upwards promoted.

The use level of curing catalysts (G) with respect to aforementioned epoxy compounds (D) 100 mass parts, preferably cooperates 0.01 to 25 mass parts, more preferably 0.1 to 15 mass parts.

As curing catalysts (G), for example can listing, four countries change into industrial system 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, imdazole derivatives such as 2P4BHZ, 1B2PZ; Guanamines classes such as methyl guanamines, benzoguanamine; Polyamine classes such as diaminodiphenyl-methane, m-phenylenediamine, m-benzene dimethylamine, diamino diphenyl sulfone, dicyano diamide, urea, urea derivative, trimeric cyanamide, polynary hydrazine; Their organic acid salt and/or epoxy adduct; The amine complex of boron trifluoride; Ethyl diamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-pyrrolotriazine derivatives classes such as S-triazine; Trimethylamine, triethylamine, N, N-dimethyl octylame, N-benzyl dimethyl amine, pyridine, N-methylmorpholine, six (N-methyl) trimeric cyanamide, 2,4, tertiary amines such as 6-three (dimethylamino phenol), tetramethyl guanidine, m-amino-phenol; Polyphenyl phenols such as polyvinylphenol, polyvinylphenol bromide, phenol phenolic varnish, alkylphenol phenolic varnish; Organic phosphine classes such as tributylphosphine, triphenylphosphine, three-2-cyanoethyl phosphine; Quaternary ammonium salts such as benzyltrimethylammon.um muriate, phenyl three fourth ammonium muriates; Aforementioned multi-anhydride; Phenylbenzene iodine a tetrafluoro borate, triphenylsulfonium hexafluoro antimonate, 2,4, light cationic polymerisation catalysts such as 6-triphenyl thiopyridines hexafluorophosphate, Ciba corporate system Irgacure 261, system オ プ ト マ one SP-170 of rising sun electrification Co., Ltd.; The phenylethylene-maleic anhydride resin; Phenyl isocyanate and methylamine reaction with same mole thing or toluene support known habitual solidifying agent such as the reaction with same mole thing of organic polymeric polyisocyanate such as two cyanates, isophorone diisocyanate and dimethyl amine or curing catalyst etc.Aforementioned solidifying agent class or curing catalyst class, can be used singly or in combination 2 kinds or more than.

As the fire retardant that can be matched with light solidified of the present invention and hot curing resin composition (H), for example so long as get final product as the fire retardant in the resin that can make an addition to electric installation use in the past, special qualification is not arranged, with regard to regard to aspects such as the intermiscibility of resin, thermotolerance, preferably use halides flame retardant, phosphorus flame retardant and Sb system fire retardant.

The use level of fire retardant (H) with for total amount 100 mass parts of the solids component of the solids component of aforementioned curable resin (A or contain F again) and epoxy compounds (D), is generally 1 to 200 mass parts, is preferably 5 to 50 mass parts.The use level of fire retardant (H) is if in above-mentioned scope the time, can make that scolding tin is difficult hot to have the balance of height with electrical insulating property, so be preferred.

As the halides flame retardant, can list for example halogenated aromatic compounds such as hexabromobenzene, pentabromoethyl benzene, hexabromo biphenyl, decabromodiphenyl, hexabromo phenyl ether, nine bromo phenyl ether, decabromo-diphenyl oxide, tribromo-benzene base glycidyl ether, tribromo-benzene base acrylate, the two tribromo phenyl ethers of ethene, the two penta-bromophenyl ethers of ethene, the two trifluorophenyl ethers of ethene, the two penta-bromophenyl ethers of ethene, 40 bromos, two phenoxy group benzene, eight naphthalene bromides, two (tribromo phenyl) fumaramide, N-methyl hexabromo diphenylamine; Tetrabromo-bisphenol and derivative thereof [two (hydroxyethyl ether), tetrabromo-bisphenols-two (2 of the two A-of tetrabromo for example, 3-dibromopropyl ether), tetrabromo-bisphenol-two (bromotrifluoromethane ether), tetrabromo-bisphenol-two (allyl ethers) etc.], halogenated bisphenol classes such as tetrabromo-bisphenol s and derivative thereof [for example two (hydroxyethyl ether), tetrabromo-bisphenol s-two (2,3-dibromopropyl ether) of the two S-of tetrabromo etc.]: halogenated epoxy resin such as brominated epoxy resin; Halogenated aromatic polymkeric substance such as brominated Polystyrene, brominated polyphenylene support oxide compound, brominated polycarbonate, poly-pentabromobenzyl acrylate; Halo alicyclic compounds such as the affixture of the diels-Alder reaction of ethene two (5,6-dibromo norbornylene-2,3-dicarboxyl imide), pentabromo-pimelinketone, hexachlorocyclopentadiene, hexabromocyclododecane; Tetrabromophthalic anhydride and derivative thereof [for example tetrabromophthalate imide, the two tetrabromophthalate imides of ethene etc.], three-[2,3-dibromopropyl-1]-isocyanic ester etc.

As phosphorus flame retardant, can list for example three (chloroethyl) phosphoric acid ester, three (2,3-two chloropropyls) phosphoric acid ester, three (2-chloropropyl) phosphoric acid ester, three (2, the 3-bromopropyl) phosphoric acid ester, three (bromine chloropropyl) phosphoric acid ester, 2,3-dibromopropyl-2, Halogen prime system phosphate flame retardants such as 3-chloropropyl phosphoric acid ester, three (tribromo phenyl) phosphoric acid ester, three (dibromo phenyl) phosphoric acid ester, three (tribromo neo-pentyl) phosphoric acid ester; Aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, Tributyl phosphate ester, trioctylphosphine phosphoric acid ester, tri butylethyl phosphate; Triphenyl, the tolyl diphenyl phosphoester, the xylyl phenyl phosphate ester, the trimethylphenyl phosphoric acid ester, three xylyl phosphoric acid ester, the xylyl diphenyl phosphoester, three (isopropyl phenyl) phosphoric acid ester, the isopropyl phenyl diphenyl phosphoester, the diisopropyl phenyl phenyl phosphate ester, three (trimethylphenyl) phosphoric acid ester, three (tert-butyl-phenyl) phosphoric acid ester, the hydroxyphenyl diphenyl phosphoester, non-halogen such as aromatic phosphoric esters such as octyl group diphenyl phosphoester is an acid esters flame retardant etc.

As Sb system fire retardant, can list for example weisspiessglanz such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide flame retardant, sodium antimonate etc.

Aforementioned fire retardant (H) can use separately or 2 kinds or above being used in combination all can.

Light solidified of the present invention and hot curing resin composition, according to promoting characteristics such as adhesivity, hardness is purpose, in case of necessity, can add known habitual inorganic fillers such as barium sulfate, barium titanate, silica powder, micro mist shape silicon oxide, soft silica, talcum, clay, magnesiumcarbonate, lime carbonate, aluminum oxide, aluminium hydroxide, mica powder etc.Its usage quantity is preferably 0 to the 60 quality % all with respect to composition of the present invention, more preferably 5 to 40 quality %.

Again, known habitual inhibitor of polymerizations such as known habitual tinting material, quinhydrones, Hydroquinone monomethylether, tert-butyl catechol, pyrogallol, phenothiazine such as in case of necessity, can cooperate that phthalocyanine blue, phthalocyanine green, iodine are green, two azophosphines, Viola crystallina, titanium oxide, carbon black, naphthalene are black; Known habitual tackifier such as asbestos, オ Le ベ Application (organic complex of colloid hydrated aluminium silicate), wilkinite, montmorillonite, defoamer and/or flow agents such as polysiloxane series, fluorine system, macromolecular, known habitual additives such as adhesivity imparting agent such as imidazoles system, thiazole system, triazole system, silane coupling agent etc.

Again, light solidified of the present invention and hot curing resin composition, the carboxyl of curable resin (A, F) composition, can be via amines such as Trimethylamine, triethylamines, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylamide, N, acrylate or methacrylate compound that N-dimethyl (methyl) acrylamide, acryloxy morpholine, N-sec.-propyl (methyl) acrylamide, N hydroxymethyl acrylamide etc. have uncle's amino form salt, and used water is developed.

Light solidified of the present invention and hot curing resin composition if aforesaid gradation composition can add according to aforementioned ratio, and use the mill uniform mixing and make.

Again, light solidified of the present invention and hot curing resin composition, for example can be following method solidify and make cured article.Promptly, on printed circuit board (PCB), use stencil printing, spray method, rolling method, the electrostatic coating method, coating processes such as curtain formula curtain coating formation thickness is that light solidified of the present invention and the hot curing resin composition of 10 to 100 μ m filmed, after in 60 to the 110 ℃ of dryings of will filming, the minus film is directly contacted with filming (or be not disposed under the contact condition film on), subsequently via uviolizing, after unexposed use dilute alkaline aqueous solution (for example 0.5 to the 2% carbonated soda aqueous solution) dissolving removal (development), for promoting various rerum naturas, use uviolizing and/or heating (for example 100 to 200 ℃, 0.5 to 1 hour) fully to solidify to make the curing tunicle.

Below, will make specific description to the present invention with synthesis example, embodiment and comparative example, but the present invention is not limited by following examples.Again, alleged in following examples " part " is not having all to be meant mass parts under the situation about specifying.

Synthesis example 1

To have in the autoclave of thermometer, nitrogen gatherer and oxirane gatherer and whipping appts, polyphenyl phenol resins (the japan epoxy resin corporate system that adds aromatic aldehyde gained condenses with phenol and phenolic hydroxyl, trade(brand)name " エ ピ キ ュ ア one YL6065 ", OH equivalent: 98) 98 parts, 98 parts of 0.98 part in potassium hydroxide and toluene, under agitation with reaction system with nitrogen replacement, and carry out heat temperature raising.Subsequently, propylene oxide is splashed into wherein for 63.8 parts slowly, and in 125 to 132 ℃, 0 to 4.8kg/cm ²Carry out 16 hours reaction down., be cooled to room temperature under, in this reaction solution, add 89% phosphatase 11 .28 part and mix, and use the potassium hydroxide neutralization, make nonvolatile component and be 63.8%, hydroxyl equivalent is the propylene oxide reaction solution of the polyphenyl phenol resins of 160.7g/eq. thereafter.It is by obtaining for 1.08 moles with respect to the average addition epoxide of per 1 equivalent of phenolic hydroxyl.

With 0.18 part of 9.6 parts of 36.0 parts in 251.8 parts of propylene oxide reaction solution, vinylformic acid, methylsulfonic acids, the toluhydroquinone of gained polyphenyl phenol resins and 217.3 parts of toluene, insert possess stirrer is arranged, thermometer, air be blown in the reactor of pipe, the speed of air with 10ml/ minute is blown into, under agitation, reacted 12 hours down at 110 ℃.The water that generated of reaction is the mode as the azeotropic mixture that forms with toluene, distillates 9.8 parts water., be cooled under the room temperature thereafter, with the gained reaction soln with 29.4 parts of neutralizations of 15% aqueous sodium hydroxide solution, and then through the washing.Subsequently, use vaporizer that toluene is heated up in a steamer with 109.0 parts of replacements of diethylene glycol monoethyl ether acetic ester and remove, obtain nonvolatile component and be 63.3% the curable resin solution that contains unsaturated group.

Secondly, 296.4 parts of the curable resin solution and 1.22 parts of triphenylphosphines that gained are contained unsaturated group, add possess agitator is arranged, thermometer, air be blown in the reactor of pipe, the speed of air with 10ml/ minute is blown into, under agitation, add 76.0 parts of Tetra Hydro Phthalic Anhydrides slowly, in 95 to 105 ℃ were reacted 6 hours down, after the cooling, with its taking-up.Prepared in this wise curable resin, its nonvolatile component are 71.8%, and the solids component acid number is 109.6mgKOH/g.

The infrared absorption spectrum of the prepared curable resin of this synthesis example (using fourier-transform infrared line spectrophotometer FT-IR to measure) figure is as shown in Figure 1.

Synthesis example 2

To have in the autoclave of thermometer, nitrogen gatherer and oxirane gatherer and whipping appts, add polyphenyl phenol resins (japan epoxy resin corporate system, trade(brand)name " エ ピ キ ュ ア one YL6065 ", OH equivalent: 98) 98 parts, 98 parts of 0.98 part in potassium hydroxide and toluene, under agitation with reaction system with nitrogen replacement, and carry out heat temperature raising.Subsequently, propylene oxide is splashed into wherein for 174.0 parts slowly, and in 125 to 132 ℃, 0 to 4.8kg/cm ²Carry out 16 hours reaction down., be cooled to room temperature under, in this reaction solution, add 89% phosphatase 11 .28 part and mix, and use the potassium hydroxide neutralization, make nonvolatile component and be 75.1%, hydroxyl equivalent is the propylene oxide reaction solution of the polyphenyl phenol resins of 264.5g/eq. thereafter.It is by obtaining for 2.87 moles with respect to the average addition epoxide of per 1 equivalent of phenolic hydroxyl.

0.18 part of 352.2 parts of the propylene oxide reaction solution of gained polyphenyl phenol resins, 43.2 parts in vinylformic acid, 11.53 parts of methylsulfonic acids, toluhydroquinone and 273.5 parts of toluene, insert possess stirrer is arranged, thermometer, air be blown in the reactor of pipe, the speed of air with 10ml/ minute is blown into, under agitation, reacted 12 hours down at 110 ℃.The water that reaction is generated is conduct and the azeotropic mixture mode that toluene forms, and distillates 9.3 parts water., be cooled under the room temperature thereafter, with the gained reaction soln with 35.35 parts of neutralizations of 15% aqueous sodium hydroxide solution, and then through the washing.Subsequently, use vaporizer that toluene is heated up in a steamer with 203.5 parts of replacements of diethylene glycol monoethyl ether acetic ester and remove, obtain nonvolatile component and be 59.4% the curable resin solution that contains unsaturated group.

Secondly, 500.0 parts of the curable resin solution and 1.22 parts of triphenylphosphines that gained are contained unsaturated group, add possess agitator is arranged, thermometer, air be blown in the reactor of pipe, the speed of air with 10ml/ minute is blown into, under agitation, add 60.8 parts of Tetra Hydro Phthalic Anhydrides slowly, in 95 to 105 ℃ were reacted 6 hours down, after the cooling, with its taking-up.Prepared in this wise curable resin, its nonvolatile component are 64.7%, and the solids component acid number is 65.5mgKOH/g.

Synthesis example 3

To have in the autoclave of thermometer, nitrogen gatherer and oxirane gatherer and whipping appts, (ball is apt to the petroleum chemistry corporate system to add the poly(4-hydroxystyrene) resin, trade(brand)name " agate and block-M ", OH equivalent: 120) 120 parts, 120 parts of 1.2 parts in potassium hydroxide and toluene, under agitation with reaction system with nitrogen replacement, and carry out heat temperature raising.Subsequently, propylene oxide is splashed into wherein for 63.8 parts slowly, in 125 to 132 ℃, 0 to 4.8kg/cm ²Carry out 16 hours reaction down., be cooled to room temperature under, mix after in this reaction solution, adding 89% phosphatase 11 .57 part, and use the potassium hydroxide neutralization, make nonvolatile component and be 62.0%, hydroxyl equivalent is the propylene oxide reaction solution of the poly(4-hydroxystyrene) resin of 182g/eq. thereafter.It is by obtaining for 1.07 moles with respect to the average addition epoxide of per 1 equivalent of phenolic hydroxyl.

0.18 part of 293.0 parts of the oxirane reaction soln of gained poly(4-hydroxystyrene) resin, 43.2 parts in vinylformic acid, 11.53 parts of methylsulfonic acids, toluhydroquinone and 252.9 parts of toluene, insert possess stirrer is arranged, thermometer, air be blown in the reactor of pipe, the speed of air with 10ml/ minute is blown into, under agitation, reacted 12 hours down at 110 ℃.The water that reaction is generated is conduct and the azeotropic mixture mode that toluene forms, and distillates 12.6 parts water., be cooled to room temperature under, the gained reaction soln with 35.35 parts of neutralizations of 15% aqueous sodium hydroxide solution, is washed and then thereafter.Subsequently, use vaporizer that toluene is heated up in a steamer with 118.1 parts of replacements of diethylene glycol monoethyl ether acetic ester and remove, must contain the curable resin solution of unsaturated group.

Secondly, 332.0 parts of the curable resin solution and 1.22 parts of triphenylphosphines that gained are contained unsaturated group, add possess agitator is arranged, thermometer, air be blown in the reactor of pipe, the speed of air with 10ml/ minute is blown into, under agitation, add 60.8 parts of Tetra Hydro Phthalic Anhydrides slowly, in 95 to 101 ℃ were reacted 6 hours down, after the cooling, with its taking-up.Prepared in this wise curable resin, its nonvolatile component are 71.8%, and the solids component acid number is 85.3mgKOH/g.

Compare synthesis example 1

(epoxy equivalent (weight): 220) 220 parts of addings have in the four-hole boiling flask of stirrer and reflux cooler for Japanese chemical drug corporate system, trade(brand)name " ECON-104S ", add to heat behind 218 parts of the Trivalin SF acetic ester to separate with the cresols phenolic resin varnish type epoxy resin.Subsequently, 0.46 part of the toluhydroquinone that adds inhibitor of polymerization with, as 1.38 parts of the triphenylphosphines of catalysts.This mixture heating up to 95 to 105 ℃, was splashed into 50.4 parts in vinylformic acid, p-hydroxylphenylethyl alcohol wherein in 41.5 minutes slowly again, make it carry out 16 hours reaction.This reaction product is cooled to 80 to 90 ℃, adds 91.2 parts of Tetra Hydro Phthalic Anhydrides, and carry out reaction in 8 hours, after the cooling, its taking-up.Prepared in this wise curable resin, its nonvolatile component are 65%, and the solids component acid number is 84mgKOH/g.

Embodiment 1 to 3 and comparative example 1

Add various compositions according to the ratio of cooperation shown in the table 1 (numerical value is mass parts), it is mixing to use 3 roller mills to carry out respectively, with the preparation curable resin composition.It is used stencil printing, with the polyester web plate of 100 meshes in 20 to 30 μ m thickness modes, on the figuratum copper vias tellite of formation, be coated with comprehensively, the hot air dryer that uses 80 ℃ of filming carries out 30 minutes drying, on the minus film that will have corrosion-resisting pattern sticks to and films, use ultraviolet exposure apparatus according (オ one Network is made limited-liability company of institute system, model HMW-680GW) subsequently, with exposure 600mJ/cm ²Uviolizing.Secondly, the sodium bicarbonate aqueous solution of use 1% was with 60 seconds, 2.0kg/cm ²The row development is compressed in spray, and the unexposed portion dissolving is removed.Subsequently, use 150 ℃ hot-air drier to carry out 60 minutes being heating and curing, to make the test substrate.

Prepared have a test substrate that solidifies tunicle, shows after then complying with that test method and appraisal procedure carry out tests such as scolding tin thermotolerance, PCT patience, adhesivity, acid resistance, alkali resistance, electroless gold plating patience.

Again, the B pattern of copper vias tellite with the tellite (thickness 1.6mm) of IPT regulation replaced, make the test substrate, measure electrical isolation resistance according to condition same as described above.And, use sheet glass Alloy instead of Copper through hole tellite, and handle according to condition same as described above, try to achieve its water-intake rate.

The result of above-mentioned test is as described in Table 2.

Table 1

Table 2

In the above-mentioned table 2, the appraisal procedure of performance test is as described below.

The scolding tin thermotolerance:

According to the test method of JIS C 6481, the dipping that the afore-mentioned test substrate was carried out 3 times 10 seconds, its appearance change is according to following benchmarking exercise.Again, back solder flux (rosin series) is to use the solder flux of JIS C 6481 regulations.

Zero: outward appearance does not change

△: solidify tunicle and produce variable color

*: solidify that tunicle produces relief, peels off, scolding tin sink etc.

PCT patience:

With above-mentioned test board, in 170 ℃ hot air dryer, to place 5 hours again, the PCT patience after the placement is assessed according to following benchmark with under 50 hours the condition in 121 ℃, saturated steam.

Zero: solidify that tunicle does not produce expansion, peels off, variable color etc.

△: solidify that tunicle produces a little expansion, peels off, variable color etc.

*: solidify tunicle produce expand, peel off, variable color etc.

Adhesivity:

Test method according to JIS D 0202 is the chessboard reticulate pattern with above-mentioned test substrate cross cut, and it uses the state of peeling off after adhesive tape carries out stripping test according to following benchmarking exercise again.

◎: 100/100 all can not peel off

Zero: 100/100 cross cut portion has a little to peel off

△：50/100-90/100

×：0/100-50/100

Acid resistance:

Above-mentioned test substrate be impregnated in 20 ℃ the 10 capacity % aqueous sulfuric acids and take out after 30 minutes, its state that solidifies tunicle is according to following benchmarking exercise.

Zero: find no variation

△: only minority changes

*: solidifying in the tunicle has fold or swelling to come off

Alkali resistance:

Outside 10 capacity % aqueous sulfuric acids of aforesaid substrate were substituted with the aqueous sodium hydroxide solution of 10 capacity %, other carried out identical assessment with acid resisting test.

Electroless gold plating patience:

According to the aftermentioned step above-mentioned test substrate is carried out electroless gold plating, observe the appearance change of this test substrate and carry out stripping test with using the glassine paper adhesive tape, the state of peeling off that solidifies tunicle can be assessed according to following benchmark.

Zero: outward appearance does not change, and it is unstripped fully to solidify tunicle

△: outward appearance does not change, and only a little is peeled off to solidify tunicle

*: phenomenons such as the curing tunicle produces relief, and scolding tin is sagging, in stripping test, solidify the tunicle generation and much more extremely to peel off

The electroless gold plating step:

1. degreasing:

To test substrate, impregnated in 30 ℃ acid degreasing fluid (Japanese マ Network ダ one ミ ッ De Co., Ltd. system, the 20 volume % aqueous solution of Metex L-5B) 3 minutes.

2. washing:

To test substrate and impregnated in the flowing water 3 minutes.

3. soft etching:

To test substrate and at room temperature impregnated in the 14.3wt% ammonium persulfate aqueous solution 3 minutes.

4. washing:

To test substrate and impregnated in the flowing water 3 minutes.

5. acid dipping:

The test substrate at room temperature be impregnated in the aqueous sulfuric acid of 10Vol.% 1 minute.

6. washing:

To test substrate and impregnated in the flowing water 30 seconds to 1 minute.

7. interpolation catalyzer:

To test substrate, impregnated in 30 ℃ catalyzer liquid (メ Le テ ッ Network ス Co., Ltd. system, the 10 volume % aqueous solution of メ Le プ レ one ト ア Network チ ベ one 1) 7 minutes.

8. washing:

To test substrate and impregnated in the flowing water 3 minutes.

9. electroless nickel plating:

Substrate be will test, 85 ℃, the nickel-plating liquid (メ Le テ ッ Network ス Co., Ltd. system, the 20 volume % aqueous solution of メ Le Port レ one ト Ni-865M) of pH=4.6 impregnated in 20 minutes.

10. acid dipping:

The test substrate at room temperature be impregnated in the aqueous sulfuric acid of 10Vol.% 1 minute.

11. washing:

To test substrate and impregnated in the flowing water 30 seconds to 1 minute.

12. electroless gold plating:

Substrate be will test, 95 ℃, the gold plating liquid (メ Le テ ッ Network ス Co., Ltd. system, the 15 volume % of オ ウ ロ レ Network ト ロ レ ス UP, the aqueous solution of potassium auric cyanide 3 volume %) of pH=6 impregnated in 10 minutes.

13. washing:

To test substrate and impregnated in the flowing water 3 minutes.

14. heating bath:

In the warm water with 60 ℃ of test substrate dippings, after fully washing in 3 minutes, drying is done in the water filter.

Make the test substrate of electroless gold plating via abovementioned steps.

Electrical insulating property:

The electrical insulating property of above-mentioned curing tunicle is according to following benchmarking exercise.

Humidified condition: 85 ℃ of temperature, river rising in Ningxia and flowing into central Shaanxi degree 85%RH, apply voltage 110V, 500 hours.

Condition determination: minute 60 seconds applies voltage 500V.

Zero: the insulation resistance behind the humidification is 10 ⁹Or more than, do not find that copper moves

△: the insulation resistance behind the humidification is 10 ⁹Or more than, send out existing copper and move

*: the insulation resistance behind the humidification is 10 ⁸Below, send out existing copper and move

Water-intake rate:

Aforesaid substrate is used PCT device (TABAI ESPEC HASTSYSTEMTPC-412MD), under 121 ℃, 100%R.H. condition, carry out handling in 24 hours, and try to achieve the water-intake rate that solidifies tunicle according to following calculating formula.

Water-intake rate (%)=[(W2-W1)/(W1-Wg)] * 100

Wherein, W1 is the quality of test substrate, and W2 is the quality that PCT handles back test substrate, and Wg is the quality of sheet glass.

Synthesis example 4

In having stirrer, thermometer, the reflux cooling pipe, drip in 2 liters of separable flasks of funnel and nitrogen ingress pipe, add 900 parts of diethylene glycol dimethyl ethers, with tert-butyl hydroperoxide 2-ethylhexanoate (NOF Corp's system, パ one Block チ Le O) 21.4 part, after being warming up to 90 ℃, with 309.9 parts of methacrylic acids, 116.4 parts of methyl methacrylates, butyrolactone modification 2-hydroxyethyl meth acrylate (ダ イ セ Le chemical industry Co., Ltd. system, プ ラ Network セ Le FM1) 109.8 parts in becoming (4-tert-butylcyclohexyl) peroxy dicarbonate (NOF Corp's system, パ one ロ イ Le TCP) 21.4 parts splashed in the ethylene glycol dimethyl ether with 3 hour time, through slaking in 6 hours, must contain the ethylenic copolymer solution of carboxyl again.Reaction is in N ₂Carry out under the air-flow.

Subsequently, acrylate (the ダ イ セ Le chemical industry Co., Ltd. system that in ethylenic copolymer solution, adds epoxy-cyclohexane methyl alcohol, サ イ Network ロ マ one A200) 363.9 part, 1.80 parts of 3.6 parts of dimethyl benzyl amines and Hydroquinone monomethylethers, after being warming up to 100 ℃, stir so that it carries out the opening of epoxy group(ing).The curable resin that makes in this wise, its nonvolatile component are 53.8%, and the solids component acid number is 107mgKOH/g.

Synthesis example 5

With cresols phenolic resin varnish type epoxy resin (big Japanese ink chemical industrial company system, エ Port コ one ト N-695, epoxy equivalent (weight): 220) 330 parts, insert have gas introduction tube, in the flask of whipping appts, cooling tube and thermometer, adding 400 parts of Trivalin SF acetic ester, heating for dissolving adds 1.38 parts of 0.46 part of quinhydrones and triphenylphosphines.This mixture heating up to 95 to 105 ℃, is added vinylformic acid wherein for 108 parts more slowly, carry out 16 hours reaction.Reaction product is cooled to 80 to 90 ℃, adds 163 parts of Tetra Hydro Phthalic Anhydrides, carry out 8 hours reaction again.Reaction is with the oxidation of potential difference titration determination reaction solution, total oxygen mensuration, and follows the trail of the markup percentage of gained, with reactivity reach 95% or more than be terminal point.The curable resin that makes in this wise, its nonvolatile component are 58%, and the solids component acid number is 102mgKOH/g.

Embodiment 4 to 6

Add various compositions according to the ratio of cooperation shown in the table 3 (numerical value is mass parts), it is mixing to use 3 roller mills to carry out respectively, to make light solidified and hot curing resin composition.It is used the screen painting method, with the polyester web plate of 100 meshes in 20 to 30 μ m thickness modes, on the figuratum copper vias tellite of formation, be coated with comprehensively, the hot air dryer that uses 80 ℃ of filming carries out 60 minutes drying, for being used for the touch dry of aftermentioned appraisal procedure to film coated surface.

Subsequently, on the minus film that will have corrosion-resisting pattern sticks to and films, use ultraviolet exposure apparatus according (オ one Network is made limited-liability company of institute system, model HMW-680GW) subsequently, with ultraviolet ray (exposure 600mJ/cm ²) irradiation, and use 1% sodium bicarbonate aqueous solution with 60 seconds, 2.0kg/cm ²The row development is compressed in spray, according to aftermentioned appraisal procedure assessment development.

Use 150 ℃ hot-air drier carry out 60 minute being heating and curing, to make test substrate thereafter.To prepared have the test substrate that solidifies tunicle according to after show that test method and appraisal procedure carry out tests such as adhesivity, scolding tin thermotolerance, acid resistance, alkali resistance, electroless gold plating patience, PCT patience.

Again, the B pattern of copper vias tellite with the printed base plate (thickness 1.6mm) of IPC regulation replaced, make the test substrate according to condition same as described above, to carry out the electrical isolation resistance test.

The result of above-mentioned each test is as described in Table 4.

Table 3

Table 4

In the above-mentioned table 4, the appraisal procedure of touch dry characteristic and development is as described below.

Touch dry:

Touch dry to the dried coating surface is estimated.

Zero: be not clamminess fully

△: only be clamminess a little

*: have the property of being clamminess

Development:

Development face is with the visual judgement of magnifying glass

Zero: during development, remove printing ink fully and develop

*: during development, residual have a little residue, and have undeveloped part

Synthesis example 6

To have in the autoclave of thermometer, nitrogen gatherer and oxirane gatherer and whipping appts, add phenolic varnish type cresol resin (clear and polymer corporate system, trade(brand)name " Xi Nuo and CRG951 ", OH equivalent: 119.4) 119.4 parts, 119.4 parts of 1.19 parts in potassium hydroxide and toluene, under agitation will react system and replace, and carry out heat temperature raising with nitrogen.Subsequently, propylene oxide is splashed into wherein for 63.8 parts slowly, and in 125 to 132 ℃, 0 to 4.8kg/cm ²Carry out 16 hours reaction down., be cooled to room temperature under, in this reaction solution, add 89% phosphatase 11 .56 part and mix, and use the potassium hydroxide neutralization, make nonvolatile component and be 62.1%, hydroxyl equivalent is the propylene oxide reaction solution of the phenolic varnish type cresol resin of 182.2g/eq. thereafter.It is by obtaining for 1.08 moles with respect to the average addition epoxide of per 1 equivalent of phenolic hydroxyl.

0.18 part of 293.0 parts of the oxirane reaction soln of gained phenolic varnish type cresols, 43.2 parts in vinylformic acid, 11.53 parts of methylsulfonic acids, toluhydroquinone and 252.9 parts of toluene, insert possess stirrer is arranged, thermometer, air be blown in the pipe reactor, the speed of air with 10ml/ minute is blown into, under agitation, reacted 12 hours down at 110 ℃.The water that reaction is generated is conduct and the azeotropic mixture mode that toluene forms, and distillates 12.6 parts water., be cooled under the room temperature thereafter, with the gained reaction soln with 35.35 parts of neutralizations of 15% aqueous sodium hydroxide solution, and then through the washing.Subsequently, use vaporizer that toluene is heated up in a steamer with 118.1 parts of replacements of diethylene glycol monoethyl ether acetic ester and remove, obtain phenolic varnish type acrylate resin solution.

Secondly, with 1.22 parts of 332.5 parts of gained phenolic varnish type acrylate resin solution and triphenylphosphines, add possess agitator is arranged, thermometer, air be blown in the reactor of pipe, the speed of air with 10ml/ minute is blown into, under agitation, add 60.8 parts of Tetra Hydro Phthalic Anhydrides slowly, in 95 to 101 ℃ were reacted 6 hours down, after the cooling, with its taking-up.Prepared in this wise curable resin, its nonvolatile component are 70.6%, and the solids component acid number is 87.7mgKOH/g.

Synthesis example 7

To have in the autoclave of thermometer, nitrogen gatherer and oxirane gatherer and whipping appts, add polyphenyl phenol resins (japan epoxy resin corporate system, trade(brand)name " エ ピ キ ュ ア one YL6065 ", OH equivalent: 98) 98 parts, 98 parts of 0.98 part in potassium hydroxide and toluene, under agitation with reaction system with nitrogen replacement, and carry out heat temperature raising.Subsequently, propylene oxide is splashed into wherein for 63.8 parts slowly, and in 125 to 132 ℃, 0 to 4.8kg/cm ²Carry out 16 hours reaction down., be cooled to room temperature under, mix after in this reaction solution, adding 89% phosphatase 11 .28 part, and use the potassium hydroxide neutralization, make nonvolatile component and be 63.8%, hydroxyl equivalent is the propylene oxide reaction solution of the polyphenyl phenol resins of 160.7g/eq. thereafter.It is by obtaining for 1.08 moles with respect to the average addition epoxide of per 1 equivalent of phenolic hydroxyl.

0.18 part of 251.8 parts of the propylene oxide reaction solution of gained polyphenyl phenol resins, 43.2 parts in vinylformic acid, 11.53 parts of methylsulfonic acids, toluhydroquinone and 217.3 parts of toluene, insert possess stirrer is arranged, thermometer, air be blown in the pipe reactor, the speed of air with 10ml/ minute is blown into, under agitation, reacted 12 hours down at 110 ℃.The water that reaction is generated is conduct and the azeotropic mixture mode that toluene forms, and distillates 12.6 parts water., be cooled under the room temperature thereafter, with the gained reaction soln with 35.35 parts of neutralizations of 15% aqueous sodium hydroxide solution, and then through the washing.Subsequently, use vaporizer that toluene is heated up in a steamer with 113.0 parts of replacements of diethylene glycol monoethyl ether acetic ester and remove, obtain the acrylic resin soln of nonvolatile component 63.4%.

Secondly, with 304.5 parts of the curable resin solution that contains unsaturated group of gained and 1.22 parts of triphenylphosphines, add possess agitator is arranged, thermometer, air be blown in the reactor of pipe, the speed of air with 10ml/ minute is blown into, under agitation, add 60.8 parts of Tetra Hydro Phthalic Anhydrides slowly, in 95 to 105 ℃ were reacted 6 hours down, after the cooling, with its taking-up.Prepared in this wise curable resin, its nonvolatile component are 70.5%, and the solids component acid number is 93.1mgKOH/g.

Embodiment 7 to 9 and comparative example 2

Add various compositions according to the ratio of cooperation shown in the table 5 (numerical value is mass parts), it is mixing to use 3 roller mills to carry out respectively, with the light solidified and the hot curing resin composition of preparation flame retardant resistance.It is used stencil printing,, be coated with in forming on the figuratum copper vias tellite in 20 to 30 μ m thickness modes with the polyester web plate of 100 meshes comprehensively, the hot air dryer that uses 80 ℃ of filming carries out 30 minutes drying.

Subsequently, on the minus film that will have corrosion-resisting pattern sticks to and films, and use ultraviolet exposure apparatus according (オ one Network is made limited-liability company of institute system, model HMW-680GW), with ultraviolet ray (exposure 660mJ/cm ²) irradiation, the sodium bicarbonate aqueous solution of use 1% was with 60 seconds, 2.0kg/cm ²The row development is compressed in spray, and the unexposed portion dissolving is removed.Use 150 ℃ hot air dryer carry out 60 minute being heating and curing, to make test substrate thereafter.

To prepared test substrate, assess tests such as its scolding tin thermotolerance, acid resistance, alkali resistance, adhesivity, PCT patience, electroless gold plating patience according to afore-mentioned test method and appraisal procedure with curing tunicle.

Again, the copper vias tellite is substituted with glass substrate, and handle according to aforementioned the same terms, it tries to achieve its water-intake rate.Again, the B pattern of copper vias printed wiring wiring substrate with the tellite (thickness 1.6mm) of IPCT regulation replaced, make the test substrate according to condition same as described above, and carry out the electrical insulating property resistance test.

Again, the substrate of copper vias printed wiring wiring substrate with the flame retardant test specification UL94V0 regulation of the macromolecular material of U.S. Underwriters Laboratories Inc. (UL) substituted, make the test substrate according to condition same as described above, and carry out flame retardant test.

The result of above-mentioned each test is as described in Table 6.

Table 5

Table 6

The appraisal procedure of the flame retardant resistance in the above-mentioned table 6 is as described below.

Flame retardant resistance:

The flame retardant resistance of test substrate is to use device based on the flame retardant test specification UL94 of UL macromolecular material, method, assesses according to following benchmark.

Zero: demonstrate the flame retardant resistance that is equivalent to V-0

*: do not demonstrate the flame retardant resistance that is equivalent to V-0

As mentioned above, curable resin of the present invention, because side chain terminal has unsaturated group or carboxyl, so have good reactivity, and because the amount of the hydrophilic alcoholic hydroxyl of low reactivity seldom or not exists, so can obtain the thermotolerance of high level and the balance of PCT patience, and can form the cured article of various characteristicses such as good adhesion or hardness, resistance to chemical reagents, anti-water absorbability to substrate.Therefore contain this cured resin, the curable resin composition that contains gained such as Photoepolymerizationinitiater initiater, photosensitivity acrylate or methacrylate compound, epoxy compounds, diluting solvent simultaneously, except that showing good alkali-developable, also can provide the cured article of needed excellent heat resistances such as solder resist, PCT patience, adhesivity, resistance to chemical reagents, electroless gold plating patience, electrical insulating property, anti-water absorbability etc. such as densification corresponding to printed circuit board (PCB), face assemblingization.

Therefore; light solidified and hot curing resin composition that aforementioned curable resin is contained as the solidified nature composition; except that ultraviolet hardening printing-ink purposes that can be used for using active energy ray to be cured etc.; it is exposed to the curing tunicle is peeled off by the base material generation; and have aforementioned various good characteristic, so the utmost point is suitable for making interlayer insulating film, the manufacturing employed permanent light shield of thin-film package of the employed solder resist of printed circuit board (PCB), multilayer circuit board even makes the employed protective layer of colored filter.When using light solidified with excellent flame retardancy and hot curing resin composition, be expected to realize the high installationization of reliability of electronics again.

Claims (9)

1. curable resin; It is by by the product (c) of the compound (a) that has 3 or above phenolic hydroxyl in 1 molecule with alkylene oxide (b) gained; React with the monocarboxylic acid that contains unsaturated group (d); The curable resin that the product of gained (e) obtains with multi-anhydride (f) reaction again; Wherein said compound (a) is from selecting by among the phenol shown in the following formula (III) and the condensation product of aromatic series aldehydes gained with phenolic hydroxyl and the poly(4-hydroxystyrene)

In the formula, R is that hydrogen atom or carbon number are 1 to 18 alkyl, and X is hydrogen atom or halogen atom, and Y is that carbon number is 1 to 18 alkyl or alkoxyl group, and k is 0,1 or 2 integer, and m is 0 or above integer.

2. curable resin as claimed in claim 1, the wherein said monocarboxylic acid (d) that contains unsaturated group is vinylformic acid and/or methacrylic acid.

3. curable resin as claimed in claim 1, wherein said multi-anhydride (f) is the ester ring type dibasic acid anhydride.

4. curable resin composition, it contains each described curable resin in the claim 1 to 3.

5. light solidified and hot curing resin composition, it contains (A) curable resin, (B) Photoepolymerizationinitiater initiater, (C) photosensitivity acrylate or methacrylate compound, (D) epoxy compounds, reach (E) diluting solvent, wherein said curable resin is by by the reaction product (c) of the compound (a) that has 3 or above phenolic hydroxyl in 1 molecule with oxirane (b) gained, react with the monocarboxylic acid that contains unsaturated group (d), the reaction product of gained (e) obtains with multi-anhydride (f) reaction again, wherein said compound (a) be from by the phenol shown in the following formula (III) with have the condenses of the aromatic series aldehydes gained of phenolic hydroxyl, and select among the poly(4-hydroxystyrene)

In the formula, R is that hydrogen atom or carbon number are 1 to 18 alkyl, and X is hydrogen atom or halogen atom, and Y is that carbon number is 1 to 18 alkyl or alkoxyl group, and k is 0,1 or 2 integer, and m is 0 or above integer.

6. light solidified and hot curing resin composition, it contains (A) curable resin, (B) Photoepolymerizationinitiater initiater, (C) photosensitivity acrylate or methacrylate compound, (D) epoxy compounds, (E) diluting solvent, and (F) has carboxyl in the molecule with unsaturated group and at room temperature be the solid curable resin, wherein said curable resin is by by the reaction product (c) of the compound (a) that has 3 or above phenolic hydroxyl in 1 molecule with oxirane (b) gained, react with the monocarboxylic acid that contains unsaturated group (d), the reaction product of gained (e) obtains with multi-anhydride (f) reaction again, described compound (a) be from by the phenol shown in the following formula (III) with have the condenses of the aromatic series aldehydes gained of phenolic hydroxyl, and select among the poly(4-hydroxystyrene)

In the formula, R is that hydrogen atom or carbon number are 1 to 18 alkyl, and X is hydrogen atom or halogen atom, and Y is that carbon number is 1 to 18 alkyl or alkoxyl group, and k is 0,1 or 2 integer, and m is 0 or above integer.

7. as claim 5 or 6 described light solidified and hot curing resin compositions, it also contains (G) curing catalysts.

8. as claim 5 or 6 described light solidified and hot curing resin compositions, it also contains (H) fire retardant.

9. light solidified as claimed in claim 8 and hot curing resin composition, wherein said fire retardant (H) are at least a kind that selects among halogenated epoxy resin, halogenated aromatic compound, halo alicyclic compound, phosphoric acid ester flame retardant and weisspiessglanz flame retardant.

Images