CN110382597A - Curable with actinic energy ray composition, the manufacturing method of cured film and hardening thing - Google Patents

Abstract

It provides curable with actinic energy ray composition, the hardening thing of the composition and the manufacturing method using cured film obtained by the composition, the curable with actinic energy ray composition to contain: silicon systems compound and absorbable light with alkoxysilane group and the photobase generator containing compound shown in set chemical formula for generating amine and living radical simultaneously.The storage stability of the curable with actinic energy ray composition, hardenability and film formation property are excellent, and its hardening thing is excellent to adaptation, the marresistance of substrate etc..

Description

Curable with actinic energy ray composition, the manufacturing method of cured film and hardening thing

Technical field

The present invention relates to curable with actinic energy ray resin combination, the hardening thing of the composition and use the composition The manufacturing method of the cured film obtained, the curable with actinic energy ray resin combination include containing the compound with specific structure Photobase generator and specific structure silicon systems compound.

Background technique

Using mobile phone, PDA as the liquid crystal display picture of the mobile communication of representative or as ATM, vehicle navigation device etc. The fields such as the touch panel of picture display input device in, although being used for the purpose of preventing the scratch to display picture more Hard coating (hard coat), but as the purposes of these display media expands, the requirement of the surface protection for showing media It is increasingly serious.

For such hard coating material, material with high hardness is contemplated to be to promote marresistance, such as in UV constrictive type In the hard coating material of organic system, it is known to improve its crosslink density to promote the technology of hardness, marresistance.But, such UV The hard coating material of constrictive type is handed over since the ring-opening polymerisation of addition polymerization, epoxide ring etc. by acrylic acid double bond improves Join density, therefore the contraction of the coating material generated in polymerization reaction itself can become problem, and only improved with organic principle hard There will be the limit for degree.

On the other hand, it can be enumerated by the feature of inorganic system's coating material of representative of polysiloxanes: apply material with organic system Material compares, and heat resistance, weatherability, hardness and marresistance etc. are excellent.With regard to the film coating of such inorganic system's coating material For forming method, make metal alkoxide hydrolysis/polycondensation using sol gel reaction, via metal oxygen alkane (metalloxane) oligomer and relatively low middle benefit gas carry out heat cross-linking/hardening method it is practical, and obtain film apply Layer has high rigidity.

Patent document 1 discloses the coating composition being made of ortho-siliformic acid partial condensate and colloidal silicon dioxide. It is therefore uneconomical however, the coating material of thermmohardening type needs a large amount of thermal energy in hardening, and have because by the heat applied so that The problems such as substrate deformation.

In order to solve these problems, that is, a kind of UV constrictive type organic and inorganic coating material is needed, UV constrictive type can be applied flexibly The excellent characteristics such as hardenability, the transparency possessed by organic coating materials, substrate adaptability, processability are had with inorganic based material The excellent characteristics such as some high rigidity, marresistance, and make up respective disadvantage.

Patent document 2 is disclosed by silicon dioxide granule, acryloxy functionality's silane or its hydrolysate and acrylate The composition that compound is constituted.But, the composition for the document hardened by Photoepolymerizationinitiater initiater, because not considering dioxy SiClx particle, silane position photo-hardening, therefore the hardness of hardening thing is insufficient.

Although patent document 3 discloses the mode in the particle surface importing polymerizable functional group of silica etc., such Improved silica is difficult in addition to production, and must have hydroxyl in the compound used to import polymerizable functional group Equal reactive groups, therefore the freedom degree designed is low are promoting the hardening thing of composition using silica obtained by by this method etc. It is limited in hardness.

Moreover, combinations of the above object is not consider the characteristic other than these for the purpose of promoting hardness, marresistance, Such as crack resistance, pliability, processability and anti-flammability etc..

That is, in the organic and inorganic coating material of UV constrictive type, storage stability is excellent, hardenability and film formation property no problem, Impact resistance, excellent abrasion and have both organic polymer various physical property UV constrictive type organic and inorganic coating material Not practical so far, in order to solve these problems simultaneously, inquiring into production hardens inorganic constituents simultaneously with organic principle, and The technology of inorganic constituents and the organic principle uniform integrated organic and inorganic mixed hardening film via covalent bond.

Patent document 4 discloses organic-nothing containing free base system Photoepolymerizationinitiater initiater and cationic system Photoepolymerizationinitiater initiater Machine mixing coating composition.But, the composition of the document must contain two kinds of different Photoepolymerizationinitiater initiaters, as a result increase group It closes the blending amount of the Photoepolymerizationinitiater initiater in object and gets higher the price of composition, it is not preferable.

And because the activity of cationic system Photoepolymerizationinitiater initiater is high and unstable, therefore the preservation for the composition that not only to worry is steady Qualitative, the acid generated by light irradiation also remained in hardening thing causes the sorrow of metal erosion.In addition, end residual Si OR When base, this hydrolysis can be made to become the step of determining rate (rate-determining step), it is possible to because the alcohol of generation makes certainly The hardening gone bad by base system Photoepolymerizationinitiater initiater, cationic system Photoepolymerizationinitiater initiater and caused composition is bad.

For the purpose of solving these problems, the importing of anionic system UV stiffening system is being inquired into recent years.Pass through light alkali Producing agent and the anion generated can directly carry out nucleation to SiOR base, can quickly generate SiOH.

Patent document 5 discloses the photoinitiator that alkali (amine) and free radical is generated by ultraviolet light irradiation.But, by this article The alkali that the Photoepolymerizationinitiater initiater offered generates is the low monofunctional amines of activity, the hardening capacity and deficiency as photobase generator.

Patent document 6 discloses the photobase generator that both alkali and free radical are generated by the irradiation of active ray.But, The photobase generator of the document is the ionic compound being made of carboxylic acid and amine, is generated because of the irradiation by active energy ray The activity of tertiary amine is very high and unstable, therefore has storage stability and deliquescent problem, and the tertiary amine is difficult to control because of alkane The hydrolysis of oxysilane base and the reaction of SiOH base generated, therefore have the molecule for the hydrolytic condensate that not can control alkoxy silane The problem of amount.Therefore, it is desirable to which Armeen or secondary amine and activity can be generated simultaneously certainly by the irradiation of active energy ray by having By the photobase generator of the neutral compound of base.

In order to solve these problems, it in non-patent literature 1 and 2, has inquired by generating Armeen or secondary amine simultaneously It is constituted with the photobase generator of the neutral compound of living radical and the silicon systems compound with alkoxysilane group Resin combination and its hardening thing.But the absorbing wavelength of the active energy ray of the photobase generator of these documents announcement is short Wavelength.Therefore, it is desirable to develop compared with the photosensitive region of previous photobase generator, for light (the active energy of more long wavelength Measure line) also there is high sensitivity, and the photobase generator of alkali is efficiently generated by the irradiation of the light of the long wavelength.

[existing technical literature]

[patent document]

[patent document 1] Japanese Patent Publication 52-039691 bulletin

[patent document 2] Japanese Unexamined Patent Application 62-256874 bulletin

No. 3474330 bulletins of [patent document 3] Japanese Patent

No. 5063915 bulletins of [patent document 4] Japanese Patent

[patent document 5] Japanese Unexamined Patent Publication 2009-58923 bulletin

[patent document 6] Japanese Unexamined Patent Publication 2011-202160 bulletin.

[non-patent literature]

[non-patent literature 1] J.Photopolym.Sci.Technol., Vol.27, No.2,223-225 (2014)

[non-patent literature 2] Chem.Lett.2014,43,612-614.

Summary of the invention

[the problem of invention is to be solved]

The object of the present invention is to provide a kind of active energy ray curable adhensive compositions, storage stability, hardenability and systems Film property is excellent, and its hardening thing while with high rigidity to the adaptation of substrate and excellent abrasion.

[mode solved the problems, such as]

It is that the inventors of the present invention inquire into as a result, finding that following active energy ray curable adhensive compositions can solve the above subject and complete At the present invention, which contains: also having for the light (active energy ray) of long wavelength highly sensitive It spends and the neutral compound of Armeen or secondary amine and living radical is generated by the irradiation of active energy ray simultaneously Photobase generator and silicon systems compound with alkoxysilane group.

That is, the present invention relates to following:

(1) a kind of curable with actinic energy ray composition, contains: with alkoxysilane group silicon systems compound and can It absorbs light and generates the photobase generator containing following formula (1) compound represented of amine and living radical simultaneously,

(in formula (1), R₁Indicate hydrogen atom, hydroxyl, alkoxy or organic group.R₂And R₃Indicate the virtue with substituent group Base.X is indicated from residue obtained by hydrogen atom of one Direct Bonding of removal on nitrogen-atoms in primary amine or secondary amine)；

(2) the curable with actinic energy ray composition as described in (1), wherein wavelength of the photobase generator in 350nm or more Have in region and absorbs；

(3) the curable with actinic energy ray composition as described in (1) or (2) also contains other than compound shown in formula (1) Photoepolymerizationinitiater initiater；

(4) the curable with actinic energy ray composition as described in any one of (1) to (3), also containing at least has 1 The compound of ammonia ester bond is as base-proliferating agent；

(5) the curable with actinic energy ray composition as described in any one of (1) to (4), also contains with acryloyl The compound of base and/or methylacryloyl；

(6) a kind of hardening thing is the hard of curable with actinic energy ray composition described in any one of aforementioned (1) to (5) Compound；And

(7) a kind of manufacturing method of cured film, wherein the cured film is using described in any one of aforementioned (1) to (5) Curable with actinic energy ray composition and obtain, which includes:

The step of (a) the curable with actinic energy ray composition is coated on substrate and forms envelope,

The step of the first heating (b) is carried out to the envelope,

(c) will carry out this first heating envelope exposure the step of and

(d) the step of envelope for having carried out the exposure being subjected to the second heating.

[The effect of invention]

Curable with actinic energy ray composition of the invention, because storage stability, hardenability and film formation property are excellent, and it is hard Compound while with high rigidity to the adaptation of substrate and excellent abrasion, therefore can be suitable for the liquid of mobile phone etc. Hard coating purposes such as crystalline substance display picture, touch panel etc..

Detailed description of the invention

Fig. 1 is the material as Examples and Comparative Examples and the suction of photobase generator (Photoepolymerizationinitiater initiater) 1 to 7 that uses Luminosity curve.

Specific embodiment

Hereinafter, the curable with actinic energy ray composition that the present invention will be described in detail, but active energy ray hardening of the invention Type composition is not limited to embodiment.

[the silicon systems compound with alkoxysilane group]

Curable with actinic energy ray composition of the invention contains the silicon systems compound with alkoxysilane group.

Contained by curable with actinic energy ray composition of the invention with alkoxysilane group silicon systems compound (with Under, referred to as " silicon systems compound ") it can be mentioned, for example with 1 to 3 alkoxysilane group silane coupling agent, with 1 to 4 alkane The alkoxysilane compound containing trialkylsilyl group in molecular structure etc. of oxysilane base, a part of alkoxysilane group can be hydrolyzed or hydrolytic polycondensation closes.Silicon systems Alkoxy in alkoxysilane group possessed by compound, for the viewpoints such as reactivity, stability, preferred carbon number 1 to 8 Alkoxy, specific preferably methoxyl group, ethyoxyl, (different) propoxyl group or (different) butoxy, more preferable methoxy or ethoxy.Separately Outside, in this specification, such as the record of " (different) propyl " refers to both n-propyl and isopropyl.Aforementioned silane coupling agent can have Functional group other than alkoxysilane group, the preferred amino of the functional group that can have, epoxy group, sulfydryl, isocyanate group or the hydroxyl, More preferable amino.

The concrete example of silane coupling agent with alkoxysilane group can be enumerated: 3- acryloxypropyl trimethoxy Silane, 3- methacryloxypropylmethyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- Methacryloxypropyl methyl diethoxysilane, 3- methacryloxypropyl, 2- (3,4- ring Oxygroup cyclohexyl) ethyl trimethoxy silane, 3- epoxy propoxy propyl methyl dimethoxysilane, 3- glycidoxypropyl group Trimethoxy silane, 3- glycidoxypropyl diethoxy silane, 3- epoxy propoxy propyl triethoxysilane；3- Aminopropyltriethoxywerene werene, 3- TSL 8330, N- (2- amino-ethyl) -3- aminopropyl trimethoxy Silane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane and 3- (N- phenyl amino propyl trimethoxy silane Equal amino silanes；2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane, 3- glycidoxypropyltrime,hoxysilane And the epoxy radicals silicone hydrides such as 3- epoxy propoxy propyl triethoxysilane；3-mercaptopropyi trimethoxy silane and 3- mercaptopropyi The hydrosulphonyl silanes such as triethoxysilane；The polysulfur silanes such as 3- octanoylthio -1- propyl-triethoxysilicane；3- isocyanates propyl Isocynate silanes such as triethoxysilane and 3- isocyanate propyl trimethoxysilane etc..These silane coupling agents, can be single 1 kind is solely used, two or more can also be applied in combination, it is possible to use the silane that partially application hydrolysis or hydrolytic polycondensation close in advance is even Join agent.

The concrete example of alkoxysilane compound containing trialkylsilyl group in molecular structure can be enumerated: trimethylmethoxysilane, dimethyldimethoxysil,ne, Methyltrimethoxysilane, tetramethoxy-silicane, methyl dimethoxysilane, trimethylethoxysilane, dimethyl diethoxy Base silane, methyltriethoxysilane, tetraethoxysilane, dimethoxydiphenylsilane, phenyltrimethoxysila,e, hexichol Base diethoxy silane, phenyl triethoxysilane, hexyl trimethoxysilane, tetrapropoxysilane and four butoxy silanes Deng.These alkoxysilane compound containing trialkylsilyl group in molecular structure can be used alone a kind, two or more can also be applied in combination, it is possible to use preparatory part Apply the alkoxysilane compound containing trialkylsilyl group in molecular structure of hydrolysis or hydrolytic polycondensation conjunction.

Silicon systems compound contained by curable with actinic energy ray composition of the invention, preferably 3- acryloxypropyl Trimethoxy silane, 3- methacryloxypropylmethyl dimethoxysilane, 3- methacryloxypropyl trimethoxy Base silane, 3- methacryloxypropyl methyl diethoxysilane, 3- methacryloxypropyl, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane, 3- epoxy propoxy propyl methyl dimethoxysilane, 3- epoxy Propoxypropyl trimethoxy silane, 3- glycidoxypropyl diethoxy silane, three second of 3- glycidoxypropyl group Oxysilane, trimethylmethoxysilane, dimethyldimethoxysil,ne, methyltrimethoxysilane, tetramethoxy-silicane, first Base dimethoxysilane, trimethylethoxysilane, dimethyl diethoxysilane, methyltriethoxysilane or tetraethoxy Silane, more preferable 3- acryloyloxypropyltrimethoxysilane, 3- methacryloxypropylmethyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl methyl diethoxysilane, 3- methyl Acryloxypropyl triethoxysilane, tetramethoxy-silicane, tetramethoxy-silicane or tetraethoxysilane.

[photobase generator]

Curable with actinic energy ray composition of the invention contains photobase generator, and the photobase generator is preferably in 350nm Have in above wavelength region and absorb, and is the specific photobase generator for absorbing light and generating amine and living radical simultaneously (hereinafter, also referred to as " photobase generator of essential component ").

[formula (1) compound represented]

Following formula (1) compound represented can be used as institute in curable with actinic energy ray composition of the invention The photobase generator contained.

In formula (1), R₁Indicate hydrogen atom, hydroxyl, alkoxy or organic group.The R of formula (1)₁The preferred carbon of the alkoxy of expression The alkoxy of number 1 to 18, concrete example can enumerate methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutyl Oxygroup, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, neopentyl oxygen, positive hexyloxy and dodecyl oxygroup etc..

The R of formula (1)₁The concrete example of the organic group of expression can enumerate the alkyl of carbon number 1 to 18, the alkene of carbon number 2 to 18 Base, the alkynyl of carbon number 2 to 18, the aryl of carbon number 6 to 12, the acyl group of carbon number 1 to 18, the aroyl of carbon number 7 to 18, nitro, cyanogen Base, the alkyl sulfenyl of carbon number 1 to 18 and halogen atom etc..

With regard to the R of formula (1)₁For the alkyl of the carbon number 1 to 18 of the concrete example of the organic group of expression, methyl, second can be enumerated Base, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive nonyl The alkyl and cyclopropyl of the straight-chains such as base, positive decyl, n-undecane base and dodecyl or branched, cyclobutyl, ring penta Base and the isothrausmatic alkyl of cyclohexyl, the preferably alkyl of carbon number 2 to 6, the straight-chain of more preferable carbon number 2 to 6 or the alkane of branched Base.

With regard to the R of formula (1)₁For the alkenyl of the carbon number 2 to 18 of the concrete example of the organic group of expression, can enumerate vinyl, Acrylic, 1- cyclobutenyl, isobutenyl, 1- pentenyl, 2- pentenyl, 2-methyl-1-butene alkenyl, 3-methyl-1-butene base, 2- Methyl-2-butene base, 2,2- dicyanoethenyl, 2- cyano -2- methyl carboxy vinyl and 2- cyano -2- methyl sulfone vinyl Deng.

With regard to the R of formula (1)₁For the alkynyl of the carbon number 2 to 18 of the concrete example of the organic group of expression, can enumerate acetenyl, 1- propinyl and 1- butynyl etc..

With regard to the R of formula (1)₁For the aryl of the carbon number 6 to 12 of the concrete example of the organic group of expression, phenyl, naphthalene can be enumerated Base and tolyl etc., the preferably aryl of carbon number 6 to 10.

With regard to the R of formula (1)₁For the acyl group of the carbon number 1 to 18 of the concrete example of the organic group of expression, can enumerate formoxyl, Acetyl group, ethylcarbonyl group, n-propyl carbonyl, Isopropylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl, isopentyl carbonyl, neopentyl Carbonyl, 2- methylbutylcarbonyl and nitrobenzene methyl carbonyl etc..

With regard to the R of formula (1)₁For the aroyl of the carbon number 7 to 18 of the concrete example of the organic group of expression, benzoyl can be enumerated Base, toluyl groups (toluoyl), naphthoyl and phthalyl etc..

With regard to the R of formula (1)₁For the alkyl sulfenyl of the carbon number 1 to 18 of the concrete example of the organic group of expression, methyl can be enumerated Sulfenyl, ethylsulfanyl, n-propyl sulfenyl, isopropylsulfanyl, n-butylthio, i-butylthio, s-butylthio, tert-butyl sulphur Base, n-pentyl sulfenyl, isopentyl sulfenyl, 2- methyl butyl sulfide, 1- methyl butyl sulfide, neopentyl sulfenyl, 1,2- dimethyl Propyl sulfenyl and 1,1- dimethyl propyl sulfenyl etc..

With regard to the R of formula (1)₁For the halogen atom of the concrete example of the organic group of expression, can enumerate fluorine atom, chlorine atom, Bromine atom and iodine atom.

R in formula (1)₁It is preferred that alkoxy, the alkoxy of more preferable carbon number 1 to 18, the even more preferably alcoxyl of carbon number 1 to 6 Base, the alkoxy of particularly preferred carbon number 1 to 4, most preferably methoxyl group.

In formula (1), R₂And R₃Indicate aryl, possessed hydrogen atom can be substituted base substitution to the aryl in its structure.R₂ And R₃It is preferred that the aryl with substituent group.

The R of formula (1)₂And R₃The aryl of expression refers to from residue obtained by one hydrogen atom of removal in aromatic hydrocarbon, the fragrance The concrete example of race's hydrocarbon can enumerate benzene, naphthalene, anthracene, phenanthrene, pyrene etc..

R in formula (1)₂And R₃It is preferred that more preferably being removed from benzene from residue obtained by a hydrogen atom is removed in benzene or naphthalene Residue obtained by one hydrogen atom.

R as the formula that may replace (1)₂And R₃The aryl of expression in the structure possessed by hydrogen atom substituent group it is specific Example, can enumerate halogen atom, hydroxyl, alkoxy, sulfydryl, sulfide base, silylation, silanol group, nitro, nitroso, cyano, Asia Sulfonic group, sulfonic group, sulfonic acid foundation (sulfonato), phosphino-, sub- phosphono (phosphinyl), phosphono (phosphono), phosphonic acids foundation (phosphonato), amino, ammonium or organic group, R₂And R₃There are it is several when, each R₂And R₃Can be identical each other, it can also be different.

It may replace the R of formula (1)₂And R₃The aryl of expression in the structure possessed by hydrogen atom halogen atom, fluorine can be enumerated Atom, chlorine atom, bromine atom and iodine atom.

It may replace the R of formula (1)₂And R₃The aryl of expression in the structure possessed by hydrogen atom alkoxy, can enumerate and formula (1) R₁The alkoxy of expression is identical.

It may replace the R of formula (1)₂And R₃The aryl of expression in the structure possessed by hydrogen atom organic group concrete example, Can enumerate alkyl, aryl, aralkyl, halogenated alkyl, isocyano group, cyanato- (cyanato), isocyanate group (isocyanato), Thiocyano (thiocyanato), isothiocyano (isothiocyanato), alkoxy carbonyl, amine formyl, amine formyl sulfide base, Carboxyl, carboxylic acid foundation, acyl group, acyloxy, oxyimino etc..

R as the formula that may replace (1)₂And R₃The aryl of expression in the structure possessed by hydrogen atom organic group tool Alkyl, aryl and the acyl group of body example can enumerate the R respectively with formula (1)₁The carbon number 1 to 18 of the concrete example of the organic group of expression Alkyl, carbon number 6 to 12 aryl and carbon number 1 to 18 the identical organic group of acyl group.

About these organic groups, containing the bonding other than the alkyl such as hetero atom, substituent group in the organic group, these Group can be straight-chain, be also possible to branched.It may replace R₂And R₃The aryl of expression in the structure possessed by hydrogen atom Organic group when the cyclic structure stated after its formation etc., can also become divalent or more although the organic group of usually monovalence Organic group.

It may replace R₂And R₃The aryl of expression in the structure possessed by hydrogen atom organic group in alkyl carbon and hydrogen Bonding (C is bonded with H's) other than bonding be not particularly limited as long as not undermining effect of the invention, can enumerate ehter bond, Thioether bond, carbonyl bond, thiocarbonyl group key, ester bond, amido bond, ammonia ester bond, carbonic acid ester bond, sulfonyl key, sulfinyl key, azo bond Deng.For heat resistance, bonding other than being bonded of the carbon of the alkyl in organic group and hydrogen, preferably ehter bond, thioether bond, carbonyl Key, thiocarbonyl group key, ester bond, amido bond, ammonia ester bond, imino group key (- N=C (- R)-,-C (=NR)-: herein R be hydrogen atom or Organic group), carbonic acid ester bond, sulfonyl key, sulfinyl key.

It may replace R₂And R₃The aryl of expression in the structure possessed by hydrogen atom organic group in alkyl other than take Dai Ji is not particularly limited as long as not undermining effect of the invention, can enumerate halogen atom, hydroxyl, sulfydryl, sulfide base, Cyano, isocyano group, cyanato-, isocyanate group, thiocyano, isothiocyano, silylation, silanol group, alkoxy, alkoxy carbonyl, Amine formyl, amine formyl sulfide base, nitro, nitroso, carboxyl, carboxylic acid foundation, acyl group, acyloxy, sulfinic acid base, sulfonic group, sulphur Acid group base, phosphino-, sub- phosphono, phosphono, phosphonic acids foundation, oxyimino, saturation or unsaturated alkyl ether, saturation or not Saturated alkyl sulfenyl ether, aryl ether and artyl sulfo ether, amino (- NH₂,-NHR ,-NRR ': herein, R and R ' are point Not independent alkyl), ammonium etc..Hydrogen contained in above-mentioned substituent group can replace through alkyl.In addition, institute in above-mentioned substituent group The alkyl contained can be straight chain, branch and cricoid any.Wherein, it may replace R₂And R₃The aryl of expression institute in the structure The substituent group other than alkyl in the organic group for the hydrogen atom having, preferably halogen atom, hydroxyl, sulfydryl, sulfide base, cyanogen Base, isocyano group, cyanato-, isocyanate group, thiocyano, isothiocyano, silylation, silanol group, alkoxy, alkoxy carbonyl, amine Formoxyl, amine formyl sulfide base, nitro, nitroso, carboxyl, carboxylic acid foundation, acyl group, acyloxy, sulfinic acid base, sulfonic group, sulfonic acid Foundation, phosphino-, sub- phosphono, phosphono, phosphonic acids foundation, oxyimino, saturation or unsaturated alkyl ether, saturation or insatiable hunger With alkyl sulfenyl ether, aryl ether and artyl sulfo ether.

In addition, may replace R₂And R₃The aryl of expression in the structure possessed by hydrogen atom substituent group in 2 or more can It is bonded and forms cyclic structure.Cyclic structure can be saturated or unsaturated ester ring type hydrocarbon, heterocycle and condensed ring, and selected from by The ester ring type hydrocarbon, heterocycle and condensed ring group in groups in two or more structure being composed.

In the photobase generator of essential component of the invention, preferably importing 1 or more may replace R₂And R₃The aryl of expression The substituent group of possessed hydrogen atom in the structure.That is, may replace R₂And R₃The aryl of expression in the structure possessed by hydrogen atom Substituent group the preferred halogen of at least one, hydroxyl, sulfydryl, sulfide base, silylation, silanol group, nitro, nitroso, sulfinic acid Base, sulfonic group, sulfonic acid foundation, phosphino-, sub- phosphono, phosphono, phosphonic acids foundation, amino, ammonium or organic group.Pass through importing For example above-mentioned substituent group of at least one is to may replace substituent R₂And R₃The aryl of expression in the structure possessed by hydrogen atom take The wavelength for the light that photobase generator absorbs is adjusted in Dai Ji, can also absorb desired wavelength by importing substituent group.Pass through The substituent group for importing the conjugated chain as extended aromatic ring, can be changed into long wavelength for absorbing wavelength.In addition, can also be promoted molten Xie Xing, the intermiscibility between combined macromolecule precursor.It whereby, can be in the absorption wave that the macromolecule precursor to be combined is contemplated While long, the sensitivity of Photosensitve resin composition is promoted.

It may replace R₂And R₃The aryl of expression in the structure possessed by hydrogen atom substituent group, preferably methyl, ethyl, third The alkyl of the carbon numbers 1 to 20 such as base；The naphthenic base of the carbon numbers 4 to 23 such as cyclopenta, cyclohexyl；The carbon numbers such as cyclopentenyl, cyclohexenyl group 4 To 23 cycloalkenyl；The carbon numbers 7 to 26 such as phenoxymethyl, 2- Phenoxyethyl, 4- phenoxy group butyl aryloxy alkyl (- ROAr yl)；The aralkyl of the carbon numbers 7 to 20 such as benzyl, 3- phenyl propyl；Cyano methyl, beta-cyano ethyl etc. have cyano The alkyl of carbon number 2 to 21；Hydroxymethyl etc. has the alkyl of the carbon number 1 to 20 of hydroxyl；The carbon numbers 1 to 20 such as methoxyl group, ethyoxyl Alkoxy, acetylamino, benzenesulfonamido- (C₆H₅SO₂The acylamino- of carbon numbers 2 to 21 such as NH-)；Methylsulfany, ethylsulfanyl The alkyl sulfenyl (- SR base) of equal carbon numbers 1 to 20；Acyl group, methoxycarbonyl, the acetyl of the carbon numbers 1 to 20 such as acetyl group, benzoyl The ester group (- COOR base and-OCOR base) of the carbon numbers 2 to 21 such as oxygroup；The carbon numbers 6 to 20 such as phenyl, naphthalene, xenyl, tolyl Aryl；The aryl of the carbon number 6 to 20 replaced through electron-donating group and/or electron-withdrawing group；Through electron-donating group and/or electrophilic Benzyl, cyano and the methylsulfany (- SCH that group replaces₃).It, can also be in addition, above-mentioned moieties can be straight chain It is branched, is also possible to ring-type.

Additionally it is necessary to may replace R in the photobase generator of ingredient₂And R₃Possessed hydrogen is former in the structure for the aryl of expression When at least one of the substituent group of son is hydroxyl, and R may replace₂And R₃The aryl of expression in the structure possessed by hydrogen atom take The compound of Dai Jizhong not hydroxyl is compared, just can long wavelength for the deliquescent promotion of alkaline aqueous solution etc. and absorbing wavelength It is preferred for change.

In formula (1), X is indicated from amine obtained by hydrogen atom of one Direct Bonding of removal on nitrogen-atoms in primary amine or secondary amine Residue.

The concrete example for the amine residue that the X of formula (1) is indicated, can enumerate from amine compounds shown in following formula (a) to (z) etc. Remove residue obtained by hydrogen atom of the Direct Bonding on nitrogen-atoms.

Hydrogen atom is removed from the amine compounds in a molecule shown in formula (a), formula (b) etc. with two amino and is made When residue, it can be from the residue for removing monovalence obtained by hydrogen atom in an amino, be also possible to remove respectively from two amino The residue of divalent obtained by one hydrogen atom.In addition, amine compounds shown in (a), formula (b) etc. are that have two ammonia in a molecule The amine compounds of base, but from have in a molecule hydrogen atom is removed in the amine compounds there are three amino and when being made residue, can be with Be one into trivalent any valence residue, from a molecule have there are four amino amine compounds in remove hydrogen atom and be made residual When base, can be one into tetravalence any valence residue.From the compound that the amino number in a molecule is five or more When being made residue except hydrogen atom, and it is the same.

The amine residue that the X of formula (1) is indicated removes a Direct Bonding preferably from amine compounds shown in formula (a) to (z) Residue obtained by hydrogen atom on nitrogen-atoms removes a direct key more preferably from amine compounds shown in formula (a) to (n) Close residue obtained by the hydrogen atom on nitrogen-atoms.

The photobase generator of silicon systems compound and essential component in active energy ray curable adhensive compositions of the invention Use ratio, stability, the transparency, wearability, marresistance, adaptation and the cracking resistance of the cured film of acquisition according to composition Property and design.Total amount relative to silicon systems compound and the photobase generator of essential component, it is necessary to the photobase generator of ingredient Usually 5 to 80 quality %, preferably 10 to 60 quality %, more preferable 20 to 40 quality %.

[can Photoepolymerizationinitiater initiater]

In curable with actinic energy ray composition of the invention, can also and with the change with part-structure shown in formula (1) Close the Photoepolymerizationinitiater initiater other than object.Can Photoepolymerizationinitiater initiater, previous known optical free radical producing agent, light can be enumerated Acid producing agent, photobase generator etc..These Photoepolymerizationinitiater initiaters, can and with a kind, can also by two or more combination and be used in combination.

In curable with actinic energy ray composition of the invention can optical free radical producing agent be have can pass through Light excites and starts the compound of the function of free radical polymerization, and it can be mentioned, for example monocarbonyl compound, dicarbonyl compound, benzene second Ketone compound, benzoin ether compound, acylphosphine oxide compound and aminocarboxyl compound etc..

Optical free radical producing agent in curable with actinic energy ray composition of the invention, with regard to the transparent of hardening thing For the viewpoint of property, preferably acetophenone compound, acylphosphine compounds etc., more preferable acetophenone compound.

In curable with actinic energy ray composition of the invention can photoacid generator, refer to by ultraviolet light, The irradiation of the radioactive ray such as the excimer laser such as far ultraviolet, KrF or ArF, X-ray and electron beam and generate cation, the sun from Son is the compound that can become polymerization initiator, and it can be mentioned, for example aromatic series iodine complex salts, aromatic matte complex salt.

The concrete example of aromatic series iodine complex salt can enumerate four (pentafluorophenyl group) boric acid diphenyl iodniums, hexafluorophosphoric acid diphenyl Salt compounded of iodine, hexafluoro-antimonic acid diphenyl iodnium, hexafluorophosphoric acid two (4- nonyl phenyl) salt compounded of iodine, four (pentafluorophenyl group) boric acid tolyl isopropyls Phenyl salt compounded of iodine (manufacture of Rhodia (Rhodia) company, trade name RHODOSIL PI2074), two (4- tert-butyl) iodine, three (trifluoro Mesyl) methide (BASF AG's manufacture, trade name CGI BBI-C1) etc..

The concrete example of aromatic matte complex salt can enumerate hexafluoro-antimonic acid 4- thienyl diphenylsulfonium hexafluoroantimonate (San Apro corporation Make, trade name CPI-101A), three (pentafluoroethyl group) three fluorophosphoric acid thienyl diphenylsulfonium hexafluoroantimonates (San Apro company manufacture, commodity Name CPI-210S), bis- (4- fluorophenyl) sulfonium salts of hexafluoro-antimonic acid 4- [4- (2- chlorobenzene formacyl) phenylsulfartyl] phenyl (ADEKA public affairs Department's manufacture, trade name SP-172), the mixing of hexafluoro-antimonic acid aromatic series sulfonium salt containing hexafluoro-antimonic acid 4- thienyl diphenylsulfonium hexafluoroantimonate Object (ACETO Corporate USA manufacture, trade name CPI-6976) and triphenylsulfonium three (trifyl) methide (BASF AG's manufacture, trade name CGI TPS-C1), three [4- (4- acetylphenyl) sulfonvlphenyl] (trifluoromethyl sulphurs of sulfonium three Acyl group) methide (BASF AG's manufacture, trade name CGID 26-1), four (2,3,4,5,6- pentafluorophenyl group) boric acid, three [4- (4- acetylphenyl) sulfonvlphenyl] sulfonium salt (BASF AG's manufacture, trade name IRGACURE PAG290) etc..

In curable with actinic energy ray composition of the invention can photobase generator, referring to can be by ultraviolet light etc. Light irradiates and the compound that generates bisguanides (biguanidium), imidazoles, pyridine, diamines and these derivative etc., concrete example Can enumerate 9- anthrylmethyl-N, N- diethylamino formic acid esters, (E) -1- [3- (2- hydroxy phenyl) -2- acryloyl group] piperidines, Imidazole formic acid 1- (anthraquinone -2- base) ethyl ester, 4- methacryloxy piperidines -1- formic acid 2- nitrobenzophenone methyl esters, 1,2- bis- are different Propyl -3- [bis- (dimethylamino) methylene] guanidine -2- (3- benzoylphenyl) propionic ester, dicyclohexyl -4,4,5 1,2-, 5- tetramethyl bisguanides-normal-butyl triph-enylborate etc..These photobase generators can be used alone a kind, can also be by two or more It is applied in combination.

Photobase generator in curable with actinic energy ray composition of the invention, can preferably generate imidazoles or two The compound of guanidine.

The content of Photoepolymerizationinitiater initiater in curable with actinic energy ray composition of the invention, preferably in active energy ray It is 10 mass % or less in constrictive type composition.

In curable with actinic energy ray composition of the invention, can also and alkali be generated with proliferative due to the effect because of alkali Base-proliferating agent.By can further promote this in curable with actinic energy ray composition of the invention and with base-proliferating agent The sensitivity of curable with actinic energy ray composition.Especially fail the depth of arrival curable with actinic energy ray composition layer in light Situation (the thicker situation of curable with actinic energy ray composition layer irradiated by light, curable with actinic energy ray of layer part Composition contains the situation etc. of a large amount of dyestuff, pigment), pass through the surface photochemistry in curable with actinic energy ray composition layer The effect of the alkali generated to property and because the alkali breeder reaction caused by base-proliferating agent starts to carry out, and thermochemistry and linksystem it is raw At alkali, therefore it is expected to generate base catalyzed reactions even if the further portion of curable with actinic energy ray composition layer.Can Base-proliferating agent is not particularly limited, although it can be mentioned, for example Japanese Unexamined Patent Publication 2000-330270 bulletins, Japanese Unexamined Patent Publication 2002- No. 128750 bulletins or K.Arimitsu, M.Miyamoto and K.Ichimura, Angew.Chem.Int.Ed., 39,3425 (2000) base-proliferating agent disclosed in such as, but preferably base-proliferating agent contains compound at least with 1 ammonia ester bond.

The content of base-proliferating agent in curable with actinic energy ray composition of the invention, although the alkali according to essential component produces The type of raw agent, silicon systems compound etc. is combined and is suitably determined, but is combined in curable with actinic energy ray of the invention Preferably 40 mass % in object are hereinafter, more preferable 5 to 20 quality %.

In curable with actinic energy ray composition of the invention, can also and with have acryloyl group and/or metering system The compound of acyl group.

Compound with acryloyl group and/or methylacryloyl can enumerate (methyl) methyl acrylate, (methyl) third Olefin(e) acid ethyl ester, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) propylene Tert-butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) stearyl acrylate, (methyl) Lauryl acrylate, (methyl) acrylic acid tetrahydrofuran methyl esters, (methyl) isobornyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) phenoxyethyl acrylate, phenoxy group ethylene glycol (methyl) acrylate, methoxyl group are poly- The alkoxy polyalkyleneglycols (methyl) third such as propylene glycol (methyl) acrylate, ethyoxyl polyethylene glycol (methyl) acrylate Olefin(e) acid esters；(methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxyl fourth Ester, (methyl) glycerol acrylate, polyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate etc. contain hydroxyl (methyl) esters of acrylic acid；(methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) third N substituted type (the first such as acrylamide, N- isopropyl (methyl) acrylamide, diacetone (methyl) acrylamide, acryloyl morpholine Base) acrylic amide；(methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- diethylamino ethyl ester etc. (methyl) esters of acrylic acid containing amino；The nitriles such as (methyl) acrylonitrile；The phenylethylenes such as styrene, α-methylstyrene； The second such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, isobutyl vinyl ether Alkenyl ethers；The fatty acid ethylenes esters such as vinyl acetate, vinyl propionate；1,6- hexane diol two (methyl) acrylate, Alkane glycol two (methyl) acrylate such as neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate；It is sweet Oily epoxy pronane modification three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane epoxy Oxide-modified three (methyl) acrylate, trimethylolpropane epoxy pronane modification three (methyl) acrylate, fulminuric acid Modified three (methyl) acrylic acid of the ethylene-oxide-modified 6-caprolactone of ethylene-oxide-modified three (methyl) acrylate, fulminuric acid Ester, 1,3,5- triacryl hexahydro-S- triazine, pentaerythrite three (methyl) acrylate, dipentaerythritol three (methyl) third Olefin(e) acid ester tripropionate etc. trifunctionals (methyl) esters of acrylic acid；Pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate mono-propionate, dipentaerythritol six (methyl) acrylate, tetramethylol methane four (methyl) acrylic acid The multifunctional (methyl) acrylates such as ester, few ester four (methyl) acrylate, three ((methyl) acryloxy) phosphate, PPZ.

In addition polyester (methyl) acrylate, polyurethane (methyl) acrylate, epoxy group (methyl) acrylic acid can be enumerated Ester, (methyl) propylene acidification maleic acid modified polybutadiene etc..

The chemical combination with acryloyl group and/or methylacryloyl in curable with actinic energy ray composition of the invention The content of object is 80 mass % hereinafter, more preferable 5 to 50 matter preferably in curable with actinic energy ray composition of the invention Measure %.

In curable with actinic energy ray composition of the invention, can also and with sensitizer so that the light alkali of essential component The absorbing wavelength region of the Photoepolymerizationinitiater initiater of producing agent expands and improves sensitivity.Can sensitizer, have no spy Other limitation, it can be mentioned, for example benzophenone, p, p '-tetramethyl-diaminobenzophenone, p, p '-tetraethyl aminodiphenyl first Ketone, 2- chlorothiaxanthenone, anthrone, 9- ethyoxyl anthracene, anthracene, pyrene, phenthazine, benzil (benzil), acridine orange, benzo it is yellow Element, thioflavine-T (setoflavin-T), 9,10- diphenylanthrancene, 9-Fluorenone, acetophenone, phenanthrene, 2- nitrofluorene, 5- nitroethane Close naphthalene, benzoquinones, the chloro- 4- nitroaniline of 2-, N- acetyl group-paranitroanilinum, paranitroanilinum, N- acetyl group -4- nitro -1- naphthalene Amine, 2,4,6- trinitroaniline (picramide), anthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 1,2 benzae thracene quinone, 3- first Base -1,3- diaza -1,9- benzanthrone, dibenzylideneacetone, 1,2- naphthoquinones, 3,3 '-carbonyls-bis- (5,7- dimethoxy Carbonyl cumarin) or coronene etc..

These sensitizers can and with a kind, and can also by two or more combination and be used in combination.

The content of sensitizer in curable with actinic energy ray composition of the invention, although the alkali according to essential component generates Sensitivity needed for agent, the type of silicon systems compound, amount and curable with actinic energy ray composition etc. and suitably determine, But it is preferred that being 30 mass % in curable with actinic energy ray composition of the invention hereinafter, more preferable 5 to 20 quality %.

In curable with actinic energy ray composition of the invention, can also and solvent be used.Can solvent if can dissolve Or the solvent of dispersed silicon based compound, i.e., it is without particular limitation, but the solvent of preferably dissolvable silicon systems compound, more preferable alcohol system Solvent.Can solvent, it can be mentioned, for example methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl-1s-the third Alcohol, cellosolvo and butoxy ethanol etc., the preferably alcohol of carbon number 1 to 4, for dissolubility, stability and coating, More preferable 2- propyl alcohol.

In addition, and with when compound with acryloyl group or methylacryloyl, it is preferable to use belonging to the compound The ketones such as the methyl ethyl ketone (MEK) of good solvent, methyl iso-butyl ketone (MIBK) (MIBK)；The esters such as ethyl acetate, butyl acetate；Glycol Ethers；Diol alcohol esters；It is aromatic hydrocarbon.

The content of solvent in curable with actinic energy ray composition of the invention is hardened in active energy ray of the invention Preferably 80 mass % in type composition are hereinafter, more preferable 0 to 50 quality %.

In curable with actinic energy ray composition of the invention, in order to promote the smooth of coating and resulting cured film Property, the purpose of appearance, the additives such as adjustable known levelling agent, defoaming agent.The content of these additives, in work of the invention Preferably 2 mass % or less in property energy line constrictive type composition.In addition, in the range for not undermining the object of the invention, it is also adjustable With ultraviolet absorbing agent, light stabilizer, dyestuff, pigment, filler etc..

Curable with actinic energy ray composition of the invention to the coating method of substrate (coated article), can be stick coating method, Dip coating, flow coat (flow coat) method, spray coating method, method of spin coating, rolling method, reverse coating or intaglio, soft version print Any coating such as brush, screen painting, ink jet printing, printing process can cooperate the shape of substrate and properly select.

In addition, curable with actinic energy ray composition of the invention can be used as coating, intaglio printing ink, soft version Print printing ink binder and the various adhesives comprising laminating adhesive such as printing ink, ink jet printing printing ink.Active energy of the invention Measure line constrictive type composition, its hardening can be made by known active energy ray method for curing, particularly preferably using ultraviolet light or Electron beam.

The light source comprising 200 to 500nm range light usually can be used in the light source of active-energy beam irradiating apparatus, such as High-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, gallium lamp, xenon lamp, carbon arc lamp etc., but it is preferable to use the waves containing 350nm or more The light source of the light in long region.The accumulative light quantity of active energy ray, since necessary lowest accumulated light quantity can be according to purposes, film thickness, coloring The presence or absence of agent, the type of Photoepolymerizationinitiater initiater are different with measuring, therefore without limitation.These ultraviolet lights, electron beam with by infrared ray, remote red Heat caused by outside line, hot wind, high-frequency heating etc. and with being effective.

The thickness of curable with actinic energy ray composition of the invention is usually 0.1 to 20 μm, preferably 2 to 10 μm, optimal Select 3 to 8 μm.When the thickness of composition layer is coated within this range, the stress that generates when due to hardening is not had and composition Layer substrate between adaptation the case where reducing, and can obtain the purpose of the present invention has abundant hardness, marresistance, wearability Hardening nitride layer.

[manufacturing method of cured film and cured film]

It is comprising following steps using the manufacturing method of cured film obtained by curable with actinic energy ray composition of the invention Rapid manufacturing method,

The step of (a) the curable with actinic energy ray composition is coated on substrate and forms envelope,

The step of the first heating (b) is carried out to the envelope,

(c) by carried out the heat treatment envelope expose the step of and

(d) the step of envelope for having carried out the exposure being subjected to the second heating.

(a) coating in step is carried out by the methods of above-mentioned stick coating method.It in the present specification, will be after coating and (b) First heating before film be known as envelope.

(b) the first heating in step is carried out by devices such as heating plate or ovens, and condition is usually at 25 to 150 DEG C In 5 to 120 minutes, 5 to 10 minutes preferably in 25 to 100 DEG C.

(c) exposure-processed in step is carried out using above-mentioned high-pressure sodium lamp etc..Although exposure cooperates silicon systems compound Type, type and content of the photobase generator of essential component etc. and properly select, but usually 100 to 1,500mJ Left and right, preferably 100 to 500mJ or so.

(d) the second heating in step is carried out using device identical with the first of (b) step the heating, and condition is logical It is often 5 to 120 minutes in 25 to 150 DEG C, 5 to 30 minutes preferably in 25 to 100 DEG C.In the present specification, second is added The film obtained after heat is known as cured film.

Curable with actinic energy ray composition of the invention, because storage stability, hardenability and film formation property are excellent, and it is hard Impact resistance, the excellent abrasion of compound, therefore can be suitable for the liquid crystal display picture of mobile phone etc., touch panel etc. For the hard coating purposes etc. of representative.

[embodiment]

Secondly, enumerating Examples and Comparative Examples to further illustrate the present invention, but the self-evident present invention not limits to In these range.In addition, " part " used in the present embodiment, unless expressly stated otherwise, otherwise refers to " mass parts ".

< synthesis example 1 has the midbody compound of the photobase generator 1 of the essential component of part-structure shown in formula (1) 1 synthesis >

In 1.9 parts of potassium cyanide be added 10 parts of water, 53 parts of ethyl alcohol make it dissolve after, with ultrasonic wave under nitrogen environment gas Processing carries out the degassing process of reaction solution.In this solution instill 10 parts of benzaldehyde of 4- (methylsulfany), heated in 80 DEG C and Start to react.After stirring 30 minutes, the crystallization that reaction solution will be made to be cooled to 3 DEG C and occurred attracts filtering and recycles.By using The solid of recycling is recrystallized and is refined by a large amount of ethyl alcohol, obtains 7.6 parts of midbody compound 1.

The synthesis > of the midbody compound 2 of the photobase generator 1 of essential component shown in 2 formula of < synthesis example (1)

In the flask equipped with blender, reflux condensing tube and agitating device, 9.0 parts of polyformaldehyde is added and dimethyl is sub- 170 parts of sulfone simultaneously stirs.Solution in 5 parts of ethyl alcohol dissolved with 1.4 parts of potassium hydroxide is instilled in flask, stirring to polyformaldehyde Until being completely dissolved.By the solution flower in 30 parts of dimethyl sulfoxide dissolved with the midbody compound 1 obtained of synthesis example 1 Take in 30 minutes instillation flasks, stirs 2 hours at room temperature.Then it instills 2.6 parts of 35% hydrochloric acid and neutralizes, reaction was completed.? Toluene and saturated salt solution are added in this reaction solution, extraction distills the intermediate for removing solvent and obtaining 40 parts in organic layer Close object 2.

The synthesis > of the photobase generator 1 of essential component shown in 3 formula of < synthesis example (1)

By 0.3 part of 2 obtained 1.0 parts of synthesis example of midbody compound 2,15 parts of toluene and triethylamine loading flask In, return stirring is carried out until uniformly.Then 0.4 part of dicyclohexyl methyl hydride -4,4- diisocyanate is added at room temperature, after After continuous stirring 12 hours, solvent is simultaneously distilled removal with evaporator by cooling.Resulting solution is instilled in hexamethylene, stirs 30 points Clock and clean, obtain photobase generator 1 shown in 1.0 parts of following formula (IV)s.

The synthesis > of the midbody compound 3 for the photobase generator 5 that < synthesis example 4 compares

N is added in 11.9 parts of 1,1,3,3- tetramethylguanidine, 13.1 parts of N '-diisopropylcarbodiimide, adds in 100 DEG C Thermal agitation 2 hours.After reaction, hexane is added in reaction solution, is cooled to 5 DEG C, the crystallization of acquisition is filtered, is obtained whereby 8.3 parts of the midbody compound 3 (1,2- diisopropyl -4,4,5,5- tetramethyl biguanides) of white solid.

The synthesis > for the photobase generator 5 that < synthesis example 5 compares

It is dissolved in 7.6 parts of Ketoprofen (ketoprofen) and 4 obtained 7.2 parts of synthesis example of midbody compound 3 In methanol 30mL, stir 30 minutes at room temperature.After reaction, reaction solution is concentrated under reduced pressure, by residue obtained with oneself It after alkane is cleaned, is dried under reduced pressure, obtains photobase generator 5 shown in following formula (V)s of 12.2 parts of white solid whereby.

The synthesis > of the midbody compound 4 for the photobase generator 6 that < synthesis example 6 compares

In the flask equipped with blender, reflux condensing tube and agitating device, 4,5- dimethoxy -2- nitrobenzene is added In room temperature (23 DEG C) after stirring 3 hours, saturation chlorination is added in 12.5 parts of formaldehyde, 1.5 parts of Sodium Borohydride and 250 parts of methanol 38 parts of ammonium salt solution.Then, the yellow solid of precipitation is recovered by filtration, after 120 parts of progress extracting operations of chloroform are added in filtrate, Solvent is evaporated and obtains gray solid.The solid of acquisition is recrystallized with ethyl acetate, obtains the centre of yellow solid whereby 8.4 parts of body compound 4 (4,5- dimethoxy -2- nitrobenzyl alcohol).

The synthesis > for the photobase generator 6 that < synthesis example 7 compares

6 obtained 8.9 parts of synthesis example of midbody compound 4,150 parts of toluene and 0.02 part of tin octoate are put into flask In, return stirring is carried out until uniformly.Then 4.6 parts of dicyclohexyl methyl hydride -4,4- diisocyanate are added under reflux, after After continuous reflux 3 hours, solvent is simultaneously distilled removal with evaporator by cooling.By the way that the brown solid of acquisition is recrystallized with ethyl alcohol, Obtain photobase generator 6 shown in 6.8 parts of following formula (VI)s.

The synthesis > of the midbody compound 5 for the photobase generator 7 that < synthesis example 8 compares

Other than midbody compound 1 is changed to styrax, with operation identical with synthesis example 2,8.1 parts are obtained Midbody compound 5.

The synthesis > for the photobase generator 7 that < synthesis example 9 compares

Other than midbody compound 2 to be changed to the midbody compound 5 obtained of synthesis example 8, with synthesis example 3 Identical operation obtains photobase generator 7 shown in 5.3 parts of following formula (VII)s.

(embodiment 1)

0.3 part of DPHA (Japanese chemical drug corporation is made), 3- acryloxypropyl trimethoxy silicon are added in brown bottle 0.075 part of alkane (manufacture of chemical company, SHIN-ETSU HANTOTAI, trade name KBM-5103), tetraethoxysilane (manufacture of Northeast chemical company) 0.3 After part, the photobase generator 1 of 3 obtained 0.0175 parts of synthesis example of addition is obtained of the invention with 0.04 part of MEK dilution Curable with actinic energy ray composition.

(embodiment 2)

In addition to the additive amount of photobase generator 1 is changed to 0.00125 part, and add Photoepolymerizationinitiater initiater 2 (Irg.184) Other than 0.01375 part, with operation same as Example 1, curable with actinic energy ray composition of the invention is obtained.

(embodiment 3)

In addition to the additive amount of photobase generator 1 is changed to 0.0025 part, and add Photoepolymerizationinitiater initiater 2 (Irg.184) Other than 0.0125 part, with operation same as Example 1, curable with actinic energy ray composition of the invention is obtained.

(embodiment 4)

In addition to the additive amount of photobase generator 1 is changed to 0.005 part, and add Photoepolymerizationinitiater initiater 2 (Irg.184) Other than 0.01 part, with operation same as Example 1, curable with actinic energy ray composition of the invention is obtained.

(comparative example 5)

Other than 0.0175 part of photobase generator 1 to be changed to 0.015 part of Photoepolymerizationinitiater initiater 2 (Irg.184), With operation same as Example 1, the curable with actinic energy ray composition compared is obtained.

(comparative example 6)

Other than 0.0175 part of photobase generator 1 to be changed to 0.015 part of Photoepolymerizationinitiater initiater 3 (Irg.369), With operation same as Example 1, the curable with actinic energy ray composition compared is obtained.

(comparative example 7)

In addition to 0.0175 part of photobase generator 1 is changed to 0.015 part of Photoepolymerizationinitiater initiater 4 (Irg.OXE-01) with Outside, with operation same as Example 1, the curable with actinic energy ray composition compared is obtained.

(comparative example 8)

In addition to 0.0175 part of photobase generator 1 is changed to 0.015 part of the light alkali relatively obtained of synthesis example 5 Other than producing agent 5, with operation same as Example 1, the curable with actinic energy ray composition compared is obtained.

(comparative example 9)

In addition to the additive amount of photobase generator 5 is changed to 0.00125 part, and the photopolymerization for adding 0.01375 part causes Other than agent 2 (Irg.184), with operation identical with comparative example 8, the curable with actinic energy ray composition compared is obtained.

(comparative example 10)

In addition to 0.0175 part of photobase generator 1 is changed to 0.015 part of the light alkali relatively obtained of synthesis example 7 Other than producing agent 6, with operation same as Example 1, the curable with actinic energy ray composition compared is obtained.

(comparative example 11)

In addition to 0.0175 part of photobase generator 1 is changed to 0.015 part of the light alkali relatively obtained of synthesis example 9 Other than producing agent 7, with operation same as Example 1, the curable with actinic energy ray composition compared is obtained.

(production of the envelope as made of curable with actinic energy ray composition and the first heating)

It is easily bonded in PET film (COSMOSHINE A4300:100 Japan twist flax fibers and weave company manufacture) on 100 μm of film thickness of two sides, Embodiment 1 to 4 is respectively coated using the rod coaters of #14 and each curable with actinic energy ray obtained of comparative example 5 to 11 combines After object, heat treatment (the first heating bakes before exposing) in 80 DEG C × 1 minute is carried out using oven, solvent is distilled and is removed.

(exposure-processed and the second heating)

For the envelope on above-mentioned PET film obtained, using belt conveyor formula high-pressure sodium lamp exposure machine, with every 1 time By light exposure be 100mJ/cm²It (carries out passing through exposure 3 times from belt conveyor to the condition of the height 100mm of high-pressure sodium lamp) Light.Then, the heat treatment (the second heating, bake after exposure) that 80 DEG C × 10 minutes are carried out using oven, obtains each active energy Measure the hardening thing (cured film) of line constrictive type composition.

By for embodiment 1 to 4 to and comparative example 5 to 11 each curable with actinic energy ray composition composition, this is each Composition or the result of the assessment carried out by the cured film that each composition obtains in following methods are shown in table 1.

(appraisal procedure)

(1) appearance of solution:

The solution of embodiment 1 to 4 and each curable with actinic energy ray composition of comparative example 5 to 11 is filled into developmental tube, With visual confirmation appearance.

(2) film outward appearance is hardened:

It is respectively combined for obtained by each curable with actinic energy ray composition for using embodiment 1 to 4 and comparative example 5 to 11 The appearance of the cured film of object, with visual confirmation whether there is or not it is muddy, tarnish, be mixed into foreign matter and rupture etc..

(3) pencil hardness:

The each of embodiment 1 to 4 and comparative example 5 to 11 is used with 750 grams of loading measurement according to the method for JIS K-5600 The pencil hardness of the cured film of each composition obtained by curable with actinic energy ray composition.

(4) adaptation:

According to the method for JIS K-5600, measurement is hard using each active energy ray of embodiment 1 to 4 and comparative example 5 to 11 Adaptation of the cured film of each composition obtained by change type composition to PET film.

(5) marresistance:

By each composition obtained by each curable with actinic energy ray composition for using embodiment 1 to 4 and comparative example 5 to 11 Cured film surface, after being wiped 20 times using #0000 steel wool with 1000 grams of loading, visually to observe the damage shape on surface State is simultaneously assessed with following evaluation criterias.

Zero: entirely without scar

△: slightly there is scar

×: there is apparent scar

(6) transparent (400nm):

Using Japan light splitting corporation UV visible light spectrophotometer V-600 with the transmitance of wavelength 400nm, assessment Use the cured film of each composition obtained by each curable with actinic energy ray composition of embodiment 1 to 4 and comparative example 5 to 11 The transparency.

(7) stability:

The solution of embodiment 1 to 4 and each curable with actinic energy ray composition of comparative example 5 to 11 is enclosed into closed container In, it is placed in 25 DEG C of thermostatic chamber after 3 months, observes its state, assessed with following evaluation criterias.

Zero: completely unchanged

×: apparent increasing stick, gelation

[table 1]

The absorbance of Photoepolymerizationinitiater initiater (photobase generator):

Modulation is dissolved with 1.0 × 10 in THF 10mL^-5Mole table 1 described in Photoepolymerizationinitiater initiater (light alkali generate Agent) 1 to 7 Photoepolymerizationinitiater initiater (photobase generator) solution.Sample is divided to obtain Photoepolymerizationinitiater initiater above-mentioned using quantitative straw (photobase generator) solution 1mL reuses THF and is diluted to the photopolymerization initiation for reaching 10mL graticule and obtaining absorbance assessment Agent (photobase generator) dilution.Use the optical path length filled with resulting Photoepolymerizationinitiater initiater (photobase generator) dilution The quartz cell of 10mm measures the absorbance of Photoepolymerizationinitiater initiater (photobase generator) 1 to 7, the measurement result according to the absorbance Molar absorption coefficient ε is calculated with following formula.The measurement result of absorbance is shown in Fig. 1 and by the calculation of molar absorption coefficient ε Value is shown in table 2 out.

Molar absorption coefficient ε=absorbance/(molar concentration of optical path length × Photoepolymerizationinitiater initiater (photobase generator))

In addition, being defined as the compound has absorption when molar absorption coefficient is 500 or more.

[table 2]

	313nm	350nm	365nm	405nm
					Photobase generator 1	28000	1380	760	20
Photoepolymerizationinitiater initiater 2	600	120	30	30
					Photoepolymerizationinitiater initiater 3	21200	3600	660	10
Photobase generator 4	10600	8500	3200	80
					Photobase generator 5	340	70	4	10
Photobase generator 6	12400	550	13100	80
					Photobase generator 7	530	17100	315	110

As shown in Table 1, the composition of curable with actinic energy ray composition of the invention compared with is compared, and is protected Deposit the good appearance of excellent in stability, solution and cured film, and its hardening thing while with high rigidity to the closely sealed of PET film Property and body are scratch resistance excellent, and the transmitance of the light of wavelength 400nm is excellent.In addition, as shown in Table 2, in embodiment The Photoepolymerizationinitiater initiater used has the optical absorption band of 350nm or more.

[industrial availability]

Curable with actinic energy ray composition of the invention, because storage stability, hardenability and film formation property are excellent, and it is hard Compound while with high rigidity to the adaptation of substrate and excellent abrasion, therefore can be suitable for mobile phone etc. Liquid crystal display picture, touch panel etc. firmly coating purposes etc..

Claims (7)

1. a kind of curable with actinic energy ray composition, contains: silicon systems compound and absorbable light with alkoxysilane group And the photobase generator containing compound shown in following formula (1) of amine and living radical is generated simultaneously,

In formula (1), R₁Indicate hydrogen atom, hydroxyl, alkoxy or organic group；R₂And R₃Indicate the aryl with substituent group；X table Show from residue obtained by hydrogen atom of one Direct Bonding of removal on nitrogen-atoms in primary amine or secondary amine.

2. curable with actinic energy ray composition according to claim 1, wherein photobase generator is 350nm's or more Have in wavelength region and absorbs.

3. curable with actinic energy ray composition according to claim 1 or 2 also contains formula (1) compound represented Photoepolymerizationinitiater initiater in addition.

4. curable with actinic energy ray composition according to any one of claim 1 to 3, also containing at least has 1 The compound of a ammonia ester bond is as base-proliferating agent.

5. curable with actinic energy ray composition according to any one of claim 1 to 4, also contains with acryloyl The compound of base and/or methylacryloyl.

6. a kind of hardening thing is the hardening thing of curable with actinic energy ray composition described in any one of claims 1 to 5.

7. a kind of manufacturing method of cured film, wherein the cured film is using activity described in any one of any one of claims 1 to 55 Energy line constrictive type composition and obtain, which includes:

The step of (a) the curable with actinic energy ray composition is coated on substrate and forms envelope,

The step of the first heating (b) is carried out to the envelope,

(c) will carry out this first heating envelope exposure the step of and

(d) the step of envelope for having carried out the exposure being subjected to the second heating.