CN107207680A - Photosensitive polymer combination and its solidfied material - Google Patents

Abstract

Shrinkage factor low resin combination when the present invention provides a kind of solidification, its cured film formed can reduce in adhesion process or solidification after exhaust generation, weatherability, excellent in light-resistance and flexibility is excellent.A kind of photosensitive polymer combination (D), it is included with the polymerizable compound (C) beyond the autohemagglutination mould assembly photopolymerizable compound (A) represented by following formulas (1), carbamate (methyl) acrylate compounds (B) and (B).(in formula (1), R represents hydrogen atom or methyl.)

Description

Photosensitive polymer combination and its solidfied material

Technical field

The present invention relates to a kind of photosensitive polymer combination and its solidfied material containing autohemagglutination mould assembly photopolymerizable compound. And then, the present invention relates to a kind of carbamate (methyl) acrylate comprising using hydrogenated butadiene polymer polyalcohol as main framing With the resin combination and its solidfied material of specific polymerizable compound, it can reduce the volatile ingredient in solidification process, its Cured film flexibility, the transparency, moisture-proof, the excellent adhesion with base material, cure shrinkage is also small, therefore the display that is particularly suitable for use in The laminating purposes of the optical thin film of device device etc..

Background technology

In with the energy ray curing resin combination of ultraviolet isoreactivity, the luminous energy being absorbed to is transferred to and aggregated into Photoepolymerizationinitiater initiater in point is neccessary composition.As its concrete example, benzophenone, benzoin ethers, benzene can be included Even acyl ketal class, Dibenzosuberone class, Anthraquinones, xanthone, thioxanthene ketone class, halo acetophenone class, dialkoxy benzene Ethyl ketone class, hydroxy acetophenone class, halo double imidazoles, halo triazines, acylphosphine oxide class, oxime esters etc..

But these compounds have the following disadvantages, problem：It can be dropped due to that will not enter polymerisation skeleton, therefore have The shortcoming of the hardness of low solidfied material；Due to Photoepolymerizationinitiater initiater in itself or the analyte that brings of the light irradiation has volatilization mostly Property/sublimability, therefore exist from solidfied material generation niff, or cause light energy illuminating apparatus, row mood Guan wu dyes etc. Problem.

In order to solve the above problems, patent document 1 proposes a kind of included in same intramolecular, and there is photopolymerization to trigger work( The skeleton of energy and the material of the double bond part with polymerism.By using this material, high rigidity, reduction exhaust can be kept Generation.In addition, for example in Photoepolymerizationinitiater initiater used in patent document 2, the analyte oozed out after for photocuring Cause also to have used same thinking in the countermeasure that Ye Jing wu contaminate, expect this thinking in order to improve the electricity of continuous densification Also found application in the reliability of the matching component of sub-information material.

Think to keep transparent ground to avoid what bubble caused by being vented was mixed into process as optical component purposes is this Situation can also apply this Photoepolymerizationinitiater initiater.In this purposes that high reliability is required in the transparency, sometimes for changing Kind xanthochromia or weatherability, meeting selective hydrogenation polybutadiene play its speciality as polyol compound.Adopted in patent document 3 Carbamate (methyl) acrylate is manufactured with hydrogenated butadiene polymer polyalcohol.But, the analyte of used initiator With volatility, above-mentioned problem is not touched.

In recent years, for research of carbamate (methyl) acrylate in terms of LCD (liquid crystal display) purposes and Practical application is in popular trend.For example in patent document 4, to use polybutadiene (methyl) acrylate oligomer and amino The photocuring used in the laminating of optics display body or touch sensor obtained from formic acid esters (methyl) acrylate oligomer The form of type adhesive composite is used.It is used as carbamate (methyl) acrylate, thus it is speculated that also may require that from now on soft The higher material of soft excellent and weatherability, light resistance.In addition, patent document 5 is described using polynary without aromatic rings Application of (methyl) acrylate of carbamate obtained from alcoholic compound on LCD optical components.It is existing on above-mentioned example Shape be they also without reference to decomposition of initiator thing the problem of.

Prior art literature

Patent document

Patent document 1:No. 4236180 publications of Japanese Patent Publication No.

Patent document 2:No. 4974344 publications of Japanese Patent Publication No.

Patent document 3:No. 4868654 publications of Japanese Patent Publication No.

Patent document 4:Japanese Unexamined Patent Publication 2012-46658 publications

Patent document 5:Japanese Unexamined Patent Publication 2011-190421 publications

The content of the invention

Problems to be solved by the invention

As these with the optical component purposes for representative such as touch panel bonding agent, various raw material are required higher Exhaust during weatherability, light resistance and raising cured film physical property, reduction laminating, improves the analyte after photocuring and causes Ooze out caused by the requirement of less reliable also gradually step up.

It is an object of the invention to：A kind of low resin combination of shrinkage factor when solidification is provided, its cured film formed The demand can be improved, the exhaust generation in adhesion process or after solidification, weatherability and excellent in light-resistance is reduced and flexibility is excellent It is different.

The solution used to solve the problem

The present inventor etc. have made intensive studies to solve the above problems, and as a result find, comprising with specific structure The photosensitive polymer combination of the autohemagglutination mould assembly photopolymerizable compound of composition can solve the above problems, so as to complete this hair It is bright.

That is, the present invention relates to following technical scheme：

(1) a kind of photosensitive polymer combination (D), it is with the autohemagglutination mould assembly optical polymerism represented by following formulas (1) Polymerizable compound (C) beyond compound (A), carbamate (methyl) acrylate compounds (B) and (B) is used as must Composition is wanted to constitute；

(in formula, R represents hydrogen atom or methyl.)

(2) photosensitive polymer combination (D) according to (1), wherein, carbamate (methyl) acrylate chemical combination Thing (B) is carbamate (methyl) acrylate obtained from aliphatic category polyisocyanate compound is used as composition Compound；

(3) photosensitive polymer combination (D) according to (1) or (2), wherein, carbamate (methyl) acrylic acid Ester compounds (B) are without xanthochromia type carbamate obtained from hydrogenated butadiene polymer polyol compound is used as composition (methyl) acrylate compounds；

(4) photosensitive polymer combination (D) according to any one of (1)~(3), wherein, carbamate (first Base) acrylate compounds (B) weight average molecular weight be more than 5000；

(5) photosensitive polymer combination (D) according to any one of (1)~(4), wherein, polymerizable compound (C) it is (methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester；

(6) photosensitive polymer combination (D) according to any one of (1)~(5), wherein, it is used as polymerism Compound (C), further (methyl) acrylate containing hydroxyl；

(7) photosensitive polymer combination (D) according to any one of (1)~(6), it also includes softening ingredient (E)；

(8) photosensitive polymer combination (D) according to any one of (1)~(7), it is optical component purposes；

(9) photosensitive polymer combination (D) according to any one of (1)~(7), it is touch panel bonding agent Purposes；

(10) solidfied material of the photosensitive polymer combination described in a kind of any one of (1)~(7).

The effect of invention

The present invention the photosensitive polymer combination containing autohemagglutination mould assembly photopolymerizable compound cured film be not vented, Niff, flexibility is excellent, and weatherability, light resistance are high, except needing to maintain transparent touch panel bonding agent etc Optical applications beyond, can also the various coatings arts such as ink, plastic paint, stationery printing, metal coating, furniture application, Insulating varnish, insulating trip, plywood, tellite, protection ink in liner, bonding agent and then electronics field Applied in the multiple fields such as (resist ink), semiconductor packages agent.

Embodiment

The autohemagglutination mould assembly photopolymerizable compound (A) represented by following formulas (1) used in the present invention can be by making Commercially available Photoepolymerizationinitiater initiater Irgacure2959 (BASF manufactures) primary hydroxyl and KarenzMOI, KarenzAOI (Showa electricity Work Co., Ltd. manufacture) NCO reaction and obtain, during reaction, the molal quantity of primary hydroxyl and the molal quantity of isocyanates Ratio be 0.8：1.2~1.2：0.8, preferably with 0.9：1.1~1.1：0.9 ratio is reacted.

(in formula, R represents hydrogen atom or methyl.)

Reaction can be in solvent-free lower progress, but the crystallinity of product is high, in order to improve workability, preferably in not containing alcohol Carried out in the solvent of hydroxyl or in polymerizable compound described later (C).As the concrete example of solvent, it can include：Acetone, first The ketones such as ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, benzene,toluene,xylene, durol etc. are aromatic hydrocarbon；Glycol dinitrate Ether, ethylene glycol diethyl ether, dimethyl ether, dipropylene glycol diethyl ether, TRIGLYME, triethylene glycol diethyl ether etc. Gylcol ether, ethyl acetate, butyl acetate, methylcellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetic acid Ester, carbitol acetate, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, DPGME second The esters such as acid esters, dialkyl glutarate, dialkyl succinate, hexanedioic acid dialkyl ester, the ring-type esters such as gamma-butyrolacton； The independent organic solvent such as petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha or mixed organic solvents.

Reaction temperature is usually 30~150 DEG C, preferably 50~100 DEG C of scope.The terminal of reaction is with amount of isocyanate Reduction confirm.In addition, for the purpose of shortening their reaction time, catalyst can be added., can be with as the catalyst Use any of base catalyst and acidic catalyst.As the example of base catalyst, it can include：Pyridine, pyrrole Cough up, the phosphine such as amine, tributylphosphine, the triphenylphosphine such as triethylamine, diethylamine, dibutyl amine, ammonia.In addition, being used as acidic catalyst Example, can include：Copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminium butoxide, tetraisopropyl titanate, the fourth of zirconic acid four The Louis acid catalysis such as ester, aluminium chloride, tin octoate, trilauryl tin octylate, dibutyl tin laurate, octyltin diacetate Agent.The addition of these catalyst is usually 0.1~1 weight relative to the parts by weight of total weight parts 100 of reacting material mixture Part.

In (methyl) acrylate compounds used as raw material, generally added with the resistance such as 4- metoxyphenols Poly- agent, but polymerization inhibitor can also be added again in reaction.As the example of such polymerization inhibitor, it can include：To benzene two Phenol, 4- metoxyphenols, 2,4 dimethyl 6 tert butyl phenol, 2,6- di-t-butyl -4- cresols, 3- hydroxythiophenols, to benzene Quinone, 2,5- dihydroxy 1,4-benzoquinone, phenthazine etc..Its consumption is 0.01 relative to 100 parts of the total weight parts of reacting material mixture ~1 parts by weight.

It can implement as needed according to known operation based on washing, the purification procedures of crystallization after reaction, remove institute under reduced pressure Solvent, the crystal drying process used, so as to obtain the autohemagglutination mould assembly photopolymerizable compound (A) used in the present invention.

In the present invention, in the synthesis of autohemagglutination mould assembly photopolymerizable compound (A), in there may be before purification procedures Irgacure2959 or following formula (3) compound.

(in above-mentioned formula, R represents hydrogen atom or methyl.)

Generally, at the end of reaction, in the test using high performance liquid chromatography (HPLC), represented by above-mentioned formula (1) The compound that compound accounts for area %, Irgacure2959 or the above-mentioned formula (3) of 70 area %~90 accounts for the face of 5 area %~20 Product %.

Therefore, by undergoing recrystallization process, the purity of the compound represented by above-mentioned formula (1) can be improved.Here, on The purity for stating the compound represented by formula (1) is preferably more than 95%, more preferably more than 97%, especially preferably 98% with On.

For being not particularly limited for the solvent for being recrystallized and being used, but from the carrying capacity of environment in drying process Aspect is set out, preferably alcohols solvent, is carried out more preferably in the primary alconols such as methanol, ethanol.

Carbamate (methyl) acrylate compounds (B) used in the present invention can be obtained by following reaction： Make hydrogenated butadiene polymer polyalcohol and/or other diol compounds and polyisocyanate compound reaction (hereinafter referred to as the first One reaction)；Then make the NCO and (methyl) acrylate compounds with least more than one hydroxyl of residual anti- (the hereinafter referred to as second reaction) is answered, is thus obtained, wherein, preferably without xanthochromia type carbamate (methyl) acrylate.

Here, referring to the carbamate (methyl) for estimating non-coloring without xanthochromia type carbamate (methyl) acrylate Acrylate, as concrete example, can include and be obtained using aliphatic category polyisocyanates as above-mentioned polyisocyanates Carbamate (methyl) acrylate.

The hydrogenated butadiene polymer polyalcohol used in being reacted as first, as long as the hydrogen of common polybutadiene polyol Change reduzate, more particularly, in terms of optical applications, can preferably remain the few hydrogenated butadiene polymer of double bond polynary to use Alcohol, is more preferably less than 20, particularly preferably less than 15 in terms of iodine number.In addition, the molecule on hydrogenated butadiene polymer polyalcohol Amount, the hydrogenated butadiene polymer polyalcohol of the molecular weight distribution that usually can be obtained can be used, but especially obtain flexibility with In the case of the balance of curability, preferred number average molecular weight is 500~5000 hydrogenated butadiene polymer polyalcohol, particularly preferably 500~3000 hydrogenated butadiene polymer polyalcohol.

The concrete example of diol compound in being reacted as first in addition to polybutadiene polyol is hydrogenated, for example, can enumerate Go out：The polyether polyols alcohols such as polyethylene glycol, polytetramethylene glycol, polytetramethylene glycol, polypropylene glycol, polyethylene glycol, polyethylene glycol The polyester polyols alcohols, ethylene glycol, propane diols, butanediol, penta such as adipate ester, poly- BDO adipate ester, polycaprolactone The glycol such as glycol, hexylene glycol and neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F, the alcohol containing spirocyclic ring scaffold, The alicyclic alcohol such as Tricyclodecane Dimethanol and pentacyclopentadecane dimethanol and these alkylene oxide addition product, hydrogenated butadiene polymer The alkylene oxide addition product of the alkyl diols of the branched such as glycol or straight-chain, the bis-phenol such as bisphenol-A, Bisphenol F, and bis-phenol, The polyalcohols such as trimethylolpropane, double trimethylolpropane, pentaerythrite and dipentaerythritol, and these polyalcohols epoxy Alkane addition product, and then pass through PEPA etc. obtained from the reaction of the polyacids such as these polyalcohols and adipic acid.On upper The molecular weight of compound is stated, the diol compound of typically available molecular weight distribution can be used, and especially obtain flexibility In the case of the balance of curability, the diol compound that mean molecule quantities are 500~6000 is preferably counted, particularly preferred 500~ 4000 diol compound.

The polyisocyanate compound used in first reaction is the change containing more than 2 NCOs in 1 molecule Compound, for example, can include：Aliphatic category diisocyanate cpd, fragrant same clan diisocyanate cpd, their three Polymers etc..Aliphatic category diisocyanate cpd said here refers to that NCO is bonded with chain carbon atoms two is different The diisocyanate cpd of the carbon atom bonding of cyanate esters and NCO and cyclic saturated hydrocarbon, aromatic series Class diisocyanate cpd refers to the isocyanate compound of the carbon atom bonding of NCO and aromatic rings.It is saturating from assigning From the viewpoint of bright property, preferred fat same clan diisocyanate cpd.

As aliphatic category diisocyanate cpd, for example, it can include：1,6- hexamethylene diisocyanates, different Buddhist That ketone diisocyanate, hydrogenated toluene diisocyanate, hydrogenation XDI, hydrogenated diphenyl methane two are different Cyanate, 1,3- cyclohexyl diisocyanates, 1,4- cyclohexyl diisocyanates, the isocyanic acid of '-two of dicyclohexyl methyl hydride -4,4 Xylylene diisocyanate, tetramethyl paraxylene diisocyanate, the isocyanic acid of 1,4- tetramethylenes two between ester, tetramethyl Ester, the dimethylene diisocyanates of 1,12- ten, 2,2,4- trimethyl-cyclohexanes diisocyanate, 2,4,4- trimethyl-cyclohexanes Diisocyanate, 2,2,4- trimethyl hexamethylene diisocyanates, 2,4,4- trimethyl hexamethylene diisocyanates, bad ammonia Sour diisocyanate, norbornene alkyl diisocyanate etc..Wherein, preferred IPDI.

As fragrant same clan's diisocyanate cpd, for example, it can include：Toluene di-isocyanate(TDI), phenylenedimethylidyne two Isocyanates, methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, dimethyl diphenyl diisocyanate, 1,6- benzene two Diisocyanate monomer classes such as isocyanates, 1,4- phenylene diisocyanates, 1,6- phenylene diisocyanates etc..

Wherein, the trimer of aliphatic category diisocyanate cpd and the aliphatic category diisocyanate cpd makes painting The weatherability of film is good, therefore preferably.As the trimer of aliphatic category diisocyanate cpd, for example, it can include：On Isocyanurate type polyisocyanates of aliphatic category isocyanates etc. is stated, specifically, hexa-methylene two can be included different Cyanate, IPDI etc..They can each be used alone, or be used with mixture.

First reaction is with such equivalent relation ([NCO]/[OH] mol ratios of the residual of NCO after the reaction：＞ 1) Fed intake.When improving rate of charge, unreacted polyisocyanate compound is largely present, sometimes to photosensitive resin composition The flexibility of thing is impacted.In addition, when reducing rate of charge, molecular weight is improved, and photosensitive polymer combination is consolidated sometimes The property changed is impacted.It is particularly preferred as：Relative to 1.0 moles of the NCO bases of polyisocyanate compound, the OH bases of alcoholic compound are excellent Elect 0.01~0.99 mole, more preferably 0.10~0.95 mole as.

First reaction can be in solvent-free lower progress, but the viscosity of product is high, in order to improve workability, further preferably not Carried out in solvent with alcohol hydroxyl group or in polymerizable compound described later (C)., can be third as the concrete example of solvent The ketones such as ketone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, benzene,toluene,xylene, durol etc. are aromatic hydrocarbon；Second two Diethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl ether, dipropylene glycol diethyl ether, TRIGLYME, triethylene glycol two The gylcol ethers such as ether, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, ethylene glycol fourth Ether acetic acid ester, carbitol acetate, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, DPG list first The esters such as base ether acetic acid ester, dialkyl glutarate, dialkyl succinate, hexanedioic acid dialkyl ester, the ring-type such as gamma-butyrolacton Esters；Individually organic solvent or mixing are organic for petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha etc. Carried out in solvent.

Reaction temperature is usually 30~150 DEG C, is preferably 50~100 DEG C of scope.The terminal of reaction is with amount of isocyanate Reduction confirm.In addition, for the purpose of shortening their reaction time, catalyst can be added., can be with as the catalyst Use any of base catalyst and acidic catalyst.As the example of base catalyst, can enumerate pyridine, pyrroles, The phosphines such as the amines such as triethylamine, diethylamine, dibutyl amine, ammonia, tributylphosphine, triphenylphosphine.In addition, being used as the example of acidic catalyst Son, can enumerate copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminium butoxide, tetraisopropyl titanate, tetrabutyl zirconate, chlorination The lewis acid catalysts such as aluminium, tin octoate, trilauryl tin octylate, dibutyl tin laurate, octyltin diacetate.These are urged The addition of agent relative to diol compound and polyisocyanate compound the parts by weight of total weight parts 100, usually 0.1~ 1 parts by weight.

Carbamate (methyl) acrylate compounds (B) used in the present invention can be by reacting followed by first Obtain the NCO of residual and (methyl) acrylate reactions (the second reaction) of hydroxyl.

(methyl) acrylate of the hydroxyl used in second reaction refers to there is hydroxyl and (methyl) third in 1 molecule The compound that olefin(e) acid ester group is at least each one, specifically, can be included：(methyl) 2-Hydroxy ethyl acrylate, propane diols Single (methyl) acrylate, butanediol list (methyl) acrylate, pentanediol list (methyl) acrylate, hexylene glycol list (methyl) Acrylate, diethylene glycol list (methyl) acrylate, DPG list (methyl) acrylate, triethylene glycol list (methyl) third Olefin(e) acid ester, tripropylene glycol list (methyl) acrylate, tetraethylene glycol list (methyl) acrylate, polyethyleneglycol (methyl) propylene Acid esters, polypropylene glycol list (methyl) acrylate, neopentyl glycol single (methyl) acrylate, ethoxyquin neopentyl glycol single (methyl) List (methyl) acrylate of the dihydric alcohols such as acrylate, 3-hydroxypivalic acid neopentyl glycol single (methyl) acrylate；

Trimethylolpropane list (methyl) acrylate, ethoxyquin trimethylolpropane list (methyl) acrylate, the third oxygen Change trimethylolpropane list (methyl) acrylate, isocyanuric acid three (2- hydroxyethyls) ester list (methyl) acrylate, glycerine Single (methyl) acrylate, trimethylolpropane two (methyl) acrylate, ethoxyquin trimethylolpropane two (methyl) propylene Acid esters, third oxidation trimethylolpropane two (methyl) acrylate, isocyanuric acid three (2- hydroxyethyls) ester two (methyl) propylene List (methyl) acrylate and two (methyl) acrylate of the trihydroxylic alcohols such as acid esters, glycerine two (methyl) acrylate or by this A part of alkyl, the 6-caprolactone of the hydroxyl of a little alcohol modified list (methyl) acrylate and two (methyl) acrylate；

Pentaerythrite list (methyl) acrylate, dipentaerythritol list (methyl) acrylate, double trimethylolpropane list (methyl) acrylate, pentaerythrite two (methyl) acrylate, dipentaerythritol two (methyl) acrylate, double trihydroxy methyls Propane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, double three Hydroxymethyl-propane three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, double trimethylolpropane four (methyl) It is more than the quaternarys such as acrylate, dipentaerythritol six (methyl) acrylate, double trimethylolpropane six (methyl) acrylate Alcohol multifunctional (methyl) acrylate with hydroxyl or a part of alkyl, the 6-caprolactone by the hydroxyl of these alcohol Modified multifunctional (methyl) acrylate with hydroxyl；Deng.

Among above-mentioned (methyl) acrylate with least one hydroxyl, hydroxyl is preferably 1, from curability and softness Property it is excellent from the viewpoint of, particularly preferred (methyl) 2-Hydroxy ethyl acrylate., can be anti-from the point of view of easy to operate Polymerizable compound (C) described later in seasonable addition this specification.

Second reaction is carried out with the equivalent relation that can exhaust the NCO of the intermediate obtained after being reacted first Feed intake.It is particularly preferred as：Relative to the NCO base 1.0mol of the intermediate obtained after being reacted first, will have more than at least one The OH bases of (methyl) acrylate of hydroxyl are set as 1.0~3.0 moles, are further preferably set as 1.0~2.0 moles.

Second reaction can also be in solvent-free lower progress, but the viscosity of product is high, in order to improve workability, preferably upper Carried out in the solvent stated and/or in the present invention in polymerizable compound (C) described later.In addition, reaction temperature be usually 30~ 150 DEG C, preferably in 50~100 DEG C of scope.The terminal of reaction is confirmed with the reduction of amount of isocyanate.To shorten the anti-of them For the purpose of between seasonable, foregoing catalyst can be added.

Generally added with the resistance such as 4- metoxyphenols in (methyl) acrylate compounds used as raw material Poly- agent, but polymerization inhibitor can also be added again in reaction.As the example of such polymerization inhibitor, it can include：To benzene two Phenol, 4- metoxyphenols, 2,4 dimethyl 6 tert butyl phenol, 2,6- di-t-butyl -4- cresols, 3- hydroxythiophenols, to benzene Quinone, 2,5- dihydroxy 1,4-benzoquinone, phenthazine etc..Its consumption is 0.01~1 weight % relative to reacting material mixture.

As carbamate (methyl) acrylate compounds (B) used in the present invention, can use usually can The commercially available product of acquisition, for example, can include the UX-3204, UX-4101, UXT-6100, UX- of Nippon Kayaku K. K's manufacture 6101, UX-7101, UX-8101, UXF-4001-M35, UXF-4002, DPHA-40H, UX-5000, UX-5002D-M20, UX- 5103D, UX-5002 etc..

The photosensitive polymer combination (D) of the present invention is with autohemagglutination mould assembly photopolymerizable compound (A), carbamate (first Base) polymerizable compound (C) beyond acrylate compounds (B) and (B) composition constitutes for neccessary composition and obtains.As can With the concrete example of the polymerizable compound (C) used, the compound with (methyl) acryloxy, maleimide can be included Amines, (methyl) acrylamide compound, unsaturated polyester (UP) etc..

There is (methyl) acryloxy as what can be applied in combination in the photosensitive polymer combination of the present invention The concrete example of compound, can be included：(poly-) ester (methyl) acrylate (C-1)；Carbamate (methyl) acrylate (C-2)；Epoxy (methyl) acrylate (C-3)；(poly-) ether (methyl) acrylate (C-4)；(methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester (C-5)；(methyl) acrylate (C-6) with aromatic rings；(first with alicyclic structure Base) acrylate (C-7)；Compound (C-8) with (methyl) acryloyl group；Compound (C- containing dimaleoyl imino 9)；(methyl) acrylamide compound (C-10)；Unsaturated polyester (UP) (C-11) etc., but it is not limited to these.

It should be noted that on reaction product, can be obtained under known reaction condition.

(poly-) ester (methyl) acrylate (C-1) that can be applied in combination in the photosensitive polymer combination of the present invention is used Make the general name of (methyl) acrylate with more than one ester bond in main chain, carbamate (methyl) acrylate (C- 2) it is used as the general name of (methyl) acrylate with more than one amino-formate bond in main chain, epoxy (methyl) acrylic acid Ester (C-3) is used as making epoxide more than 1 function and (methyl) acrylate obtained from (methyl) propylene acid reaction General name, (poly-) ether (methyl) acrylate (C-4) is used as (methyl) acrylate with more than one ehter bond in main chain It is straight chained alkyl, branched alkane that general name, (methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester (C-5), which are used as main chain, Base, can be in straight chain or end has the general name of (methyl) acrylate of halogen atom and/or hydroxyl, with aromatic rings (methyl) acrylate (C-6) is used as the general name of (methyl) acrylate with aromatic rings in main chain or side chain, with fat (methyl) acrylate (C-7) of ring structure be used as having in main chain or side chain can in construction unit containing oxygen atom or The general name of (methyl) acrylate of the alicyclic structure of nitrogen-atoms.

It is used as (poly-) ester (methyl) acrylate (C- that can be applied in combination in the photosensitive polymer combination of the present invention 1), it can such as include：Caprolactone modification (methyl) 2-Hydroxy ethyl acrylate, oxirane and/or epoxy pronane modification are adjacent Phthalic acid (methyl) acrylate, ethylene-oxide-modified butanedioic acid (methyl) acrylate, caprolactone modification (methyl) propylene The simple functions such as sour tetrahydrochysene chaff ester (poly-) ester (methyl) esters of acrylic acid；3-hydroxypivalic acid ester neopentyl glycol two (methyl) acrylic acid Ester, (methyl) acrylate of caprolactone modification 3-hydroxypivalic acid ester neopentyl glycol two, epoxychloropropane modified phthalic acid two (methyl) acrylate；To trimethylolpropane or the 6-caprolactone of 1 mole of glycerine, more than 1 mole of addition, gamma-butyrolacton, δ- List (methyl) acrylate, two (methyl) acrylate or three of trihydroxylic alcohol obtained from the annular lactone compound such as valerolactone (methyl) acrylate；

To pentaerythrite or 6-caprolactone, gamma-butyrolacton, the δ-penta of 1 mole of double trimethylolpropane, more than 1 mole of addition List (methyl) acrylate of tetrahydroxylic alcohol obtained from the annular lactone compound such as lactone, two (methyl) acrylate, three (first Base) acrylate or four (methyl) acrylate；6-caprolactone, γ-fourth to 1 mole of dipentaerythritol, more than 1 mole of addition List (methyl) acrylate of hexahydroxylic alcohols obtained from the annular lactone compound such as lactone, δ-valerolactone or many (methyl) propylene Acid esters；

It is used as (poly-) ethylene glycol, (poly-) propane diols, (poly-) tetramethylene glycol, (poly-) butanediol, 3- methyl isophthalic acids, 5- penta 2 The glycol components such as alcohol, hexylene glycol and maleic acid, fumaric acid, butanedioic acid, adipic acid, phthalic acid, M-phthalic acid, hexahydro The polyacids such as phthalic acid, tetrahydrophthalic acid, dimeric dibasic acid, decanedioic acid, azelaic acid, 5-sodium sulfo isophthalate and (methyl) acrylate of the PEPA of the reaction product of their acid anhydrides；Comprising above-mentioned glycol component, polyacid and (methyl) propylene of the annular lactone modified poly ester glycol of their acid anhydrides and 6-caprolactone, gamma-butyrolacton, δ-valerolactone etc. Multifunctional (poly-) ester (methyl) esters of acrylic acid such as acid esters etc., but it is not limited to these.

Carbamate (methyl) acrylate (C- that can be applied in combination in the photosensitive polymer combination of the present invention 2) it is by the hydroxy compounds (C-2-A) with least one (methyl) acryloxy and isocyanate compound (C-2- B the general name of (methyl) acrylate obtained from reaction).

As the concrete example of the hydroxy compounds (C-2-A) with least one (methyl) acryloxy, for example, it can arrange Enumerate：(methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -2- hydroxybutyls, (methyl) acrylic acid -4- hydroxybutyls, cyclohexanedimethanol list (methyl) acrylate, polyethyleneglycol (methyl) acrylic acid Ester, polypropylene glycol list (methyl) acrylate, pentaerythrite three (methyl) acrylate, (methyl) acrylic acid -2- hydroxyl -3- benzene Various (methyl) acrylate compounds and above-mentioned (methyl) acroleic acid esterification with hydroxyl with hydroxyl such as epoxide propyl ester Ring-opening reaction product of compound and 6-caprolactone etc..

As isocyanate compound (C-2-B) concrete example, for example, it can include：PPDI, isophthalic two Isocyanates, paraxylene diisocyanate, m xylene diisocyanate, 2,4 toluene diisocyanate, 2,6- toluene two The aromatic diisocyanate class such as isocyanates, 4,4 '-methyl diphenylene diisocyanate, naphthalene diisocyanate；Isophorone Diisocyanate, hexamethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate, the isocyanic acid of hydrogenated xylylen two The diisocyanates of the aliphatic such as ester, ENB diisocyanate, lysine diisocyanate or alicyclic structure；Isocyanic acid More than one biuret type of ester monomer or by isocyanates shape obtained from above-mentioned diisocyanate cpd trimerizing The polyisocyanates such as formula；Reacted and obtained by the urethane of above-mentioned isocyanate compound and above-mentioned polyol compound Polyisocyanates arrived etc..

It should be noted that when obtaining carbamate (methyl) acrylate, with (methyl) acryloxy Hydroxy compounds (C-2-A) and isocyanate compound (C-2-B) reaction in, carry out arbitrarily polyalcohol anti- Should.

As the polyalcohol that can be used, for example, it can include：Neopentyl glycol, 3- methyl isophthalic acids, 5- pentanediols, ethylene glycol, The carbon numbers such as propane diols, 1,4- butanediols, 1,6-HD are 1~10 aklylene glycol, trimethylolpropane, pentaerythrite etc. Trihydroxylic alcohol, Tricyclodecane Dimethanol, double (methylol) hexamethylenes etc. have alcohol of cyclic skeleton etc.；And pass through these polyalcohols With polyacid (such as butanedioic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid (TPA), adipic acid, azelaic acid, tetrahydrochysene Phthalic anhydride etc.) reaction obtained from PEPA, by obtained from the reaction of polyalcohol and 6-caprolactone oneself Lactone alcohol, polycarbonate polyol (for example pass through makrolon two obtained from the reaction of 1,6-HD and diphenyl carbonate Alcohol etc.) or PPG (such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene-oxide-modified bisphenol-A) Deng.

Epoxy (methyl) acrylate (C-3) that can be applied in combination in the photosensitive polymer combination of the present invention is to make The general name of epoxy resin containing the epoxy radicals of more than 1 and (methyl) acrylate obtained from (methyl) propylene acid reaction. As the concrete example of the epoxy resin of the raw material of epoxy (methyl) acrylate, it can include：Hydroquinones 2-glycidyl The phenyl diglycidyl ether such as ether, diglycidyl ether catechol, resorcinolformaldehyde resin；Bisphenol type epoxy tree Double (4- the hydroxy phenyls) -1,1,1,3,3,3- HFC-236fas of fat, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2,2- The biphenol type epoxy compound such as epoxide；Bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F types epoxy resin, A Hydrogenated Bisphenol A The A Hydrogenated Bisphenol As such as S types epoxy resin, the epoxide of double (4- the hydroxy phenyls) -1,1,1,3,3,3- HFC-236fas of hydrogenation 2,2- Type epoxide；The halogenated bisphenol type epoxides such as brominated bisphenol-A type epoxy resin, bromobisphenol F type epoxy resin；Ring The ester ring type 2-glycidyl ether compounds such as hexane dimethanol 2-glycidyl ether compound；1,6-HD 2-glycidyl The aliphatic diglycidylether compounds such as ether, 1,4- butanediol diglycidyl ethers, diethylene glycol diglycidyl glycerin ether；Many sulphur The polysulfide type 2-glycidyl ether compounds such as compound (polysulfide) diglycidyl ether；Phenol novolak type ring Oxygen tree fat, cresol novolak type epoxy resin, three oxybenzene methylmethane type epoxy resin, dicyclopentadiene phenol type epoxy tree Fat, united phenol-type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, the epoxy resin containing naphthalene skeleton, hetero ring type asphalt mixtures modified by epoxy resin Fat etc..

It is used as (poly-) ether (methyl) acrylate (C- that can be applied in combination in the photosensitive polymer combination of the present invention 4), it can such as include：(methyl) acrylate, butoxy ethyl, butoxytriglycol (methyl) acrylate, epoxy chloropropionate Alkane is modified (methyl) butyl acrylate, dicyclopentenyl epoxide ethyl (methyl) acrylic acid, (methyl) acrylic acid -2- ethyoxyl second Ester, ethyl carbitol (methyl) acrylate, (methyl) acrylate, Nonylphenoxy polyethylene glycol (methyl) third The simple functions such as olefin(e) acid ester (poly-) ether (methyl) esters of acrylic acid；

Polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) third Aklylene glycol two (methyl) esters of acrylic acids such as olefin(e) acid ester, polytetramethylene glycol two (methyl) acrylate；By epoxy second The copolymer of alkane and expoxy propane, the copolymer of propane diols and tetrahydrofuran, poly- isoprene, the poly- isoprene of hydrogenation, poly- fourth The polyols such as the hydrocarbon polyols class such as cyclohexadienediol, hydrogenated polybutadiene diol and many officials derived from (methyl) acrylic acid Can (methyl) esters of acrylic acid；Oxirane, expoxy propane, epoxy butane to 1 mole of neopentyl glycol, more than 1 mole of addition etc. Two (methyl) acrylate of dihydric alcohol obtained from cyclic ether；

Two (methyl) acrylate of the alkylene oxide modifier of the bisphenols such as bisphenol-A, Bisphenol F, bisphenol S；Hydrogenated bisphenol A, Alkylene oxide modifier two (methyl) acrylate of the A Hydrogenated Bisphenol A classes such as A Hydrogenated Bisphenol A F, A Hydrogenated Bisphenol A S；To trimethylolpropane Or three obtained from the cyclic ether compound such as oxirane, expoxy propane, the epoxy butane of 1 mole of glycerine, more than 1 mole of addition List (methyl) acrylate, two (methyl) acrylate or three (methyl) acrylate of first alcohol；

To pentaerythrite or oxirane, expoxy propane, the epoxy of 1 mole of double trimethylolpropane, more than 1 mole of addition List (methyl) acrylate, two (methyl) acrylate, three (methyl) of trihydroxylic alcohol obtained from the cyclic ether compounds such as butane Acrylate or four (methyl) acrylate；To the oxirane of 1 mole of dipentaerythritol, more than 1 mole of addition, expoxy propane, Multifunctional (poly-) ether (first such as 3~6 functions (methyl) acrylate of hexahydroxylic alcohols obtained from the cyclic ether compounds such as epoxy butane Base) esters of acrylic acid etc..

It is used as (methyl) alkyl acrylate or (first that can be applied in combination in the photosensitive polymer combination of the present invention Base) acrylic acid alkylene ester (C-5), it can such as include：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) Propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) third The own ester of olefin(e) acid, (methyl) acrylic acid-2-ethyl caproite, (methyl) lauryl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) third The different monooctyl ester of olefin(e) acid, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) stearyl acrylate ester, (methyl) The different stearyl ester of acrylic acid, (methyl) isobornyl acrylate, dicyclopentenyl (methyl) acrylate, bicyclopentyl (methyl) third Olefin(e) acid ester, dicyclopentenyl (methyl) acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 3-methyl cyclohexanol ester, Simple function (methyl) acrylate such as (methyl) acrylic acid 1- adamantane esters, 2- ethylhexyls carbitol (methyl) acrylate Class；

Ethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, 1,4- butanediols two (methyl) propylene Acid esters, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 2- methyl isophthalic acids, 8- ethohexadiols two The hydrocarbon glycol such as (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, 1,10- decanediols two (methyl) acrylate Two (methyl) esters of acrylic acids；

List (methyl) acrylate of trimethylolpropane, two (methyl) acrylate or three (methyl) acrylate (with Under, use " many " as two, three, the polyfunctional general name of the fourth class), list (methyl) acrylate of glycerine or many (methyl) acrylic acid Ester, single or multiple (methyl) acrylate of pentaerythrite, single or multiple (methyl) acrylate of double trimethylolpropane, two seasons penta Single or multiple (methyl) acrylic acid of the polyalcohols such as trihydroxylic alcohol, tetrahydroxylic alcohol, the hexahydroxylic alcohols such as single or multiple (methyl) acrylate of tetrol Esters；

(methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxyl fourths (methyl) acrylic compounds containing hydroxyl such as ester, (methyl) acrylic acid -2- hydroxybutyls；Deng.

It is used as (methyl) propylene with aromatic rings that can be applied in combination in the photosensitive polymer combination of the present invention Acid esters (C-6), for example, can include：(methyl) phenyl acrylate, (methyl) benzyl acrylate etc. simple function (methyl) acrylic acid Esters；Two (methyl) esters of acrylic acids such as bisphenol-A two (methyl) acrylate, Bisphenol F two (methyl) acrylate etc., but do not limit In these.

It is used as (methyl) third with alicyclic structure that can be applied in combination in the photosensitive polymer combination of the present invention Olefin(e) acid ester (C-7), for example, can include：(methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) acrylic acid are different Norbornene ester, (methyl) acrylic acid dicyclopentenyl base ester etc. have simple function (methyl) esters of acrylic acid of alicyclic structure；Hydrogenation is double Two (methyl) acrylate of the A Hydrogenated Bisphenol A classes such as phenol A, A Hydrogenated Bisphenol A F；Tricyclodecane Dimethanol two (methyl) acrylate etc. Multi-functional (methyl) esters of acrylic acid with cyclic structure；(methyl) tetrahydrofurfuryl acrylate etc. has oxygen former in the structure Ester ring type (methyl) acrylate of son etc.；Deng, but it is not limited to these.

In addition, there is (methyl) acryloyl group as what can be applied in combination in the photosensitive polymer combination of the present invention Compound (C-8), in addition to above-mentioned compound, can also use for example：(methyl) acrylate copolymer and (methyl) The reaction product of glycidyl acrylate or (methyl) glycidyl acryiate polymer are anti-with (methyl) acrylic acid Answer poly- (methyl) acrylate copolymer (methyl) acrylate such as product；(methyl) acrylate etc. has ammonia (methyl) acrylate of base；Isocyanuric acid three (methyl) acryloyloxyethyl ester etc. isocyanuric acid (methyl) acrylate；Tool (methyl) acrylate of polysiloxane skeleton；Polybutadiene (methyl) acrylate, melamine (methyl) acrylate Deng.

In addition, as can be applied in combination in the photosensitive polymer combination of the present invention containing dimaleoyl imino Compound (C-9), for example, can include：N- normal-butyls maleimide, N- hexyls maleimide, 2- dimaleoyl imino second Base-ethyl carbonate ester, 2- maleimidoethyls-propyl carbonate, N- ethyls (2- maleimidoethyls) amino first Monofunctional aliphatic's maleimide such as acid esters；The ester ring type simple function maleimide such as N- N-cyclohexylmaleimides； N, N- hexa-methylene BMI, polypropylene glycol double (3- dimaleoyl iminos propyl group) ether, double (2- dimaleoyl imino second Base) the aliphatic bismaleimide amine such as carbonic ester；1,4- dimaleimides butylcyclohexane, isophorone double carbamate Ester ring type BMIs such as double (NEMs)；Maleimide guanidine-acetic acid and polytetramethylene glycol are entered Maleimide compound, the tetraoxane addition product by maleimidocaproic acid and pentaerythrite obtained from row esterification Carboxyl maleimide derivatives and various (polynary) alcohol are carried out ester by maleimide compound obtained from being esterified etc. (poly-) ester (poly-) maleimide compound etc. obtained from change, but it is not limited to these.

It is used as (methyl) acrylamide compound (C- that can be applied in combination in the photosensitive polymer combination of the present invention 10), it can such as include：Simple function (methyl) acrylic amides such as acryloyl morpholine, N- isopropyls (methyl) acrylamide；It is sub- Multifunctional (methyl) acrylic amides such as double (methyl) acrylamides of methyl etc..

As the unsaturated polyester (UP) (C-11) that can be applied in combination in the photosensitive polymer combination of the present invention, for example may be used Include：The fumaric acid esters such as dimethyl maleate, diethyl maleate；The multi-unsaturated carboxylic acids such as maleic acid, fumaric acid with The esterification reaction product of polyalcohol.

On the polymerizable compound (C) that can be applied in combination in the photosensitive polymer combination of the present invention, preferably group Close and use low viscosity and excellent (methyl) alkyl acrylate of light resistance, workability or (methyl) acrylic acid alkylene ester (C- 5), but it is not limited to above-claimed cpd, as long as the compound for having copolymerizable with above-mentioned (A), (B) composition just can be without special The compound of one or more is applied in combination to limitation.

Wherein, desirably belong to (methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester etc. and with C5~ C35, more preferably C15~C35 compound long-chain, with (methyl) acryloxy.Because, by with this The structure of sample, can obtain compatibility and the excellent photosensitive polymer combination of the transparency.

In the photosensitive polymer combination of the present invention, the ratio for above-mentioned (A) and (B), (C) composition is not limited especially System, relative to the weight % of (A) composition 1, preferably comprises 10~3000 weight % (B) composition, 10~3000 weight % (C) into Point, (B) composition particularly preferably containing 20~2000 weight %, 20~2000 weight % (C) composition.

In the photosensitive polymer combination of the present invention, softening ingredient (E) can be used as needed.It is used as workable softening The concrete example of composition, can include polymer compatible in the composition, oligomer, phthalate, phosphoric acid ester, Diol-lipid, citric acid ester type, aliphatic dibasic acid ester, fatty acid ester, epoxy plasticiser, castor-oil plant oils, terpenes Resin, hydriding terpene resinoid and liquid terpene etc..As above-mentioned oligomer, the example of polymer, can include has Polyisoprene skeleton, hydrogenated polyisoprene skeleton, polybutadiene skeleton, hydrogenated butadiene polymer skeleton or dimethylbenzene skeleton Oligomer or polymer and its carboxylate, polybutene etc..From the point of view of the transparency, preferably hydriding terpene resinoid, hydrogenation Polyisoprene, hydrogenated butadiene polymer, polybutene, liquid terpene.And then, from bonding Strong degree and with the compatibility of other materials Angle considers have the hydriding terpene resinoid of hydroxyl particularly preferably on end or side chain, have hydroxyl on end or side chain The hydrogenated polyisoprene of base, the polymer containing hydroxyl, the liquid such as hydrogenated butadiene polymer with hydroxyl on end or side chain State terpene resin.Alternatively, it is also possible to which two or more above-mentioned softening ingredients (E) are applied in combination.

On part by weight of the softening ingredient in photosensitive polymer combination, in the softening ingredient using solid When, usually 5~40 weight %, preferably 10~35 weight %.In the softening ingredient using liquid, usually 10~70 weight Measure %, preferably 20~60 weight %.

In the photosensitive polymer combination of the present invention, existing Photoepolymerizationinitiater initiater can be applied in combination as needed, as Its concrete example, can be included：The benzene such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether Acyloin class；Acetophenone, 2,2- diethoxy -2- phenyl acetophenones, 1,1- dichloroacetophenones, 2- hydroxy-2-methyls-phenyl third Alkane -1- ketone, diethoxy acetophenone, 1- hydroxycyclohexylphenylketones, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinoes The acetophenones such as propane -1- ketone；The Anthraquinones such as 2- EAQs, 2- tert-butyl groups anthraquinone, 2- chloroanthraquinones, 2- amyl anthraquinones；2,4- The thioxanthene ketone class such as diethyl thioxanthone, ITX, CTX；The double first of acetophenone dimethyl ketal, styrax The ketal class such as ether；The hexichol such as benzophenone, 4- -4 '-methyldiphenyls of benzoyl thioether, 4,4 '-bis- methylamino benzophenone Ketone class；Diphenyl (2,4,6- trimethylbenzoyls) phosphine oxide, double (2,4,6- trimethylbenzoyls) phenyl phosphine oxides Deng phosphinoxides etc..As their adding proportion, when the solid constituent of photosensitive polymer combination is set into 100 weight %, Usually 0.01~30 weight %, be preferably 0.1~25 weight %.

They can be used alone or are used in the form of mixture of more than two kinds, furthermore, it is possible to triethanolamine, The tertiary amines such as methyl diethanolamine, N, N- dimethyl ethyl aminobenzoates, N, the benzoic acid such as N- dimethylaminobenzoic acid isopentyl ester spread out Accelerator such as biology etc. are applied in combination.As the addition of these accelerator, it is added as needed on relative to Photoepolymerizationinitiater initiater For the amount below 100 weight %.

In the photosensitive polymer combination of the present invention, antioxidant can be added as needed on, it is organic solvent, silane coupled Agent, polymerization inhibitor, levelling agent, antistatic additive, surface lubricant, fluorescent whitening agent, light stabilizer (such as hindered amine compound), The additives such as filler.

As the concrete example of antioxidant, for example, it can include：BHT, 2,4- pairs-(n-octylthio) -6- (4- hydroxyls - 3,5- di-tert-butyls amido) -1,3,5- triazines, pentaerythrite four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], 2,2- is thio-di ethylene bis [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], triethylene glycol-bis- [3- (the tertiary fourths of 3- Base -5- methyl -4- hydroxy phenyls) propionic ester], 1,6-HD-bis- [3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic acid Ester], octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester, N, N- hexamethylene bis (3,5- di-t-butyls -4- Hydroxy-hydrocineamide), 1,3,5- trimethyls -2,4,6- three (3,5- di-t-butyl -4- acrinyls) benzene, three-(3,5- bis- The tert-butyl group -4- acrinyls)-isocyanuric acid ester, octylated diphenylamine, double [(pungent sulfenyl) the methyl]-orthoresols of 2,4-, iso-octyl - 3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], dibutyl hydroxy toluene etc..

As the concrete example of organic solvent, for example, it can include：The alcohols such as methanol, ethanol, isopropanol, dimethyl sulfone, diformazan Sulfoxide, tetrahydrofuran, dioxanes, toluene, dimethylbenzene etc..

As the concrete example of silane coupler, for example, it can include：3- glycidoxypropyltrime,hoxysilanes, 3- rings Oxygen propoxypropyl methyl dimethoxysilane, 3- glycidoxypropyls dimethoxysilane, 2- (3,4- epoxy hexamethylenes Base) ethyl trimethoxy silane, N- (2- aminoethyls) 3- aminopropyltriethoxies dimethoxysilane, γ-mercaptopropyi trimethoxy Silane, N- (2- aminoethyls) 3- aminopropyltriethoxies trimethoxy silane, 3- aminopropyl triethoxysilanes, 3- mercaptopropyi front threes TMOS, vinyltrimethoxy silane, N- (2- (vinyl-benzylamino) ethyl) 3- aminopropyl trimethoxysilane salt Hydrochlorate, 3- methacryloxypropyl trimethoxy silanes, 3- chloro hydroxypropyl methyls dimethoxysilane, 3- chloros propyl group three The silane coupling agents such as methoxy silane；Isopropyl (N- ethylaminoethyls amino) titanate esters, the isostearoyl base of isopropyl three Titanate esters, two (dioctylphyrophosphoric acid acyloxy) epoxide acetic acid titanium (titanium di (dioctyl pyrophosphate) Oxyacetate), tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters, (p-N- (β-aminoethyl) ammonia of new alkoxy three Phenyl) the titanium class coupling agent such as titanate esters；Acetylacetone,2,4-pentanedione zirconium, methacrylic acid zirconium, propionic acid zirconium, new alkoxy zirconium ester, new alcoxyl The new trineodecanoyl zirconate of base three, new alkoxy three (dodecane acyl group) benzenesulfonyl zirconate, (the ethylidene diamino of new alkoxy three Base ethyl) zirconate, new alkoxy three (m-aminophenyl base) zirconate, zirconium carbonate ammonium, aluminium acetylacetonate, aluminium methacrylate, The zirconiums such as propionic acid aluminium or aluminium class coupling agent etc..

As the concrete example of polymerization inhibitor, such as can include p methoxy phenol, methylnaphthohydroquinone.

As the concrete example of light stabilizer, for example, it can include：1,2,2,6,6- pentamethyl -4- piperidyls alcohol, 2,2,6, 6- tetramethyl -4- piperidyls alcohol, the pentamethyl -4- piperidine esters of (methyl) acrylic acid 1,2,2,6,6- (ADEKA Corp. manufacture, LA-82), 1,2,3,4- ethylene-dimalonic acids four (1,2,2,6,6- pentamethyl -4- piperidyls) ester, 1,2,3,4- ethylene-dimalonic acids four (2,2,6,6- tetramethyl -4- piperidyls) ester, 1,2,3,4- ethylene-dimalonic acids and 1,2,2,6,6- pentamethyl -4- piperidine alcohols and 3,9- double (2- hydroxyl -1,1- dimethyl ethyls) -2,4,8,10- four oxaspiro [5.5] undecanoic mixed ester compound, decane two Sour bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, double (1- hendecane epoxide -2,2,6,6- tetramethyl piperidines -4- Base) carbonic ester, methacrylic acid 2,2,6,6- tetramethyl -4- piperidine esters, decanedioic acid be double (2,2,6,6- tetramethyl -4- piperidyls) Ester, decanedioic acid double (1,2,2,6,6- pentamethyl -4- piperidyls) ester, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, 1- (2- (3- (3,5- di-tert-butyl-hydroxy phenyls) propionyloxy) ethyl) -4- (3- (3,5- di-tert-butyl-hydroxy phenyls) Propionyloxy) -2,2,6,6- tetramethyl piperidines, methacrylic acid 1,2,2,6,6- pentamethyl -4- piperidine esters, it is double (1,2,2,6, 6- pentamethyl -4- piperidyls) ((3,5- double (1,1- dimethyl ethyls) -4- hydroxy phenyls) methyl) butylmalonic acid ester, the last of the ten Heavenly stems two Sour double (2,2,6,6- tetramethyls -1 (octyl group epoxide) -4- piperidyls) esters, 1,1- dimethyl ethyls hydrogen peroxide and octane it is anti- Answer product, N, N ', N ", N " '-four-(4,6- couples-(butyl-(N- methyl -2,2,6,6- tetramethyl piperidine -4- bases) amino)-three Piperazine -2- bases) -4,7- diaza decane -1,10- diamines, dibutylamine 1,3,5- triazines N, N '-bis- (2,2,6,6- tetramethyls Condensation polymer, the poly- ((6- of base -4- piperidyl -1,6- hexamethylene diamines and N- (2,2,6,6- tetramethyl -4- piperidyls) butylamine (1,1,3,3- tetramethyl butyls) amino -1,3,5- triazine -2,4- diyls) ((2,2,6,6- tetramethyl -4- piperidyls) imines Base) hexa-methylene ((2,2,6,6- tetramethyl -4- piperidyls) imido grpup)), dimethyl succinate and 4- hydroxyls -2,2,6,6- four Polymer, 2,2,4,4- tetramethyls -20- (β-bay Epoxide carbonyl) ethyl -7- oxa-s -3,20- two of methyl isophthalic acid-piperidine ethanol The spiral shell of azepine two (51112) heneicosane -21- ketone, Beta-alanine, N- (2,2,6,6- tetramethyl -4- piperidyls)-ten two Arrcostab/tetradecane base ester, N- acetyl group -3- dodecyls -1- (2,2,6,6- tetramethyl -4- piperidyls) pyrroles -2,5- two Ketone, 2,2,4,4- tetramethyl -7- oxa-s -3,20- diaza two spiral shell (5,1,11,2) heneicosane -21- ketone, 2,2,4,4- tetramethyls Base -21- oxa- -3,20- diazabicylos-(5,1,11,2)-heneicosane -20- propionic acid dodecyl ester/tetradecane base ester, Malonic acid ((4- methoxyphenyls)-methylene)-bis- (1,2,2,6,6- pentamethyl -4- piperidyls) ester, 2,2,6,6- tetramethyls - High-grade aliphatic ester, the N of 4- piperidine alcohols, N '-bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides etc. are obstructed Amine, the benzophenone compound, 2- (2H- BTA -2- bases) -4- (1,1,3,3- tetramethyl butyl) benzene such as octabenzone Phenol, 2- (2- hydroxy-5-methyl bases phenyl) BTA, 2- (2- hydroxyls -3- (3,4,5,6- tetrahydric phthalimides-first Base) -5- aminomethyl phenyls) BTA, 2- (the 3- tert-butyl group -2- hydroxy-5-methyl bases phenyl) -5- chlorobenzotriazoles, 2- (2- hydroxyls Base -3,5- di-tert-pentyl-phenyls) BTA, 3- (3- (2H- BTA -2- bases) -5- tert-butyl-hydroxy phenyls) propionic acid The BTAs such as reaction product, 2- (2H- BTA -2- bases) -6- dodecyl -4- methylphenols of methyl esters and polyethylene glycol Class compound, the benzoates, 2- (4,6- hexichol such as 2,4- di-tert-butyl-phenyl -3,5- di-tert-butyl-4-hydroxybenzoic acid esters Base -1,3,5-triazines -2- bases) compound in triazine class such as -5- ((hexyl) epoxide) phenol etc., particularly preferred hindered amines chemical combination Thing.

As the concrete example of filler, for example, it can include：Crystalline silica, fused silica, aluminum oxide, zirconium Stone, calcium silicates, calcium carbonate, carborundum, silicon nitride, boron nitride, zirconium oxide, forsterite, steatite, spinelle, titanium dioxide, The powder of talcum etc. or bead obtained from making their spheroidizations etc..

In the case of there are various additives in the composition, weight of the various additives in photosensitive polymer combination Ratio is usually 0.01~3 weight %, preferably 0.01~1 weight %, more preferably 0.02~0.5 weight %.

The present invention photosensitive polymer combination can by by above-mentioned each composition at normal temperature~80 DEG C mixed dissolution and Obtain, can be operated as desired by filtering etc. by inclusion removal.In view of coating, photoresist group of the invention Compound is preferably by the proportioning for the viscosity appropriate modifying ingredients in the way of 300~40000mPas scope for making 25 DEG C.

The photosensitive polymer combination of the present invention does not need solvent substantially, but it is also possible to utilize such as MEK, methyl Aromatic hydrocarbons such as the acetate esters such as the ketones such as isobutyl ketone, ethyl acetate, butyl acetate, benzene,toluene,xylene etc. and other Typically conventional organic solvent dilutes the photosensitive polymer combination of the present invention to use.

The present invention photosensitive polymer combination can by irradiate 180~500nm wavelength ultraviolet or visible ray come It is polymerize.Alternatively, it is also possible to by the irradiation of the energy-ray beyond ultraviolet or utilize heat to solidify it.

As 180~500nm of wavelength ultraviolet or the light emitting source of visible ray, for example, it can include：Low pressure mercury lamp, high pressure Mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, chemical lamp, black light lamp, mercury xenon lamp, Excimer lamp, short-arc lamp, helium cadmium laser, argon Laser, PRK, sunshine.

The photosensitive polymer combination flexibility of the present invention is excellent, and weatherability, light resistance are high, except needing to maintain the transparency Optical applications beyond, also in various coatings arts such as ink, plastic paint, stationery printing, metal coating, furniture applications, liner, Insulating varnish, insulating trip, laminate in bonding agent and then electronics field, printed circuit board (PCB), protection ink (resist Ink it is), useful in the multiple fields such as semiconductor packages agent.As more specifically purposes, plano-convex version ink, flexo ink, gravure ink, The ink such as screen printed inks field, gloss paint field, paper coating agent field, carpenter are with paint field, beverage can coating agent or print The black field of brush, flexible packaging film smears, printer's ink or adhesive, heat-sensitive paper, thermosensitive film coating agent, printer's ink, bonding Agent, adhesive or coating optical fibers agent, liquid crystal display device, organic EL display, touching control panel image display device etc. show It is useful in the purposes such as the air gap filler (filler in the gap between display device and surface plate) of showing device.

In the present invention, carry out in vacuum abutted field in use, due to after vacuum abutted air gap filler etc. is estimated The generation of bubble is reduced, therefore is the application field being particularly useful.

Embodiment

Hereinafter, more specific description is carried out to the present invention by embodiment, but the invention is not restricted to following embodiments.

Synthesis example 1

In possessing reflux condenser, mixer, thermometer, thermostatic reactor, addition Irgacure2959 (BASF manufactures) 224.3g, methyl iso-butyl ketone (MIBK) (MIBK) 130g as reaction dissolvent, it is used as polymerization inhibitor 4- metoxyphenol 0.8g, the mixed dissolution at 80 DEG C.KarenzMOI (Showa Denko K. K's manufacture) is added after dissolving 155.2g, reacts 12 hours at 80 DEG C, is detected by infrared absorption spectroscopy (IR) and confirms that the peak from NCO disappears. By obtained reaction solution carry out 3 times washing, by concentration, can obtain crystalline crude product, make its in methanol solvate again Crystallization, the crystal that leaching is obtained is dried in vacuo, so as to obtain the autohemagglutination mould assembly optical polymerism shown in following formulas (2) Compound (A-1) 182g.Purity is more than 98%.

Embodiment 1~5, comparative example 1

The photosensitive polymer combination of compounding will be constituted as shown in table 1 below and is applied to easy bonding with bar coater (No.20) (Co., Ltd.'s manufacture is spun to processing polyester film by Japan：A-4300,188 μm of thickness) on, placed 1 minute in 80 DEG C of drying oven Afterwards, in air atmosphere, the distance with 120W/cm high-pressure sodium lamp from the high 10cm of lamp is purple with the transfer rate irradiation of 5m/ minutes Outside line, obtains the film with cured film (10~15 μm).

For the film obtained in embodiment or comparative example, evaluated by following projects, the results are shown in following tables 1。

(pencil hardness)

According to JISK5400, scratched using pencil, measure the pencil hardness of coat film.That is, with the solidification to be measured On the polyester film of film, the load for being applied from above 1kg with pencil with 45 degree of angle scratches 5mm or so, confirms scuffing degree. 5 measurements are carried out, the number of times without wound is counted.

Evaluate 5/5：In 5 times 5 times without wound

0/5：All there is wound in 5 times

(scratch resistance experiment)

Apply 200g/cm on steel wool #0000²Reciprocal 10 times of load, range estimation judges scratch situation.

Evaluate zero：Without wound

×：There is wound

(adaptation)

According to JISK5400,100 gridiron patterns of longitudinal and transverse 11 cut channels formation are marked with 1mm intervals on the surface of film. After the closely sealed cellophane adhesive tape (registration mark) in its surface, property is torn again, and display now goes out grid that is unstripped and remaining Number.

Evaluate zero：More than 80

×：Less than 79

(bad smell)

According to smell, following judgement is carried out to the bad smell remained in cured film.

Evaluate zero：Without bad smell

×：There is bad smell

[table 1]

Table 1

Irg.184：BASF is manufactured；1- hydroxycyclohexylphenylketones

DPHA-40H：Nippon Kayaku K. K manufactures；Polyfunctional carbamate acrylate

UX-5000：Nippon Kayaku K. K manufactures；Polyfunctional carbamate acrylate

UXT-6100：Nippon Kayaku K. K manufactures；Two function urethane acrylates

UX-5102D-M20：Nippon Kayaku K. K manufactures；Polyfunctional carbamate acrylate

UX-8101：Nippon Kayaku K. K manufactures；Two function urethane acrylates

DPHA：Nippon Kayaku K. K manufactures；The mixture of dipentaerythritol acrylate and five acrylate

MEK：2- butanone

Knowable to result as shown in Table 1, the photoresist of the autohemagglutination mould assembly photopolymerizable compound (A) containing the present invention Composition (D) has the photoreactivity equal with common commercially available Photoepolymerizationinitiater initiater, can be formed and in the past equal solidification Film.And then, the film of photosensitive polymer combination (D) of the present invention is coated with the basis of adaptation is maintained, and pencil is hard Degree, excellent scratch resistance, compared with conventional initiator, bad smell is also subtracted caused by coming from the residue of initiator It is few, it is also useful in terms of based on environmental issue/security caused by impure residue compound.

Synthesis example 2

In possessing reflux condenser, mixer, thermometer, thermostatic reactor, addition is poly- as hydrogenation GI-2000 (the iodine numbers of Tso Tat Co., Ltd., Japan's manufacture of butadiene polyol compound：12.2, hydroxyl value：46.8mg·KOH/ G) 569.73g (0.24mol), as diol compound Asahi Glass Co., Ltd manufacture EXCENOL3020 (polypropylene glycol, Hydroxyl value：35.9mgKOH/g) 7.50g (0.0024mol), KCC of the Xin Zhong villages manufacture as polymerizable compound S-1800A (the different stearyl ester of acrylic acid) 171.49g, the 4- metoxyphenol 0.41g as polymerization inhibitor, stirring until uniform, Internal temperature is set as 50 DEG C.Then, the IPDI 80.03g as polyisocyanate compound is added (0.36mol), is allowed to reaction until reaching the NCO content of target at 80 DEG C.Then, addition is as with least more than one Hydroxyl (methyl) acrylate compounds Osaka Organic Chemical Industry Co., Ltd. manufacture 2-Hydroxy ethyl acrylate 28.70g (0.247mol), the tin octoate 0.20g as urethane catalysts, are reacted at 80 DEG C, will As the terminal of reaction when NCO content reaches less than 0.1%, urethanes (B-1) are resulting in.

Embodiment 6~8, comparative example 2

Formula according to being constituted shown in table 2 below has made photosensitive polymer combination, and carries out following evaluate.Need Bright, curability is equal extent in embodiment and comparative example.

[table 2]

Table 2

(viscosity)

Use E type viscosimeters (TV-200：Toki Sangyo Co., Ltd. manufactures) measured at 25 DEG C.

(refractive index)

With Abbe refractomecer (DR-M2：Atagi Corp. manufactures) measure the refractive index (25 DEG C) of resin.

(cure shrinkage)

Preparation is coated with the thickness 1mm of fluorine-containing type releasing agent slide two panels, wherein a piece of releasing agent coated face Photosensitive polymer combination obtained by coating causes thickness to be 200 μm.Afterwards, two panels slide is applied with respective releasing agent The opposed facing mode of cloth cover is fitted.The resin combination is shone across glass high-pressure sodium lamp (80W/cm, ozone free) Penetrate accumulative light quantity 3000mJ/cm²Ultraviolet so that the resin composition.Afterwards, two panels slide is peeled off, so that The solidfied material of film specific gravity test is made.According to JIS K 7112B methods, the proportion (DS) of solidfied material is determined.In addition, 25 DEG C determine the liquid specific gravity (DL) of resin combination.According to DS and DL measurement result, cure shrinkage is calculated by following formula, tied Fruit is less than 3.0%.

Cure shrinkage (%)=(DS-DL) ÷ DS × 100

(rigidity modulus)

Prepare the PET film two panels after demoulding processing, be coated with resulting photonasty tree on a piece of stripping surface wherein Oil/fat composition causes thickness to be 200 μm.Afterwards, two panels PET film is pasted in the opposed facing mode of respective stripping surface Close.Accumulative light quantity 3000mJ/cm is irradiated to the resin combination across PET film high-pressure sodium lamp (80W/cm, ozone free)²'s Ultraviolet, so that the resin composition.Afterwards, two panels PET film is peeled off, so that having made rigidity modulus determines use Solidfied material.Rigidity modulus is determined with ARES (TA Instruments companies manufacture).

(transmissivity)

Prepare thickness 1mm slide two panels, the photosensitive polymer combination obtained by a piece of upper coating causes wherein Thickness after solidification is 200 μm.Afterwards, two panels slide is fitted.Shone across glass high-pressure sodium lamp (80W/cm, ozone free) Penetrate accumulative light quantity 3000mJ/cm²Ultraviolet so that the resin composition, has thus made transmissivity measure Solidfied material.For the transparency of resulting solidfied material, use spectrophotometer (U-3310, new and high technology Co., Ltd. of Hitach) Determine the transmissivity in 400~800nm and 400~450nm wavelength region.As a result, 400~800nm transmissivity For more than 90%, and 400~450nm transmissivity is more than 90%.

(heat-resisting, moisture-proof cementability)

Prepare thickness 1mm slide and thickness 1mm glass plate or post the thickness 1mm's of polarizing film in one side Glass plate, the photosensitive polymer combination obtained by being coated with one is so that thickness is 200 μm, then in the laminating of its coated face Another one.Accumulative light quantity 3000mJ/cm is irradiated to the resin combination across glass high-pressure sodium lamp (80W/cm, ozone free)² Ultraviolet so that the resin composition, has thus made cementability sample for evaluation.Using the sample, 85 are carried out DEG C heat resistant test, 60 DEG C of 90%RH humidity test, and place 100 hours.In the sample for evaluation, with visually to resin Solidfied material is confirmed from the stripping on glass or polarizing film, not peeling-off.

(bad smell)

According to smell, following judgement is carried out to the bad smell remained in cured film.

Evaluate zero：Without bad smell

×：There is bad smell

Although the present invention is described in detail with reference to specific embodiment, those skilled in the art, which understand, not to be taken off It can be made various changes and modifications in the case of from the spirit and scope of the present invention.

It should be noted that the application is based on the Japanese patent application (2015- proposed on January 26th, 2015 012349), it is incorporated herein entirely through the mode of reference.In addition, all references cited herein are totally integrating Herein.

Industrial applicability

The photosensitive polymer combination curability containing autohemagglutination mould assembly photopolymerizable compound of the present invention is excellent, can drop The harmful effects such as the exhaust generation caused by the low conventional impurity from Photoepolymerizationinitiater initiater.And then, photonasty of the invention Resin combination has low-shrinkage, and weatherability, light resistance are high, and the transparency is excellent, therefore for transparent display body of fitting It is useful in the optical component purposes such as bonding agent of substrate.

Claims (10)

1. a kind of photosensitive polymer combination (D), it is with the autohemagglutination mould assembly photopolymerizable compound represented by following formulas (1) (A), polymerizable compound (C) beyond carbamate (methyl) acrylate compounds (B) and (B) as it is necessary into Divide and constitute,

In formula (1), R represents hydrogen atom or methyl.

2. photosensitive polymer combination (D) according to claim 1, wherein, carbamate (methyl) acroleic acid esterification Compound (B) is carbamate (methyl) acrylic acid obtained from aliphatic category polyisocyanate compound is used as composition Ester compounds.

3. photosensitive polymer combination (D) according to claim 1 or 2, wherein, carbamate (methyl) acrylate Compound (B) is without xanthochromia type carbamate obtained from hydrogenated butadiene polymer polyol compound is used as composition (methyl) acrylate compounds.

4. the photosensitive polymer combination (D) according to any one of claims 1 to 3, wherein, carbamate (first Base) acrylate compounds (B) weight average molecular weight be more than 5000.

5. the photosensitive polymer combination (D) according to any one of Claims 1 to 4, wherein, polymerizable compound (C) it is (methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester.

6. the photosensitive polymer combination (D) according to any one of Claims 1 to 5, wherein, it is used as polymerism chemical combination Thing (C), further (methyl) acrylate containing hydroxyl.

7. the photosensitive polymer combination (D) according to any one of claim 1~6, it also includes softening ingredient (E)。

8. the photosensitive polymer combination (D) according to any one of claim 1~7, it is optical component purposes.

9. the photosensitive polymer combination (D) according to any one of claim 1~7, it is touch panel bonding agent Purposes.

10. the solidfied material of the photosensitive polymer combination described in a kind of any one of claim 1~7.