CN101652396A

CN101652396A - Resin composition for optical material, resin film for optical material, and optical waveguide using them

Info

Publication number: CN101652396A
Application number: CN200880004478A
Authority: CN
Inventors: 牧野龙也; 高桥敦之; 山口正利; 高崎俊彦; 柴田智章; 落合雅美
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Showa Denko Materials Co ltd
Priority date: 2007-02-14
Filing date: 2008-02-08
Publication date: 2010-02-17

Abstract

Disclosed is a resin composition for optical material, which contains a carboxylic acid-modified phenoxy resin (A), a polymerizable compound (B) and a polymerization initiator (C). Also disclosed area resin film for optical material obtained from such a resin composition, and an optical waveguide having a core portion and/or a cladding layer, each formed by using the resin composition and/or theresin film. The resin composition for optical material is excellent in heat resistance and transparency, while being soluble in an aqueous alkaline solution.

Description

Resin composition for optical material, resin for optical material film and used these optical waveguides

Technical field

The present invention relates to resin composition for optical material, resin for optical material film and used these optical waveguides, relate in particular to thermotolerance and transparency excellence, and dissolve in the resin composition for optical material of the alkaline aqueous solution, resin for optical material film of making by this resin combination and the optical waveguides of having used these.

Background technology

In recent years, in the transmission of the high speed between electronic component or between wiring substrate, high density signal, with regard to the transmission of in the past dependence electric wiring, the mutual interference or the decay of signal become obstacle, begin to see at a high speed, the limit of densification.Studying to use up and connecting between electronic component or the technology between wiring substrate, promptly so-called optical interconnection in order to break this limit.From the degree of freedom height of the easiness of processing, low cost, distribution and angle that can densification, polymer optical wave guide receives publicity as the transmission road of light.As the form of polymer optical wave guide, the imagination of studying that has is applicable to the type of making, the imagination web plate softish type that does not have hard support substrate each other of optical/electrical mixed mounting substrate on the glass epoxy resin substrate.

From viewpoints such as the environment for use of the machine that is suitable for or parts installations, also require high heat resistance when requiring high transparent (low propagation loss) for polymer optical wave guide, as such optical waveguide material, known have (methyl) acrylate copolymer (for example referring to

Patent Document

1 and 2)., though (methyl) acrylate copolymer has the high transparent of 0.3dB/cm to wavelength 850nm, stable on heating evaluation is indeterminate, for example, does not have concrete record about the concrete experimental results such as loss of light propagation after the experiment of backflow scolding tin.

As the excellent heat resistance and the photosensitive polymer combination that can develop with alkaline aqueous solution, known have a resin combination (for example referring to Patent Document 3 and 4) that contains carboxyl acid modified phenoxy resin.But this based resin composition is the material of inventing at the electro-cladding in the printed circuit board manufacturing process, though excellent heat resistance, the transparency is low, is not suitable as resin composition for optical material.

Patent documentation 1: Japanese kokai publication hei 06-258537 communique

Patent documentation 2: TOHKEMY 2003-195079 communique

Patent documentation 3: TOHKEMY 2000-47383 communique

Patent documentation 4: TOHKEMY 2000-147765 communique

Summary of the invention

The present invention carries out in order to solve above-mentioned problem, it is excellent and dissolve in the resin composition for optical material of the alkaline aqueous solution that purpose provides thermotolerance and the transparency, resin for optical material film of being made up of this resin combination and the optical waveguides of having used these.

The result that the inventor furthers investigate repeatedly, discovery contain (A) carboxyl acid modified phenoxy resin by use and contain simultaneously (B) polymerizable compound and (C) polymerization starter the resin composition for optical material that dissolves in the alkaline aqueous solution, by the resin for optical material thin film fabrication optical waveguides that this resin combination is made, can solve above-mentioned problem.

That is the optical material of, the invention provides the resin composition for optical material that contains (A) carboxyl acid modified phenoxy resin, (B) polymerizable compound, (C) polymerization starter, being made by this resin combination is with film and have and use the core that described resin composition for optical material or described resin for optical material film form and/or the optical waveguides of covering.Wherein, described (A) carboxyl acid modified phenoxy resin contains by the repeating unit (A-1) of following general formula (1) expression and the repeating unit of being represented by following general formula (2) (A-2).

[changing 1]

(in the formula, X ¹Expression

[changing 2]

In the group of divalent arbitrarily.X ²The organic group of the divalent of expression carbonatoms 1～20.

Y ¹Expression

[changing 3]

In divalent group arbitrarily.R ¹～R ¹⁹Represent in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 any one independently of one another.A represents 2～10 integer.)

[changing 4]

(in the formula, X ³Expression

[changing 5]

In the group of divalent arbitrarily.

Y ²Expression

[changing 6]

In the group of divalent arbitrarily.R ²⁰～R ³⁸Represent in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 any one independently of one another.B represents 2～10 integer.)

Resin composition for optical material of the present invention and the optical material of being made by this resin combination dissolve in the alkaline aqueous solution with film, use the thermotolerance and the transparency excellence of the optical waveguides of these manufacturings.

Description of drawings

Fig. 1 is the figure of the mode of explanation optical waveguides of the present invention, is sectional view.

Temperature profile in the reflow ovens in the backflow experiment that Fig. 2 represents to implement in the present invention.

Nomenclature

The 1st, optical waveguides; The 2nd, core; The 3rd, upper clad layer; The 4th, following wrap; The 5th, substrate or overlay film.

Embodiment

Resin composition for optical material of the present invention contains (A) carboxyl acid modified phenoxy resin, (B) polymerizable compound and (C) polymerization starter.Further preferred irradiation meeting solidified resin combination by heating or active ray.

Below, (A) of the present invention to being used for composition describes.

The carboxyl acid modified phenoxy resin of (A) of the present invention as being used for composition is preferably dissolved in the developing solution of being made by alkaline aqueous solution, and has the deliquescent phenoxy resin of practicable development treatment degree as purpose.From the transparency, thermotolerance, to the deliquescent viewpoint of alkaline aqueous solution, use and contain on the main chain by the repeating unit (A-1) of following general formula (1) expression with by the carboxyl acid modified phenoxy resin of the repeating unit (A-2) of following general formula (2) expression.

[changing 7]

(in the formula, X ¹Expression

[changing 8]

Y ¹Expression

[changing 9]

In the group of divalent arbitrarily.R ¹～R ¹⁹Represent in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 any one independently of one another.A represents 2～10 integer.)

[changing 10]

(in the formula, X ³Expression

[changing 11]

In the group of divalent arbitrarily.

Y ²Expression

[changing 12]

As the organic group in general formula (1) and (2); can enumerate for example alkyl; cycloalkyl; aryl; aralkyl; carbonyl; carboxyl; ester group; amide group; carbonate group; urethano; alkoxyl group; aryloxy; alkyl thio-base; the aryl thio group; amino; silyl; vinyl; allyl group; the group of 1 valencys such as (methyl) acryl or divalent, these can be further by hydroxyl; halogen atom; alkyl; cycloalkyl; aryl; aralkyl; carbonyl; carboxyl; ester group; amide group; carbonate group; urethano; alkoxyl group; aryloxy; alkyl thio-base; the aryl thio group; amino; silyl; vinyl; allyl group; replacements such as (methyl) acryl.In addition, (methyl) acryl is represented acryl and/or methacryloyl.

In the carboxyl acid modified phenoxy resin of (A) composition, have preferred 10～99 quality % of containing ratio of the repeating unit (A-1) of 2 officials energy phenol skeleton and carboxyl.If more than 10 quality %, will be soluble in the developing solution of making by alkaline aqueous solution etc., if below 99 quality %, optionally remove the layer of photosensitive polymer combination and in the developing procedure of formation pattern, make anti-development fluidity (can not be removed the part that becomes pattern and not be developed liquid erosive character) good by development described later by development.From above viewpoint, more preferably 20～95 quality %, preferred especially 30～90 quality %.

2 officials can phenol skeleton and have the structure of the repeating unit (A-1) of carboxyl, so long as can just have no particular limits with the structure that general formula (1) is represented.Can phenol skeleton X as 2 officials that are used for repeating unit (A-1) ¹Can enumerate and for example derive from quinhydrones, Resorcinol, catechol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1, monokaryon 2 officials such as 7-naphthalenediol energy phenol, their organic group substituent and the skeleton of fluorine-containing organic group substituent; Derive from 2,2 '-biphenyl, 4, the skeleton of fluorine-containing organic group substituents such as multinuclear 2 officials such as 4 '-biphenyl, dihydroxyphenyl propane, tetrabromo-bisphenol, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, fluorenes type bis-phenol can phenol, their organic group substituent and bisphenol AF etc.Wherein, from the transparency and stable on heating viewpoint, preferably derive from above-mentioned multinuclear 2 officials energy phenol, their organic group substituent and the skeleton of fluorine-containing organic group substituent such as bisphenol AF.These skeletons can separately or will be used in combination more than 2 kinds.

As the organic group X that is used for repeating unit (A-1) ², so long as the divalent organic group of carbonatoms 1～20 just has no particular limits, can enumerate for example following groups:

[changing 13]

Wherein, from the transparency, thermotolerance and deliquescent viewpoint, preferred

[changing 14]

Here, above-mentioned illustrated organic group X ²" * " marked carbon atoms that is contained be with above-mentioned general formula (1) in X ²The carbon atom combination of adjacent carboxyl, organic group X ²" * * " marked carbon atoms adjacent that is contained with carboxyl be with above-mentioned general formula (1) in X ²Adjacent Sauerstoffatom combination.

These organic groups can separately or will be used in combination more than 2 kinds.

In the carboxyl acid modified phenoxy resin of (A) composition, has preferred 1～90 quality % of containing ratio of the repeating unit (A-2) of 2 officials energy phenol skeleton and hydroxyl.If more than 1 quality %, form in the developing procedure of pattern at the layer of optionally removing photosensitive polymer combination according to developing described later, anti-development fluidity is good, if will be soluble in the developing solution of being made up of alkaline aqueous solution etc. below 90 quality %.From above viewpoint, further preferred 5～80 quality %, especially preferred 10～70 quality %.

Structure with repeating unit (A-2) of 2 officials energy phenol skeleton and hydroxyl is so long as just having no particular limits with general formula (2) expression.Can phenol skeleton X as 2 officials that are used for repeating unit (A-2) ³, can enumerate and derive from for example quinhydrones, Resorcinol, catechol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1, monokaryon 2 officials such as 7-naphthalenediol energy phenol, their organic group substituent and the skeleton of fluorine-containing organic group substituent; Derive from 2,2 '-biphenyl, 4, the skeleton of fluorine-containing organic group substituents such as multinuclear 2 officials such as 4 '-biphenyl, dihydroxyphenyl propane, tetrabromo-bisphenol, Bisphenol F, dihydroxyphenyl propane D, bisphenol S, fluorenes type bis-phenol can phenol, their organic group substituent and bisphenol AF etc.Wherein, from the transparency and stable on heating viewpoint, preferably derive from above-mentioned multinuclear 2 officials energy phenol, their organic group substituent and the skeleton of fluorine-containing organic group substituent such as bisphenol AF.These skeletons can separately or will be used in combination more than 2 kinds.

(A) the carboxyl acid modified phenoxy resin of composition, have no particular limits for its synthetic method, for example can obtain by the following method: phenoxy resin is dissolved in the solvent, use suitable catalyzer as required, in 60～115 ℃ of temperature, carry out the addition reaction of multi-anhydride, be formed on carboxylic phenoxy resin in its molecule.Can adjust the usage quantity of multi-anhydride, make above-mentioned repeating unit (A-1) and containing ratio (A-2) reach above-mentioned scope.

Can enumerate succinyl oxide, Pyroglutaric acid, itaconic anhydride, maleic anhydride, citraconic anhydride, Tetra hydro Phthalic anhydride, tetrahydronaphthalic anhydride, hexahydro phthalic anhydride, trimellitic acid 1,2-anhydride, hexahydro-trimellitic acid 1,2-anhydride etc. as multi-anhydride.

Can enumerate methane amide, N-methylformamide, N as suitable solvents, acid amides series solvents such as dinethylformamide, ethanamide, N-methylacetamide, N,N-dimethylacetamide, 2-Pyrrolidone, N-Methyl pyrrolidone; Ketone series solvents such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), propione, diisobutyl ketone, cyclopentanone, pimelinketone, methylcyclohexanone, methyl phenyl ketone, methyl ethyl diketone; Ether series solvents such as ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Glycol Monomethyl ether, propylene glycol monomethyl ether acetic ester, Diethylene Glycol monomethyl ether, diethylene glycol dimethyl ether.

Can enumerate organo phosphorous compoundss such as hexamethyl phosphoric triamide, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (chloropropyl) ester, trimethyl phosphite 99, tri-n-butyl phosphine, tri isopropyl phosphine, tricyclohexyl phosphine, triphenyl phosphite, phenyl-phosphonic acid, triphenylphosphine, diphenylphosphine as catalyzer; Secondary amine such as tri-n-butyl amine, benzyl methylamine, monomethylaniline; Triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, diethyl Isopropylamine, benzyldimethylamine, N, accelerine, N, N, N ', N '-tertiary amines such as Tetramethyl Ethylene Diamine; Tetramethyleneimine, N-crassitude, piperidines, N-methyl piperidine, morpholine, N-methylmorpholine, piperazine, N, N '-lupetazin, 1,4-diazabicylo [2.2.2] octane, 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, 1,8-diazabicylo [5.4.0] 11 carbon-cyclic amine such as 7-alkene; Imidazoles, the 1-Methylimidazole, glyoxal ethyline, 4-methylimidazole, the 1-ethyl imidazol(e), the 2-ethyl imidazol(e), the 4-ethyl imidazol(e), the 1-isopropylimdazole, 2 isopropyl imidazole, the 4-isopropylimdazole, the 2-undecyl imidazole, 2-heptadecyl imidazoles, the 1-phenylimidazole, the 2-phenylimidazole, the 4-phenylimidazole, 2, the 4-methylimidazole, 2,4-diethyl imidazoles, 2,4-di-isopropyl imidazoles, 2, the 4-diphenyl-imidazole, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, the 1-1-cyanoethyl-2-methylimidazole, benzoglyoxaline, the glyoxal ethyline quinoline, 2-undecyl imidazole quinoline, imidazoles such as 2-heptadecyl tetrahydroglyoxaline; Quaternary ammonium salts such as tetrabutylammonium chloride, tetra-n-butyl ammonium bromide, tetrabutylammonium iodide, benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide etc.

These compounds can separately or will be used in combination more than 2 kinds.

Further, (A) the carboxyl acid modified phenoxy resin of composition can contain the ethene unsaturated group as required on side chain.Its composition or synthetic method are had no particular limits, for example can make above-mentioned (A) the carboxyl acid modified phenoxy resin and the compound of 1 functional group containing at least 1 ethene unsaturated group and epoxy group(ing), oxetanyl, isocyanate group, hydroxyl, carboxyl etc. carry out addition reaction or condensation reaction, and on its side chain, import the ethene unsaturated group.

Be not particularly limited as this compounds, can enumerate Racemic glycidol (methyl) acrylate, α-ethyl Racemic glycidol (methyl) acrylate, α-n-propyl Racemic glycidol (methyl) acrylate, α-normal-butyl Racemic glycidol (methyl) acrylate, 2-methyl Racemic glycidol (methyl) acrylate, 2-ethyl Racemic glycidol (methyl) acrylate, 2-propyl group Racemic glycidol (methyl) acrylate, 3,4-epoxy butyl (methyl) acrylate, 3,4-epoxy heptyl (methyl) acrylate, α-ethyl-6,7-epoxy heptyl (methyl) acrylate, 3,4-epoxycyclohexyl methyl (methyl) acrylate, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, the compound that vinyl benzyl glycidyl ether etc. is contained ethene unsaturated group and epoxy group(ing); (2-ethyl-2-oxetanyl) methyl (methyl) acrylate, (2-methyl-2-oxetanyl) methyl (methyl) acrylate, 2-(2-ethyl-2-oxetanyl) ethyl (methyl) acrylate, 2-(2-methyl-2-oxetanyl) ethyl (methyl) acrylate, 3-(2-ethyl-2-oxetanyl) propyl group (methyl) acrylate, 3-(2-methyl-2-oxetanyl) propyl group (methyl) acrylate etc. contains the compound of ethene unsaturated group and oxetanyl; Isocyanic acid ethyl (methyl) acrylate etc. contains the compound of ethene unsaturated group and isocyanate group; 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-chloro-2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate etc. contain the compound of ethene unsaturated group and hydroxyl; (methyl) vinylformic acid, Ba Dousuan, styracin, succsinic acid (2-(methyl) acryloyl-oxy ethyl ester), 2-phthalyl ethyl (methyl) acrylate, 2-tetrahydro-phthalyl ethyl (methyl) acrylate, 2-hexahydro-phthalyl ethyl (methyl) acrylate, ω-carboxyl-polycaprolactone one (methyl) acrylate, 3-vinyl M-nitro benzoic acid, 4-vinyl M-nitro benzoic acid etc. contain the compound of ethene unsaturated group and carboxyl etc.Wherein (methyl) acrylate is meant acrylate and methacrylic ester.

Wherein, from the transparency and reactive viewpoint, preferred Racemic glycidol (methyl) acrylate, 3,4-epoxycyclohexyl methyl (methyl) acrylate etc. contains the compound of ethene unsaturated group and epoxy group(ing); Isocyanic acid ethyl (methyl) acrylate isocyanic acid ethyl (methyl) acrylate etc. contains the compound of ethene unsaturated group and isocyanate group; 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-chloro-2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate etc. contain the compound of ethene unsaturated group and hydroxyl; (methyl) vinylformic acid, Ba Dousuan, 2-hexahydro-phthalyl ethyl (methyl) acrylate etc. contain the compound of ethene unsaturated group and carboxyl.These compounds can separately or will be used in combination more than 2 kinds.

(A) weight-average molecular weight of the carboxyl acid modified phenoxy resin of composition preferred 1,000～300,000.If more than 1,000, owing to molecular weight makes the intensity when making resin combination enough greatly, if 3,000, below 000, for the solvability of the developing solution of forming by alkaline aqueous solution, or good with the intermiscibility of (B) composition polymerizable compound.From above viewpoint further preferred 3,000～2,000,000, especially preferred 5,000～1,000,000.In addition, weight-average molecular weight of the present invention is to measure with gel permeation chromatography (GPC), and the value that converts with polystyrene standard.

(A) the carboxyl acid modified phenoxy resin of composition forms in the developing procedure of pattern at the layer of optionally removing photosensitive polymer combination by developing described later, acid number can be defined as and can develop by enough known various developing solutions.

For example, under the situation that alkaline aqueous solutions such as using yellow soda ash, salt of wormwood, Tetramethylammonium hydroxide, trolamine develops, the preferred 20～300mg KOH/g of acid number.If more than 20mg KOH/g, just develop easily, if below 300 mg KOH/g, anti-development fluidity just can not be low.From above viewpoint, further preferred 30～250mg KOH/g, especially preferred 40～200mg KOH/g.

Under the situation of using the alkaline aqueous solution development of forming by water or alkaline aqueous solution and the organic solvent more than a kind, the preferred 10～250mg KOH/g of acid number.If more than 10mg KOH/g, just develop easily, if below 250 mg KOH/g, anti-development fluidity just can not be low.From above viewpoint, further preferred 20～200mg KOH/g, especially preferred 30～150mg KOH/g.

(A) use level of the carboxyl acid modified phenoxy resin of composition preferably for (A) composition and (B) total amount of composition be 10～85 quality %.If more than 10 quality %, form in the developing procedure of pattern at the layer of optionally removing photosensitive polymer combination by developing described later, can develop with known various developing solutions, if below 85 quality %, be entangled to and curing easily by (B) composition during exposure, anti-development fluidity can be sufficient.From above viewpoint, further preferred 20～80 quality %, especially preferred 25～75 quality %.

Below, (B) of the present invention to being used for composition describes.

The polymerizable compound of (B) of the present invention as being used for composition is so long as by heating or irradiation such as ultraviolet ray and polymeric just has no particular limits, can enumerate the compound that for example contains the ethene unsaturated group.Concrete can enumerate (methyl) acrylate, vinylidene halide, Vinyl Ether, vinyl acetate, vinyl pyridine, vinylamide, arylation ethene etc., wherein from the viewpoint of the transparency, and preferred (methyl) acrylate or the arylation ethene of using.As (methyl) acrylate, can use 1 functional (methyl) acrylate, 2 officials can (methyl) acrylate or 3 officials any one in can above polyfunctional (methyl) acrylate.

As simple function (methyl) acrylate, can enumerate for example methyl (methyl) acrylate, ethyl (methyl) acrylate, butyl (methyl) acrylate, isobutyl-(methyl) acrylate, the tertiary butyl (methyl) acrylate, butoxyethyl group (methyl) acrylate, isopentyl (methyl) acrylate, hexyl (methyl) acrylate, 2-ethylhexyl (methyl) acrylate, heptyl (methyl) acrylate, octyl group (methyl) acrylate, nonyl (methyl) acrylate, decyl (methyl) acrylate, undecyl (methyl) acrylate, dodecyl (methyl) acrylate, tridecyl (methyl) acrylate, tetradecyl (methyl) acrylate, pentadecyl (methyl) acrylate, hexadecyl (methyl) acrylate, stearyl (methyl) acrylate, docosyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-chloro-2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, oxyethyl group polyoxyethylene glycol (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, oxyethyl group polypropylene glycol (methyl) acrylate, aliphatics (methyl) acrylate such as single (2-(methyl) acrylyl oxy-ethyl) succinate; Ester ring type (methyl) acrylate such as cyclopentyl (methyl) acrylate, cyclohexyl (methyl) acrylate, 2-tetrahydrofuran (THF) (methyl) acrylate, two cyclopentyl (methyl) acrylate, dicyclopentenyl (methyl) acrylate, isobornyl (methyl) acrylate, list (2-(methyl) acrylyl oxy-ethyl) tetrahydrophthalic acid ester, list (2-(methyl) acrylyl oxy-ethyl) hexahydrophthalic acid ester; Benzyl (methyl) acrylate, phenyl (methyl) acrylate, adjacent biphenyl (methyl) acrylate, 1-naphthyl (methyl) acrylate, 2-naphthyl (methyl) acrylate, phenoxy group ethyl (methyl) acrylate, to cumyl phenoxy group ethyl (methyl) acrylate, adjacent phenyl phenoxy group ethyl (methyl) acrylate, 1-naphthyloxy ethyl (methyl) acrylate, 2-naphthyloxy ethyl (methyl) acrylate, 2-(methyl) acrylyl oxy-ethyl-N-carbazole, phenoxy group polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, phenoxy group polypropylene glycol (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 2-hydroxyl-3-(adjacent phenyl phenoxy group) propyl group (methyl) acrylate, 2-hydroxyl-3-(1-naphthyloxy) propyl group (methyl) acrylate, 2-hydroxyl-3-(2-naphthyloxy) propyl group (methyl) acrylate, aromatic series (methyl) acrylate such as single (2-(methyl) acrylyl oxy-ethyl) phthalic ester; And their caprolactone modification body etc.

Wherein, from the transparency and stable on heating viewpoint, preferred above-mentioned ester ring type (methyl) acrylate; Benzyl (methyl) acrylate, phenyl (methyl) acrylate, adjacent biphenyl (methyl) acrylate, 1-naphthyl (methyl) acrylate, 2-naphthyl (methyl) acrylate, phenoxy group ethyl (methyl) acrylate, to cumyl phenoxy group ethyl (methyl) acrylate, adjacent phenyl phenoxy group ethyl (methyl) acrylate, 1-naphthyloxy ethyl (methyl) acrylate, 2-naphthyloxy ethyl (methyl) acrylate, 2-(methyl) acrylyl oxy-ethyl-N-carbazole, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 2-hydroxyl-3-(adjacent phenyl phenoxy group) propyl group (methyl) acrylate, 2-hydroxyl-3-(1-naphthyloxy) propyl group (methyl) acrylate, 2-hydroxyl-3-(2-naphthyloxy) propyl group (methyl) acrylate, aromatic series (methyl) acrylate such as single (2-(methyl) acrylyl oxy-ethyl) phthalic ester.

Can enumerate ethylene glycol bisthioglycolate (methyl) acrylate by (methyl) acrylate as 2 officials, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, four propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, ethoxylation polypropylene glycol two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, the 3-methyl isophthalic acid, 5-pentanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 2-butyl-2-ethyl-1, ammediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,1 0-decanediol two (methyl) acrylate, glycerol two (methyl) acrylate, ethoxylation 2-methyl isophthalic acid, aliphatics (methyl) acrylate such as ammediol two (methyl) acrylate; Cyclohexanedimethanol (methyl) acrylate, ethoxylation cyclohexanedimethanol (methyl) acrylate, propoxylation cyclohexanedimethanol (methyl) acrylate, ethoxylation propoxylation cyclohexanedimethanol (methyl) acrylate, tristane dimethanol (methyl) acrylate, ethoxylation tristane dimethanol (methyl) acrylate, propoxylation tristane dimethanol (methyl) acrylate, ethoxylation propoxylation tristane dimethanol (methyl) acrylate, ethoxylation Hydrogenated Bisphenol A two (methyl) acrylate, propoxylation Hydrogenated Bisphenol A two (methyl) acrylate, ethoxylation propoxylation Hydrogenated Bisphenol A two (methyl) acrylate, ethoxylation A Hydrogenated Bisphenol A F two (methyl) acrylate, propoxylation A Hydrogenated Bisphenol A F two (methyl) acrylate, ester ring type (methyl) acrylate such as ethoxylation propoxylation A Hydrogenated Bisphenol A F two (methyl) acrylate; Ethoxylation dihydroxyphenyl propane two (methyl) acrylate, propoxylated bisphenol two (methyl) acrylate, ethoxylation propoxylated bisphenol two (methyl) acrylate, ethoxylation Bisphenol F two (methyl) acrylate, propoxylation Bisphenol F two (methyl) acrylate, ethoxylation propoxylation Bisphenol F two (methyl) acrylate, ethoxylation bisphenol AF two (methyl) acrylate, propoxylated bisphenol F two (methyl) acrylate, ethoxylation propoxylated bisphenol F two (methyl) acrylate, ethoxylation fluorenes type two (methyl) acrylate, propoxylation fluorenes type two (methyl) acrylate, aromatic series (methyl) acrylate such as ethoxylation propoxylation fluorenes type two (methyl) acrylate; And caprolactone modification body; Aliphatic epoxy (methyl) acrylate such as neopentyl glycol type epoxy (methyl) acrylate; Ester ring type epoxy (methyl) acrylate such as cyclohexanedimethanol type epoxy (methyl) acrylate, Hydrogenated Bisphenol A type epoxy (methyl) acrylate A Hydrogenated Bisphenol A F type epoxy (methyl) acrylate; Aromatic epoxies (methyl) acrylate such as Resorcinol type epoxy (methyl) acrylate, bisphenol type epoxy (methyl) acrylate, Bisphenol F type epoxy (methyl) acrylate, bisphenol AF type epoxy (methyl) acrylate, fluorenes type epoxy (methyl) acrylate etc.

Wherein, from the transparency and stable on heating viewpoint, preferred above-mentioned ester ring type (methyl) acrylate; Above-mentioned aromatic series (methyl) acrylate; Above-mentioned ester ring type epoxy (methyl) acrylate; Above-mentioned aromatic epoxies (methyl) acrylate.

As above multifunctional (methyl) acrylate of 3 officials energy, can enumerate for example trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, ethoxylation propoxylation trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, ethoxylation tetramethylolmethane three (methyl) acrylate, pentaerythritol propoxylate three (methyl) acrylate, ethoxylation pentaerythritol propoxylate three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, ethoxylation tetramethylolmethane four (methyl) acrylate, pentaerythritol propoxylate four (methyl) acrylate, ethoxylation pentaerythritol propoxylate four (methyl) acrylate, the ditrimethylolpropane tetraacrylate, aliphatics (methyl) acrylate such as Dipentaerythritol six (methyl) acrylate; Hetero ring type (methyl) acrylate such as ethoxylation tricarbimide three (methyl) acrylate, propoxylation tricarbimide three (methyl) acrylate, ethoxylation propoxylation tricarbimide three (methyl) acrylate; And caprolactone modification body; Aromatic epoxies (methyl) acrylate such as phenol phenolic varnish type epoxy (methyl) acrylate, cresols phenolic varnish type epoxy (methyl) acrylate.

Wherein, from the transparency and stable on heating viewpoint, hetero ring type (methyl) acrylate such as preferred ethoxylation tricarbimide three (methyl) acrylate, propoxylation tricarbimide three (methyl) acrylate, ethoxylation propoxylation tricarbimide three (methyl) acrylate; Aromatic epoxies (methyl) acrylate such as phenol phenolic varnish type epoxy (methyl) acrylate, cresols phenolic varnish type epoxy (methyl) acrylate.These compounds can separately or will be used in combination more than 2 kinds, can also be used in combination with other polymerizable compound.

And, as (B) composition polymerizable compound, contain at least a kind and more than a kind of from the group who forms by alicyclic structure, aryl, aryloxy and aralkyl, selecting of compound of ethene unsaturated group the molecule from preferred use of stable on heating viewpoint.Concrete can enumerate at least a kind (methyl) acrylate containing selection among the group who forms by alicyclic structure, aryl, aryloxy and aralkyl or N-vinylcarbazole etc.In addition, aryl is represented for example heteroaromatic formula groups such as aromatic hydrocarbyl such as phenyl, naphthyl, carbazyl.

More particularly, preferably use by at least 1 in the compound of following general formula (3)～(6) expression as (B) composition polymerizable compound.Perhaps, be more preferably use by at least a kind in the compound that contains aryl and ethene unsaturated group of following general formula (3)～(6) expression as (B) composition polymerizable compound.

[changing 15]

(in the formula, Ar represents

[changing 16]

In 1 valency group arbitrarily.X ⁴Expression Sauerstoffatom, sulphur atom or OCH ₂, SCH ₂, O (CH ₂CH ₂O) _c, O (CH ₂CH (CH ₃) O) _d, OCH ₂CH (OH) CH ₂The group of divalent arbitrarily among the O.

Y ³Expression

[changing 17]

In the group of divalent arbitrarily.

R ³⁹In expression hydrogen atom, the methyl any one.R ⁴⁰～R ⁵⁶Represent in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 any one independently of one another.C and d represent 1～20 integer independently of one another, and e represents 2～10 integer.)

[changing 18]

(in the formula, R ⁵⁷Expression

[changing 19]

R ⁵⁸～R ⁶⁰Represent any one in hydrogen atom, the methyl independently of one another.F represents 1～10 integer.)

[changing 20]

(in the formula, X ⁵, X ⁷Represent Sauerstoffatom, sulphur atom or O (CH independently of one another ₂CH ₂O) _g, O[CH ₂CH (CH ₃) O] _hIn the group of divalent arbitrarily.

X ⁶Expression

[changing 21]

In the group of divalent arbitrarily.R ⁶¹, R ⁶⁶Represent any one in hydrogen atom, the methyl independently of one another.R ⁶²～R ⁶⁵Represent in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 any one independently of one another.G and h represent 1～20 integer independently of one another, and i represents 2～10 integer.)

[changing 22]

(in the formula, X ⁸Expression

[changing 23]

In the group of divalent arbitrarily.R ⁶⁷, R ⁷²Represent any one in hydrogen atom, the methyl independently of one another.R ⁶⁸～R ⁷¹Represent in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 any one independently of one another.J represents 1～5 integer, and k represents 2～10 integer.)

In addition, as the organic group in general formula (3)～(6), can enumerate identical example with explanation in general formula (1) and (2).

And, beyond (methyl) acrylate as preferred (B) composition polymerizable compound, from the viewpoint of the intermiscibility of the carboxyl acid modified phenoxy resin of (A) composition, can also enumerate and contain the material that molecule includes the compound of the epoxy group(ing) more than 2.

Specifically can enumerate 2 officials energy phenol glycidyl ethers such as bisphenol A type epoxy resin, tetrabromo-bisphenol type Resins, epoxy, bisphenol f type epoxy resin, bisphenol AF type Resins, epoxy, dihydroxyphenyl propane D type Resins, epoxy, biphenyl type epoxy resin, naphthalene type Resins, epoxy, fluorenes type Resins, epoxy; Bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type Resins, epoxy, hydrogenation 2,2 '-Lian phenol-type epoxy resin, hydrogenation 4, hydrogenation 2 officials such as 4 '-Lian phenol-type epoxy resin energy phenol glycidyl ether; Multifunctional phenol glycidyl ethers such as phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, Dicyclopentadiene (DCPD)-phenol type Resins, epoxy, four phenol ethane type Resins, epoxy; Polyethylene glycol type Resins, epoxy, polypropylene glycol type Resins, epoxy, neopentyl glycol type Resins, epoxy, 1,2 officials such as 6-hexylene glycol type Resins, epoxy energy fatty alcohol glycidyl ether; 2 officials such as cyclohexanedimethanol type Resins, epoxy, tristane dimethanol type Resins, epoxy energy ester ring type alcohol glycidyl ether; Trimethylolpropane type Resins, epoxy, multifunctional aliphatics such as Sorbitol Powder type Resins, epoxy, glycerol type Resins, epoxy alcohol glycidyl ether; 2 officials such as o-phthalic acid diglycidyl ester energy aromatic series glycidyl ester; 2 officials such as tetrahydrophthalic acid 2-glycidyl ester, hexahydro-phthalic acid 2-glycidyl ester energy ester ring type glycidyl ester; N, N-diglycidylaniline, N, 2 officials such as N-diglycidyl 5-trifluoromethylaniline energy aromatic series glycidyl amine; N, N, N ', N '-four glycidyl group-4,4-diaminodiphenyl-methane, 1, two (N, the N-glycidyl-amino methyl) hexanaphthenes of 3-, N, N, multifunctional aromatic series glycidyl amines such as O-triglycidyl group-p-aminophenol; 2 officials such as ester ring type bicyclic oxygen acetal, ester ring type bicyclic oxygen adipic acid ester, ester ring type bicyclic oxygen carboxylicesters, vinyl cyclohexene dioxide energy alicyclic epoxy resin; 2,1 of two (the methylol)-1-butanols of 2-, multifunctional alicyclic epoxy resins such as 2-epoxy-4-(2-Oxyranyle) hexanaphthene affixture; Multifunctional hetero ring type Resins, epoxy such as triglycidyl group chlorinated isocyanurates; 2 officials such as organopolysiloxane type Resins, epoxy can or the multifunctional epoxy silicone etc. that contains.

Wherein, from the transparency and stable on heating viewpoint, the 2 officials energy phenol glycidyl ether of preferred bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type Resins, epoxy, dihydroxyphenyl propane D type Resins, epoxy, biphenyl type epoxy resin, naphthalene type Resins, epoxy, fluorenes type Resins, epoxy etc.; Above-mentioned hydrogenation 2 officials energy phenol glycidyl ether; Above-mentioned multifunctional phenol glycidyl ether; Above-mentioned 2 officials energy ester ring type alcohol glycidyl ether; Above-mentioned 2 officials energy aromatic series glycidyl ester; Above-mentioned 2 officials energy ester ring type glycidyl ester; Above-mentioned 2 officials energy alicyclic epoxy resin; Above-mentioned multifunctional alicyclic epoxy resin; Above-mentioned multifunctional hetero ring type Resins, epoxy; Above-mentioned 2 officials can or the multifunctional epoxy silicone that contains.These compounds can separately or will be used in combination more than 2 kinds, can also be used in combination with other polymerizable compound.

(B) use level of the polymerizable compound of composition is for (A) composition and (B) total amount of composition, preferred 15～90 quality %.If more than 15 quality %, be entangled to the carboxyl acid modified phenoxy resin of (A) composition and curing easily, do not have the insufficient situation of anti-development fluidity, if below 90 quality %, then develop easily.From above viewpoint, further preferred 20～80 quality %, especially preferred 25～75 quality %.

Below, (C) of the present invention to being used for composition describes.

(C) of the present invention as being used for composition polymerization starter, so long as can be by heating or irradiation such as ultraviolet ray and just the having no particular limits of initiated polymerization, for example use under the situation of the compound that contains the ethene unsaturated group as (B) composition polymerizable compound, can enumerate hot radical polymerization starter, optical free radical polymerization starter etc., but preferably use the optical free radical polymerization starter, because curing speed can carry out ambient cure soon.

As the hot radical polymerization starter, can enumerate for example ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, peroxidation methylcyclohexanone; 1, two (tert-butyl peroxide) hexanaphthenes, 1 of 1-, two (the tert-butyl peroxide)-2-methylcyclohexanes, 1 of 1-, two (tert-butyl peroxide)-3,3 of 1-, 5-trimethyl-cyclohexane, 1, two (the peroxidation uncle hexyl) hexanaphthenes, 1 of 1-, two (the peroxidation uncle hexyls)-3,3 of 1-, ketal peroxides such as 5-trimethyl-cyclohexane; Hydrogen peroxide is to hydroperoxide such as menthanes; α, α '--dialkyl peroxides such as two (tert-butyl peroxide) diisopropylbenzene(DIPB), dicumyl peroxide, tertiary butyl cumyl peroxide, ditertiary butyl peroxide; Diacyl peroxides such as peroxidation decoyl, lauroyl peroxide, stearoyl, benzoyl peroxide; Peroxycarbonates such as two (4-tert-butylcyclohexyl) peroxy dicarbonate, two-2-ethoxyethyl group peroxy dicarbonate, two-2-ethylhexyl peroxy dicarbonate, two-3-methoxyl group butyl peroxy carbonic ether; The peroxidation trimethylacetic acid tert-butyl ester, the own ester of peroxidation trimethylacetic acid uncle, 1,1,3,3-tetramethyl butyl peroxidation-2-ethylhexanoate, 2,5-dimethyl-2, two (peroxidation of the 2-ethyl hexanoyl) hexanes of 5-, uncle's hexyl peroxidation-2-ethylhexanoate, tert-butyl hydroperoxide-2-ethylhexanoate, the tert-butyl hydroperoxide isobutyrate, uncle's hexyl peroxidation sec.-propyl one carbonic ether, tert-butyl hydroperoxide-3,5,5-tri-methyl hexanoic acid ester, the tert-butyl hydroperoxide laurate, tert-butyl hydroperoxide sec.-propyl one carbonic ether, tert-butyl hydroperoxide-2-ethylhexyl one carbonic ether, tert butyl peroxy benzoate, uncle's hexyl peroxide benzoate, 2,5-dimethyl-2, two (benzoyl peroxidation) hexanes of 5-, peroxyesters such as tert-butyl hydroperoxide acetic ester; 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two azo-compounds such as (4-methoxyl groups-2 '-methyl pentane nitrile).

Wherein, from solidified nature, the transparency and stable on heating viewpoint, diacyl peroxides such as preferred peroxidation decoyl, lauroyl peroxide, stearoyl, benzoyl peroxide; 1,1,3,3-tetramethyl butyl peroxidation-2-ethylhexanoate, 2,5-dimethyl-2, two (peroxidation of the 2-ethyl hexanoyl) hexanes of 5-, uncle's hexyl peroxidation-2-ethylhexanoate, tert-butyl hydroperoxide-2-ethylhexanoate, the tert-butyl hydroperoxide isobutyrate, uncle's hexyl peroxidation sec.-propyl one carbonic ether, tert-butyl hydroperoxide-3,5,5-tri-methyl hexanoic acid ester, the tert-butyl hydroperoxide laurate, tert-butyl hydroperoxide sec.-propyl one carbonic ether, tert-butyl hydroperoxide-2-ethylhexyl one carbonic ether, tert butyl peroxy benzoate, uncle's hexyl peroxide benzoate, 2,5-dimethyl-2, two (benzoyl peroxidation) hexanes of 5-, peroxyesters such as tert-butyl hydroperoxide acetic ester; 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two azo-compounds such as (4-methoxyl groups-2 '-methyl pentane nitrile).

As the optical free radical polymerization starter, can enumerate 2,2-dimethoxy-1,2-diphenylethane-bitter almond oil camphor ketals such as 1-ketone; 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-alpha-alcohol ketones such as 1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 1,2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-alpha-amino group ketone such as 1-ketone; 1-[4-(thiophenyl) phenyl]-1, oxime esters such as 2-octadione-2-(benzoyl) oxime; Two (2,4,6-Three methyl Benzene formyl) phenylphosphine oxide, two (2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide, 2,4, phosphine oxides such as 6-Three methyl Benzene formyl diphenylphosphine superoxide; 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-two (p-methoxy-phenyl) imidazole dimer, 2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dipolymer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer etc. 2,4,5-triarylimidazoles dipolymer; Benzophenone, N, N '-tetramethyl--4,4 ' diaminobenzophenone, N, N '-tetraethyl--4,4 ' diaminobenzophenone, 4-methoxyl group-4 '-benzophenones such as dimethylamino benzophenone; 2-ethyl-anthraquinone, phenanthrenequione, 2-tertiary butyl anthraquinone, prestox anthraquinone, 1,2-benzo anthraquinone, 2,3-benzo anthraquinone, 2-phenyl anthraquinone, 2,3-phenylbenzene anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinones, 9,10-phenanthrenequione, 2-methyl isophthalic acid, 4-naphthoquinones, 2, quinones such as 3-dimethyl anthraquinone; Benzoin ether such as benzoin methylether, ethoxybenzoin, bitter almond oil camphor phenyl ether; Bitter almond oil camphor classes such as bitter almond oil camphor, methylbenzene acyloin, ethylbenzene acyloin; Dibenzoyl classes such as dibenzoyl dimethyl acetal; 9-phenylacridine, 1, the two acridines such as (9,9 '-acridyl heptane) of 7-; N-phenylglycine, tonka bean camphor etc.

And above-mentioned 2,4, in the 5-triarylimidazoles dipolymer, the substituting group of the aryl at 2 triarylimidazoles positions can be identical and becomes symmetric compound, also can be different and become asymmetrical compound.And, as the combination of diethyl thioxanthone and dimethylamino M-nitro benzoic acid, can also be with thioxanthene ketone and tertiary amine combination.

Wherein, from solidified nature, the transparency and stable on heating viewpoint, preferred above-mentioned alpha-alcohol ketone; Above-mentioned phosphine oxide.This type of light and heat radical polymerization initiator can separately or will be used in combination more than 2 kinds.Further, can also be used in combination with suitable sensitizing agent.

And, use as (B) composition polymerizable compound under the situation of Resins, epoxy, as (C) composition polymerization starter, can enumerate hot cationic polymerization initiators or light cationic polymerization initiators etc., curing speed preferably makes and uses the light cationic polymerization initiators, because can carry out ambient cure soon.

As hot cationic polymerization initiators, can enumerate for example benzyl sulfonium salt such as palkoxy benzene base benzyl methyl sulfonium hexafluoro antimonate; Benzyl is to pyridinium salts such as cyanopyridine hexafluoro antimonate, the adjacent cyanopyridine hexafluoro antimonate of 1-naphthyl methyl, the adjacent cyanopyridine hexafluoro antimonates of cinnamyl; Benzyl ammonium salts such as benzyl dimethyl phenyl ammonium hexafluoro antimonate etc.Wherein, from solidified nature, the transparency and stable on heating viewpoint, benzyl sulfonium salts such as preferred palkoxy benzene base benzyl methyl sulfonium hexafluoro antimonate.

As the light cationic polymerization initiators, can enumerate for example to aryl two nitrogen salts such as anisole phenodiazine phosphofluoric acid esters; Diaryl group iodized salts such as phenylbenzene iodine phosphofluoric acid ester, phenylbenzene iodine hexafluoro antimonate; Triphenylsulfonium phosphofluoric acid ester, triphenylsulfonium hexafluoro antimonate, phenylbenzene-4-sulfo-Phenoxyphenyl sulfonium phosphofluoric acid ester, phenylbenzene-4-sulfo-Phenoxyphenyl sulfonium hexafluoro antimonate, phenylbenzene-triarylsulfonium salts such as 4-sulfo-Phenoxyphenyl sulfonium five fluorine hydroxyl stibnates; Triaryl selenium salt such as triphenyl selenium hexafluorophosphate, triphenyl selenium a tetrafluoro borate, triphenyl selenium hexafluoro antimonate; Dialkyl group benzoyl methyl sulfonium salts such as dimethyl benzoyl methyl sulfonium hexafluoro antimonate, diethyl benzoyl methyl sulfonium hexafluoro antimonate; Dialkyl group-4-hydroxy salts such as 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-hydroxy phenyl benzyl methyl sulfonium hexafluoro antimonate; Alpha-hydroxy methylbenzene acyloin sulphonate, N-hydroxyl imide sulphonate, α-sulfonyloxy ketone, β-sulphonates such as sulfonyloxy ketone etc.

Wherein, from solidified nature, the transparency and stable on heating viewpoint, be preferably above-mentioned triarylsulfonium salt.These light and heat radical polymerization initiators can separately or will be used in combination more than 2 kinds.Further, can also be used in combination with suitable sensitizing agent.

For (A) composition and (B) total amount 100 mass parts of composition, (C) preferred 0.1～10 mass parts of the use level of composition polymerization starter.Will be abundant if more than 0.1 mass parts, solidify, if below 10 mass parts, just can obtain sufficient light transmission.From above viewpoint, further preferred 0.3～7 mass parts, especially preferred 0.5～5 mass parts.

And, in addition as required, can in resin composition for optical material of the present invention, add antioxidant according to effect of the present invention is not caused dysgenic ratio, xanthochromia prevents so-called additives such as agent, UV light absorber, visible light absorber, tinting material, softening agent, stablizer, weighting agent.

Below, resin composition for optical material of the present invention is described.

Resin composition for optical material of the present invention also can use as the resin for optical material lacquer with the appropriate organic solvent dilution.As employed organic solvent here, so long as can dissolve just having no particular limits of this resin combination, for example can enumerate tetrahydrofuran (THF), methyl alcohol, ethanol, Virahol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ethyl acetate, butylacetate, gamma-butyrolactone, methyl lactate, ethyl lactate, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ethyl cellosolve acetate, the propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic ester, toluene, dimethylbenzene, N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone etc.

Wherein, viewpoint from solvability and boiling point, be preferably methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, methyl lactate, ethyl lactate, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic ester, toluene, dimethylbenzene, N, dinethylformamide.This type of organic solvent may be used singly or in combination of two or more.And the solid component concentration in the resin paint is preferably 20～80 quality % usually.

When being in harmonious proportion the resin for optical material lacquer, preferably by mixing.Stirring means has no particular limits, and from the viewpoint of stirring efficiency, has preferably used the stirring of water screw.The speed of rotation of water screw has no particular limits during stirring, and is preferred 10～1,000rpm.If more than 10rpm, (A)～(C) each composition of composition and organic solvent is by thorough mixing, if 1, below the 000rpm, because the bubble that the rotation of water screw produces will lack.From above viewpoint, more preferably 50～800rpm, especially preferred 100～500rpm.For churning time without limits, but preferred 1～24 hour.If 1 hour, (A)～(C) each composition of composition and organic solvent if below 24 hours, can shorten the mediation time of lacquer with regard to the energy thorough mixing.

Resin for optical material lacquer after the mediation preferably uses 50 μ m following strainer in aperture to filter.If big foreign matter just can be removed less than 50 μ m in the aperture, when dope, can not take place not to be stained with etc., and the scattering of light of propagating at core is suppressed.More preferably use the strainer below the 30 μ m of aperture to filter from above viewpoint, especially preferably use 10 μ m following strainer in aperture to filter.

Resin for optical material lacquer after the mediation preferably under reduced pressure carries out deaeration.Defoaming method has no particular limits, and as object lesson, can use the defoaming device that has vacuum pump and bell glass, vacuum unit.Pressure during decompression has no particular limits, but the organic solvent that preferred resin lacquer is contained ebullient pressure not.Have no particular limits preferred 3～60 minutes for the vacuum deaerator time.If more than 3 minutes, just can remove dissolved bubble in the resin paint.If below 60 minutes, the organic solvent that resin paint contained just can not volatilize.

To contain (A) of the present invention carboxyl acid modified phenoxy resin, (B) polymerizable compound and (C) resin composition for optical material of polymerization starter carry out polymerization, solidify the cured film that forms, its specific refractory power under 25 ℃ of temperature, wavelength 830nm is preferably 1.400～1.700.If be 1.400～1.700, because do not have big difference, so can not impair versatility as optical material with the specific refractory power of common optical resin.From above viewpoint, further preferred 1.425～1.675, especially preferred 1.450～1.650.

To contain (A) of the present invention carboxyl acid modified phenoxy resin, (B) polymerizable compound and (C) resin composition for optical material of polymerization starter to carry out polymerization, solidify the thickness that forms be the cured film of 50 μ m, its transmitance under wavelength 400nm is preferred more than 80%.If more than 80%, the optical transmission amount is abundant.From above viewpoint, further preferred more than 85%.In addition, the upper limit of transmitance is not done special restriction.

Below, resin for optical material film of the present invention is described.

Resin for optical material film of the present invention is formed by above-mentioned resin composition for optical material, and resin for optical material lacquer that can above-mentioned with containing (A)～(C) composition is coated on the suitable substrates film, easily makes by removing to desolvate.And, resin composition for optical material directly can also be coated on the base material film and make.

As base material film, have no particular limits, can enumerate for example polyester such as polyethylene terephthalate, polybutylene terephthalate, PEN; Polyolefine such as polyethylene, polypropylene; Polycarbonate, polymeric amide, polyimide, polyamidoimide, polyetherimide, polythioether, polyethersulfone, polyetherketone, polyphenylene oxide, polyphenylene sulfide, poly-aryl compound, polysulfones, liquid crystalline polymers etc.Wherein, from the viewpoint of flexibility and obdurability, polyester, polypropylene, polycarbonate, polymeric amide, polyimide, polyamidoimide, polyphenylene oxide, polyphenylene sulfide, poly-aryl compound, polysulfones such as preferred polyethylene terephthalate, polybutylene terephthalate, PEN.

The thickness of base material film can be according to the flexibility appropriate change as purpose, preferred 3～250 μ m.If more than 3 μ m, film strength is just abundant, if just can obtain sufficient flexibility below 250 μ m.From above viewpoint, further preferred 5～200 μ m, especially preferred 7～150 μ m.In addition, from the viewpoint of raising, can use as required by silicon-type compound, fluorochemicals etc. and implement the film that the demoulding is handled with the separability of resin layer.

The resin for optical material film that is coated with resin for optical material lacquer or resin composition for optical material and makes on base material film, pasting protective film on resin layer becomes the 3-tier architecture of being made up of base material film, resin layer and protective membrane as required.

As protective membrane, have no particular limits, can enumerate polyester such as polyethylene terephthalate, polybutylene terephthalate, PEN; Polyolefine such as polyethylene, polypropylene etc.Wherein, from the viewpoint of flexibility and obdurability, polyester such as preferred polyethylene terephthalate; Polyolefine such as polyethylene, polypropylene.In addition, from the viewpoint of raising, can use as required by silicon-type compound, fluorochemicals etc. and implement the film that the demoulding is handled with the separability of resin layer.The thickness of overlay film can be according to the flexibility appropriate change as purpose, preferred 10～250 μ m.If more than 10 μ m, film strength is just abundant, if below 250 μ m, just can obtain sufficient flexibility.From above viewpoint, further preferred 15～200 μ m, especially preferred 20～150 μ m.

Resin layer thickness for resin for optical material film of the present invention is not done special qualification, but dried thickness is generally 5～500 μ m.If more than 5 μ m, because thickness is abundant, the intensity of the cured article of resin film or this film will be abundant, if below 500 μ m, since dry carry out fully, the residual solvent amount in the resin film just can not increase, and can not foam when heating the cured article of this film.

Resin composition for optical material of the present invention is fit to do optical waveguides formation and uses resin combination, same resin for optical material film of the present invention to be fit to do optical waveguides formation resin film.

Below, optical waveguides of the present invention is described.

The sectional view of (a) expression optical waveguides of Fig. 1.Optical waveguides 1 is formed on the substrate 5, is formed the core 2 made with resin combination and formed following wrap 4 and the upper clad layer 3 made with resin combination with the covering of low-refraction by the core with high refractive index to constitute.Resin composition for optical material of the present invention and resin for optical material film are preferred at least 1 in following wrap 4, core 2 and the upper clad layer 3 of optical waveguides 1.Wherein, from can form the viewpoint of pattern by the developing solution of forming by alkaline aqueous solution, further preferably be used for core 2 at least.

By using the resin for optical material film, the pattern in the time of can improving interlayer adaptation between covering and the core or waveguide core pattern more and form forms property (fine rule or narrow distance between centers of tracks correspondence), can form the little fine pattern of wire spoke or distance between centers of tracks.And, the technology of so-called productivity excellence that can disposable manufacturing big area optical waveguides can be provided.

In optical waveguides 1, can use hard substrate as the glass epoxy resin substrate of silicon substrate, glass substrate or FR-4 etc. as substrate 5.Also can use aforementioned substrates film to replace aforesaid substrate, make optical waveguides 1 become flexible optical waveguides with flexibility and obdurability.

And, using under the situation of base material film as substrate 5 with flexibility and obdurability, substrate 5 can be brought into play the function of the overlay film of optical waveguides 1.By configuration overlay film 5, give the flexibility or the obdurability of overlay film 5 can for optical waveguides 1.And,, therefore can improve the easness of operation because optical waveguides 1 can not made dirty or sustain damage.From above viewpoint, can shown in Fig. 1 (b),, or shown in Fig. 1 (c), dispose overlay films 5 in two outsides of following wrap 4 and upper clad layer 3 at the outside of upper clad layer 3 configuration overlay film 5.If optical waveguides 1 possesses sufficient flexibility or obdurability, can shown in Fig. 1 (d), not dispose overlay film 5 yet.

The thickness of following wrap 4 has no particular limits, but preferred 2～200 μ m.If more than 2 μ m, just can easily propagates light be enclosed in in-core portion, if below 200 μ m, all thickness of optical waveguides 1 is just not too large.In addition, the thickness of following wrap 4 be from the border of 4 of core 2 and following wraps to wrap 4 down below value.

The thickness that forms with resin film for following wrap has no particular limits, and can adjust its thickness and make the thickness of the following wrap 4 after the curing in above-mentioned scope.

The height of core 2 has no particular limits, but preferred 10～100 μ m.If the height of core is more than 10 μ m, align tolerance limit with being subjected to after optical waveguides forms in the combining of luminous element or optical fiber just can not be little, if below 100 μ m, with being subjected in the combining of luminous element or optical fiber after optical waveguides forms, joint efficiency just can not be little.From above viewpoint, the height of core is preferred 15～80 μ m further, especially preferred 20～70 μ m.In addition, the thickness that forms with resin film for core has no particular limits, and can adjust thickness and make the height of the core after the curing in above-mentioned scope.

The thickness of upper clad layer 3 is as long as in scope that can embedding core 2, just have no particular limits, but preferred dried thickness is 12～500 μ m.As the thickness of upper clad layer 3, with the thickness of the following wrap 4 of initial formation identical or different all can, but from the viewpoint of embedding core 2, preferably the thickness than wrap 4 down is thick.In addition, the thickness of upper clad layer 3 is meant from the value of border above upper clad layer 3 of 4 of core 2 and following wraps.

With regard to optical waveguides of the present invention, the preferred light propagation loss is below 0.3dB/cm.If below 0.3dB/cm, the loss of light is little, the intensity abundance of transmitting signal.From above viewpoint further preferably below 0.2dB/cm.

And, with regard to optical waveguides of the present invention, implement loss of light propagation behind the backflow test of 265 ℃ of 3 top temperatures preferably below 0.3dB/cm.If below 0.3dB/cm, the loss of light is little, can carry out installing according to the parts of reflux technique in the sufficient while of the intensity of transmitting signal, and it is extensive that subject range becomes.In addition, the backflow test of 265 ℃ of top temperatures is meant the unleaded Reflow Soldering test of implementing based on JEDEC standard (JEDECJESD22A113E).

Below, to being that the suitable example that optical waveguides forms situation about using with resin is elaborated as optimal purposes with resin for optical material film of the present invention.

Optical waveguides forms also can be according to the method manufacturing same with above-mentioned resin for optical material film with resin film.In addition, as the base material that uses in the manufacturing processed that forms at core with resin film, so long as be used for the exposure permeable base material of active ray that core pattern described later forms, just have no particular limits, can enumerate for example polyester such as polyethylene terephthalate, polybutylene terephthalate, PEN; Polyolefine such as polyethylene, polypropylene; Polycarbonate, polyphenylene oxide, poly-aryl compound etc.Wherein, from the viewpoint of exposure with transmitance, flexibility and the obdurability of active ray, polyester such as preferred polyethylene terephthalate, polybutylene terephthalate; Polyolefine such as polypropylene.Further, expose with the transmitance of active ray and the viewpoint that reduces the sidewall be full of cracks of core pattern, further preferably use the base material film of high transparent type from improving.As the base material film of so high transparent type, can enumerate COSMOSHINE A1517, COSMOSHINE A4100 that Toyo Boseki K.K makes.In addition, from the viewpoint of raising, can use as required by silicon-type compound, fluorochemicals etc. and implement the film that the demoulding is handled with the separability of resin layer.

Core forms the scope with preferred 5～50 μ m of thickness of the base material film of resin film.If more than 5 μ m, enough as the intensity of support, below the 50 μ m, the gap that photomask and core formed with the resin combination layer when core pattern formed can not become greatly, and pattern formation property is good.From above viewpoint, the thickness of base material film is the scope of preferred 10～40 μ m further, especially preferred 15～30 μ m.

The optical waveguides that is provided with on base material that so obtains forms uses film, can for example preserve easily by being rolled into the cylinder shape.And, the film of cylinder shape can also be cut into suitable size, with flaky preservation.

Below, the manufacture method that wrap, core and upper clad layer under optical waveguides formation is used for resin film is formed optical waveguides 1 describes.

At first, will descend wrap to form with the resin film lamination at wrap 4 on the substrate 5 and under forming.As the lamination method, can enumerate limit heating edge crimping and method of lamination etc.Here, from the preferred lamination under reduced pressure of the viewpoint of adaptation and tracing ability.Preferred 40～130 ℃ of the Heating temperature of optical waveguides formation usefulness resin film, the preferred 0.1～1.0MPa degree of crimping pressure (1～10kgf/cm ²Degree), still these conditions are had no particular limits.Exist under the situation of protective membrane on forming with resin film at following wrap, carry out lamination after removing protective membrane.

Then, will descend wrap to form with resin film by light and/or be heating and curing, and peel off down wrap and form base material film, and core formed use resin film according to method lamination same as described above with resin film.Here, core forms the specific refractory power height that preferably is designed to form than following wrap the usefulness resin film with resin film, and by making by the photosensitive polymer combination that active ray forms the core pattern.Then, exposure core, the core pattern (core 2) of formation optical waveguides.Be exactly to shine active ray with the image shape particularly by the egative film or the positive mask pattern case that are called as former figure.And, can also directly draw method with laser, not by photomask and directly with image shape irradiation active ray.As the light source of active ray, can enumerate carbon arc lamp, mercury vapor arc lamp, extra-high-pressure mercury vapour lamp, high pressure mercury vapour lamp, xenon lamp etc. and radiate ultraviolet known light source effectively.And other can also enumerate the lamp that photoflood lamp, sun lamp etc. radiate visible light effectively.In addition, after the exposure, from improving the viewpoint of resolving power and raising core pattern adaptation, also can be at the exposure post-heating.Time from uviolizing to the exposure post-heating is preferably in 10 minutes.If in 10 minutes, just can not inactivation by the spike that uviolizing causes.Preferred 40～160 ℃ of the temperature of exposure post-heating, preferred 30 seconds～10 minutes of time.

Peel off core after the exposure and form base material film, form developing solution corresponding to above-mentioned core, by known method development such as for example spray, shake dipping, brush, scrape with the composition of resin film with alkaline aqueous solution, water system developing solution etc. with resin film.And, can be as required also with the developing method more than 2 kinds.

Alkali as above-mentioned alkaline aqueous solution, have no particular limits, can enumerate for example alkali hydroxides such as oxyhydroxide of lithium, sodium or potassium, carbonic acid alkali such as the carbonate of lithium, sodium, potassium or ammonium or supercarbonate, alkali metal phosphate such as potassiumphosphate, sodium phosphate, alkali metal pyrophosphate such as trisodium phosphate, potassium pyrophosphate, sodium salt such as borax, Starso, Tetramethylammonium hydroxide, trolamine, quadrol, Diethylenetriamine, 2-amino-2-methylol-1, ammediol, 1,3-diamino-propanol-organic basess such as 2-morpholine.The scope of the pH of the alkaline aqueous solution that is used to develop preferred 9～11, its temperature form according to core and adjust with the development of resin combination layer.And, can sneak into tensio-active agent, defoamer in the alkaline aqueous solution, for a spot of organic solvent of promoting to develop etc.

As above-mentioned water system developing solution, so long as the solution of being made up of water or alkaline aqueous solution and the organic solvent more than a kind just has no particular limits.The pH of water system developing solution is preferably little as far as possible in above-mentioned core forms the scope that can fully carry out with the development of resin film, preferred pH8～12, further preferred pH9～10.As above-mentioned organic solvent, can enumerate for example tri acetylacetonate alcohol, acetone, ethyl acetate, methyl alcohol, ethanol, Virahol, butanols, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methyl carbitol, Diethylene Glycol one ether, Diethylene Glycol monobutyl ether etc.These can separately or will be used in combination more than 2 kinds.The concentration of organic solvent is preferred 2～90 quality % usually, and its temperature forms according to core and adjusts with the development of resin combination layer.And, can sneak into tensio-active agent, defoamer etc. on a small quantity in the aqueous solution.

As the processing after developing, heating or 0.1～1000mJ/cm as required by carrying out 60～250 ℃ of degree ²The exposure of degree is further solidified the core pattern and is used.

Then, upper clad layer is formed with resin film and use and above-mentioned same method lamination forms upper clad layer 3.Here, upper clad layer forms with resin film and is designed to form with the specific refractory power of resin film low than core.Then, can use and above-mentioned same method,, then peel off base material film if necessary, make optical waveguides 1 by light and/or thermofixation.

Optical waveguides of the present invention is used so can be used as the light propagation road of optical module because the thermotolerance and the transparency are excellent.Form as optical module, can enumerate the band fiber optical waveguide that has for example connected optical fiber at the two ends of optical waveguides, the optical waveguides that has connected the Belt connector of junctor at the two ends of optical waveguides, with the compound Optoelectric composite substrate of having changed of optical waveguides and printing distributing board, light/the electricity that has made up optical waveguides and mutual transmitting photo-signal and electrical signal changes the photoelectric conversion module of element, has made up the Wavelength channel join-splitting device of optical waveguides and wavelength division spectral filter etc.In addition, in Optoelectric composite substrate, the printing distributing board as compoundization is not particularly limited, and can use rigid substrates such as glass epoxy substrate, any one in the flexible base, boards such as polyimide.

Embodiment

Below, embodiments of the invention are carried out more specific description, but the invention is not restricted to these embodiment.

Production Example 1

[making of carboxyl acid modified phenoxy resin]

In the flask that possesses stirrer, cooling tube, rare gas element introducing port and thermometer, the weighing bisphenol A-type phenoxy resin (PKHB that InChem company makes, hydroxyl equivalent 284.35g/eq) 100 mass parts, tetrahydroxy Tetra hydro Phthalic anhydride (anhydride group equivalent 152.15g/eq) 37 mass parts, 1,4-diazabicylo [2.2.2] octane 0.3 mass parts, N, N-N,N-DIMETHYLACETAMIDE 321 mass parts, under nitrogen atmosphere, continue to stir 6 hours at 100 ℃, obtained carboxyl acid modified phenoxy resin solution (solids component 30 quality %) (P-1).

[mensuration of acid number]

The result of the acid number of the carboxyl acid modified phenoxy resin (P-1) that mensuration obtains is 100mgKOH/g.In addition, acid number is to be calculated by the potassium hydroxide aqueous solution amount of the required 0.1mol/L of the carboxyl acid modified phenoxy resin solution of neutralization (P-1).At this moment, with the phenolphthalein that adds as indicator by the colourless point of pink colour that becomes as the point of neutralization.

[mensuration of weight-average molecular weight]

For the weight-average molecular weight (polystyrene standard conversion) of the carboxyl acid modified phenoxy resin solution (P-1) that obtains, the result who uses GPC (SD-8022/DP-8020/RI-8020 that TOSOH Co., Ltd makes) to measure is 54,000.In addition, post has been to use the GelpackGL-A160-S that Hitachi Chemical Co., Ltd. makes.

Production Example 2

[making of carboxyl acid modified phenoxy resin]

Use the bisphenol A-type phenoxy resin (PKHB that InChem company makes, hydroxyl equivalent 284.35g/eq) 100 mass parts, succinyl oxide (anhydride group equivalent 100.07g/eq) 22 mass parts, 1,4-diazabicylo [2.2.2] octane 0.3 mass parts, N, N-N,N-DIMETHYLACETAMIDE 285 mass parts, method with same with Production Example 1 has obtained carboxyl acid modified phenoxy resin solution (solids component 30 quality %) (P-2).

With the method same with Production Example 1, the result who measures acid number and weight-average molecular weight is 100mgKOH/g and 53,000.

Production Example 3

[making of acrylate copolymer]

In the flask that possesses stirrer, cooling tube, rare gas element introducing port and thermometer, weighing propylene glycol monomethyl ether acetic ester 180 mass parts, under nitrogen atmosphere, be warming up to 90 ℃, when keeping 90 ℃, splash into methacrylic acid 15 mass parts, two cyclopentyl-methyl acrylate, 35 mass parts, n-butyl acrylate 30 mass parts, vinylbenzene 25 mass parts, 2,2 '-Diisopropyl azodicarboxylate, 3 mass parts, continue to stir 6 hours at 80 ℃, obtained acrylic acid polymer solution (solids component 35 quality %) (P-3).

With the method same with Production Example 1, the result who measures acid number and weight-average molecular weight is 98mgKOH/g and 30,000.

Production Example 4

[covering forms the mediation with resin paint]

Weighing is about pimelinketone solution (solids component 12 quality %) 333.3 mass parts (solids component 40 mass parts) of 850,000 acrylic rubber (HTR-860P-3 that Nagase chemteX Co., Ltd. makes) as the molecular weight of binder polymer in the PE wide-necked bottle, as Hydrogenated Bisphenol A (BPA) the type Resins, epoxy of polymerizable compound (YX-8000 that japan epoxy resin Co., Ltd. makes) 60 mass parts and as light acid producing agent triphenylsulfonium hexafluoro antimonate (SP-170 that Asahi Denka Kogyo K. K makes) 4 mass parts of polymerization starter, use mechanical stirrer, axle and water screw, 25 ℃ of temperature, stirred 6 hours under the condition of revolution 400rpm, modulated covering formation resin paint.Then, with the aperture is the tetrafluoroethylene synthetic resins strainer (PF020 that ADVANTEC Toyo Co., Ltd. makes) of 2 μ m, pressure filtration under the condition of 25 ℃ of temperature, pressure 0.4MPa, and then with vacuum pump and bell glass vacuum deaerator 15 minutes under the condition of decompression degree 50mmHg.

[covering forms the making with resin film]

(the Multicoater TM-MC that HIRANO TECSEED Co., Ltd. makes) is coated on the PET film (A1517 that Toyo Boseki K.K makes with covering formation with resin paint with coating machine; thickness 16 μ m) on the non-treated side; 100 ℃ of dryings 20 minutes; then stick the polyethylene film (NF-13 that TAMAPOLY Co., Ltd. makes as protective membrane; thickness 25 μ m), obtained covering formation resin film.In this Production Example, the film thickness that is adjusted to after the curing reaches wrap 30 μ m, upper clad layer 80 μ m down.

Embodiment 1

[core forms the mediation with resin paint]

The carboxyl acid modified phenoxy resin of weighing in the PE wide-necked bottle (A) (P-1) solution (solids component 30 quality %) 200 mass parts (solids component 60 mass parts), as (B) polymerizable compound to cumyl phenoxyethyl acrylate (Xin Zhong village chemical industry Co., Ltd. make A-CMP-1E) 20 mass parts, ethoxylated bisphenol a diacrylate (A-BPE-6 that Xin Zhong village chemical industry Co., Ltd. makes) 20 mass parts, as two (2 of (C) polymerization starter, 4,6-Three methyl Benzene formyl) phenylphosphine oxide (IRGACURE 819 that Ciba company makes) 2 mass parts, use mechanical stirrer, axle and water screw, 25 ℃ of temperature, stirred 6 hours under the condition of revolution 400rpm, modulated core formation resin paint.Then, with the aperture is the tetrafluoroethylene synthetic resins strainer (PF020 that ADVANTEC Toyo Co., Ltd. makes) of 2 μ m, pressure filtration under the condition of 25 ℃ of temperature, pressure 0.4MPa, and then with vacuum pump and bell glass vacuum deaerator 15 minutes under the condition of decompression degree 50mmHg.Weighing, and its stirring is in harmonious proportion out core forms and to use resin paint.

[core forms the making with resin film]

(the Multicoater TM-MC that HIRANO TECSEED Co., Ltd. makes) is coated on the PET film (A1517 that Toyo Boseki K.K makes with core formation with resin paint with coating machine; thickness 16 μ m) on the non-treated side; 100 ℃ of dryings 20 minutes; then stick the polyethylene film (NF-13 that TAMAPOLY Co., Ltd. makes as protective membrane; thickness 25 μ m), obtained core formation resin film.Can adjust the thickness of resin layer this moment by the gap of regulating coating machine arbitrarily, and in the present embodiment, the film thickness that is adjusted to after the curing reaches 50 μ m.

[making of cured film of the mensuration of specific refractory power and transmitance]

Use vacuum pressure type laminating machine (Co., Ltd. Mingji Koito makes MVLP-500/600); the core that to peel off the above-mentioned gained of protective membrane (NF-13) forms uses resin film; at the PET film (A4100 that Toyo Boseki K.K makes; thickness 50 μ m) on the non-treated side, under pressure 0.5MPa, 50 ℃ of temperature and the condition of 30 seconds clamping times, carry out lamination.Then, use ultraviolet exposure machine (MAP-1200-L that DAINIPPON SCREEN Co., Ltd. makes), irradiation ultraviolet radiation (wavelength 365nm) 1000mJ/cm ²After, peel off PET film (A1517 and A4100), under 160 ℃, carried out drying 1 hour, obtained the cured film of thickness 50 μ m.

[mensuration of specific refractory power]

Use prism coupler (Mode12010 that Metricon company makes), the result who measures the specific refractory power of gained cured film under 25 ℃ of temperature, wavelength 830nm is 1.553.

[mensuration of transmitance]

Use spectrophotometer (the U-3410 spectrophotometer that Hitachi Co., Ltd makes), the result who measures the transmitance of gained cured film under 25 ℃ of temperature, wavelength 400nm is 85%.

[making of optical waveguides]

Use vacuum pressure type laminating machine (Co., Ltd. Mingji Koito makes MVLP-500/600); the following wrap that to peel off protective membrane (NF-13) forms uses resin film; on FR-4 substrate (Hitachi Chemical Co., Ltd. makes E-679F), under pressure 0.5MPa, 50 ℃ of temperature and the condition of 30 seconds clamping times, carry out lamination.Then, use ultraviolet exposure machine (DAINIPPON SCREEN Co., Ltd. makes MAP-1200-L), irradiation ultraviolet radiation (wavelength 365nm) 1000mJ/cm ²After, peel off and support film PET film (A1517), formed time wrap 4.And then, on this time wrap 4, use above-mentioned vacuum pressure type laminating machine, core is formed use resin film, under pressure 0.5MPa, 50 ℃ of temperature and the condition of 30 seconds clamping times, carry out lamination.

Then, by the minus photomask of wide 50 μ m, with above-mentioned ultraviolet exposure machine irradiation ultraviolet radiation (wavelength 365nm) 500mJ/cm ², then, under 80 ℃, carry out 5 minutes exposure post-heating.Then, peel off and support film PET film (A1517), use developing solution (2.38 quality % tetramethylammonium hydroxide aqueous solution), development core pattern (core 2).Then, clean, 100 ℃ of heat dryings 1 hour with pure water.Then, use method and condition same when forming down wrap 4, advance-go on foot the lamination upper clad layer and form and use resin film, and irradiation ultraviolet radiation (wavelength 365nm) 3000mJ/cm ², peel off support film PET film (A1517),, form upper clad layer 3, obtained the optical waveguides 1 of the subsidiary substrate 5 shown in Fig. 1 (a) by 160 ℃ of heat treated 1 hour thereafter.Then, use slitting saw (DISCO of Co., Ltd. makes DAD-341) to cut out the optical waveguides 1 of the long 10cm of waveguide.

[mensuration of loss of light propagation]

Use in the light source with the light of wavelength 850cm as the VCSEL (EXFO company makes FLS-300-01-VCL) of centre wavelength, be subjected to optical sensor (ADVANTEST of Co., Ltd. makes Q82214), incident optical (GI-50/125 multimode optical fibers, NA=0.20) and outgoing optical fiber (SI-114/125, NA=0.22), the result of loss of light propagation who measures the optical waveguides of gained by successive subtraction method (measure waveguide is long by 10,5,3,2cm) is 0.15dB/cm.

[backflow test]

With the optical waveguides (the long 10cm of waveguide) that obtains,, carry out the backflow test of 265 ℃ of 3 top temperatures based on JEDEC standard (JEDEC JESD22A113E) with backflow test machine (The Furakawa Electric Co., Ltd. makes Salamander XNA-645PC).Detailed reflux conditions is as shown in table 1, and the temperature distribution in the reflow ovens as shown in Figure 2.

Table 1

Use with above-mentioned same light source, be subjected to optical sensor, incident optical and outgoing optical fiber, mensuration is implemented the insertion loss value of the flexible optical waveguides behind the backflow test, and the result is 0.26dB/cm.

Embodiment 2～4 and comparative example 1

According to the proportioning compounding ingredient shown in the table 2, obtained being used to measure the cured film and the optical waveguides of specific refractory power and transmitance according to method similarly to Example 1.Measured the propagation loss before and after the backflow test of specific refractory power, transmitance and optical waveguides of gained cured film.The result is as shown in table 3.

Table 2

^*The 1st, the carboxyl acid modified phenoxy resin solution of in Production Example 1, making;

^*The 2nd, the carboxyl acid modified phenoxy resin solution of in Production Example 2, making;

^*The 3rd, the acrylic acid polymer solution of in Production Example 3, making;

^*The 4th, to cumyl phenoxyethyl acrylate (Xin Zhong village chemical industry Co., Ltd. makes A-CMP-1E);

^*The 5th, adjacent phenyl phenoxyethyl acrylate (Xin Zhong village chemical industry Co., Ltd. makes A-L4);

^*The 6th, ethoxylated bisphenol a diacrylate (Xin Zhong village chemical industry Co., Ltd. makes A-BPE-6);

^*The 7th, ethoxylation fluorenes type diacrylate (Xin Zhong village KCC makes A-BPEF, and 9, two [4-(the 2-acryloyl-oxy oxyethyl group) phenyl] fluorenes of 9-);

^*The 8th, two (2,4,6-Three methyl Benzene formyl) phenylphosphine oxide (Ciba company makes IRGACURE819)

^*The 9th, acrylic rubber (Nagase chemteX Co., Ltd. makes HTR-860P-3)

^*The 10th, hydrogenation BPA type Resins, epoxy (japan epoxy resin Co., Ltd. makes YX-8000)

^*The 11st, triphenylsulfonium hexafluoro antimonate (Asahi Denka Kogyo K. K makes SP-170)

Table 3

^*1 wavelength 830nm, 25 ℃ ^*2 wavelength 400nm, 25 ℃

Application possibility on the industry

Resin composition for optical material of the present invention and the optical material usefulness tree of being made by this resin combination Membrane of lipoprotein dissolves in the alkaline aqueous solution, and heat resistance and transparency excellence, is particularly suitable for fiber waveguide. The resin composition for optical material of the application of the invention and the optical material of being made by this resin combination Use resin film, can be with make heat resistance and transparency excellence than the alkaline aqueous solution of organic solvent safety Fiber waveguide.

Claims

1. resin composition for optical material, it is characterized in that, contain (A) carboxyl acid modified phenoxy resin, (B) polymerizable compound and (C) polymerization starter, described (A) carboxyl acid modified phenoxy resin contains by the repeating unit (A-1) of following general formula (1) expression with by the repeating unit (A-2) of following general formula (2) expression:

In the formula, X ¹Expression

In the group of divalent arbitrarily; X ²The organic group of the divalent of expression carbonatoms 1～20;

Y ¹Expression

In the group of divalent arbitrarily; R ¹～R ¹⁹Represent any one in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 independently of one another; A represents 2～10 integer;

In the formula, X ³Expression

In the group of divalent arbitrarily;

Y ²Expression

In the group of divalent arbitrarily; R ²⁰～R ³⁸Represent any one in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 independently of one another; B represents 2～10 integer.

2. resin composition for optical material according to claim 1 is characterized in that, for (A) composition and (B) total amount of composition, the use level of described (A) composition is 10～85 quality %; For (A) composition and (B) total amount of composition, the use level of described (B) composition is 15～90 quality %; For (A) composition and (B) total amount 100 mass parts of composition, the use level of described (C) composition is 0.1～10 mass parts.

3. resin composition for optical material according to claim 1 and 2 is characterized in that, described (B) polymerizable compound is for containing at least a kind compound in ethene unsaturated group and the epoxy group(ing) more than 2 in its molecule.

4. according to each described resin composition for optical material of claim 1～3, it is characterized in that described (B) polymerizable compound contains at least a kind and the compound of selecting of ethene unsaturated group in its molecule from the group of being made of alicyclic structure, aryl, aryloxy and aralkyl.

5. according to each described resin composition for optical material of claim 1～4, it is characterized in that described (B) polymerizable compound is at least a kind in the compound of following general formula (3)～(6) expressions:

In the formula, Ar represents

In 1 valency group arbitrarily; X ⁴Expression Sauerstoffatom, sulphur atom or OCH ₂, SCH ₂, O (CH ₂CH ₂O) _c, O[CH ₂CH (CH ₃) O] _d, OCH ₂CH (OH) CH ₂The group of divalent arbitrarily among the O;

Y ³Expression

In the group of divalent arbitrarily;

R ³⁹In expression hydrogen atom, the methyl any one; R ⁴⁰～R ⁵⁶Represent any one in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 independently of one another; C and d represent 1～20 integer independently of one another, and e represents 2～10 integer;

In the formula, R ⁵⁷Expression

R ⁵⁸～R ⁶⁰Represent any one in hydrogen atom, the methyl independently of one another; F represents 1～10 integer;

In the formula, X ⁵, X ⁷Represent Sauerstoffatom, sulphur atom or O (CH independently of one another ₂CH ₂O) _g, O[CH ₂CH (CH ₃) O] _hIn the group of divalent arbitrarily;

X ⁶Expression

In the group of divalent arbitrarily; R ⁶¹, R ⁶⁶Represent any one in hydrogen atom, the methyl independently of one another; R ⁶²～R ⁶⁵Represent any one in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 independently of one another; G and h represent 1～20 integer independently of one another, and i represents 2～10 integer;

In the formula, X ⁸Expression

In the group of divalent arbitrarily; R ⁶⁷, R ⁷²Represent any one in hydrogen atom, the methyl independently of one another; R ⁶⁸～R ⁷¹Represent any one in the fluorine-containing organic group of organic group, carbonatoms 1～20 of hydrogen atom, fluorine atom, carbonatoms 1～20 independently of one another; J represents 1～5 integer, and k represents 2～10 integer.

6. according to each described resin composition for optical material of claim 1～5, it is characterized in that described (C) polymerization starter is the optical free radical polymerization starter.

7. according to each described resin composition for optical material of claim 1～6, it is characterized in that the specific refractory power of cured film under 25 ℃ of temperature, wavelength 830nm that described resin composition for optical material polymerization, curing are formed is 1.400～1.700.

8. according to each described resin composition for optical material of claim 1～7, it is characterized in that, with described resin composition for optical material polymerization, to solidify the thickness form be that the transmitance of cured film under 25 ℃ of temperature, wavelength 400nm of 50 μ m is more than 80%.

9. a resin for optical material film is characterized in that, is made by each described resin composition for optical material of claim 1～8.

10. an optical waveguides is characterized in that, has the core and/or the covering of each described resin composition for optical material formation of using claim 1～8.

11. an optical waveguides is characterized in that, has the core and/or the covering that use the described resin for optical material film of claim 9 to form.

12. an optical waveguides is characterized in that, has the core that uses the described resin for optical material film of claim 9 to form.

13. each the described optical waveguides according to claim 10～12 is characterized in that loss of light propagation is below 0.3dB/cm.

14. each the described optical waveguides according to claim 10～13 is characterized in that, implements 3 top temperatures and be loss of light propagation behind 265 ℃ the backflow test below 0.3dB/cm.