CN1839169A - Photosensitive composition and cured product thereof - Google Patents

Abstract

There is provided a photosensitive composition excellent in photo-curability which comprises an epoxy compound having two or more epoxy groups, a polynuclear phenol compound having a specific structure and an energy beam-sensitive cationic polymerization initiator, and optionally a predetermined percentage of a hydroxyl group-containing compound having one or more hydroxyl groups and one or more of at least one of a vinyl ether group and an oxetanyl group in a molecule, and a cured product of the same whose film is excellent in adhesion to various substrates, water resistance and flexibility.

Description

Photosensitive composite and cured article thereof

Technical field

The present invention relates to irradiation by energy line, the photosensitive composite that in atmosphere, forms cured coating film with and cured article; Described filming can be used as coating, tackiness agent, printing ink, film coating; more specifically, can form material, form antireflection film coated material, hard coat (hard coating) material as the sealer of display pannels such as ink-jet UV printing ink, liquid crystal or organic EL with the Blu-ray Disc (Blue-ray disk) of the stickup tackiness agent of sealing material, CD, CD of future generation.

Background technology

On aspect raising productivity or the solution environmental problem in recent years, the curing system that uses ultraviolet homenergic line is strong method.Though present photocuring system mainly is to use the radically curing system of (methyl) esters of acrylic acid material, but, used the cationic curing system material of materials such as epoxy group(ing), vinyl ether, trimethylene oxide to compare speciality with the radically curing system with excellence, for example, (a) because the curing that is difficult to be subjected to caused by oxygen hinders excellence on aspect surface and the film hardening; (b) cure shrinkage is little, and the base material of relative broad range is had good tackiness; (c) because life-span of active substance is long,, still can be cured (dark reaction) lentamente, can make residual amount of monomer low etc. even after rayed.So, in recent years, studied the application (for example, with reference to non-patent literature 1) of described cationic curing system material on aspects such as coating, tackiness agent, indicating meter sealing agent, printing-ink, three-dimensional contouring, silicone interleaving paper, photoresist, electronic component-use sealing agent.

As the main compound that uses in cation photocuring system, can enumerate epoxy compounds, wherein, use hyperergic alicyclic epoxy compound (with reference to patent documentation 1) especially mostly.Even do not hinder owing to also can not produce the curing that is caused by oxygen in atmosphere, thereby compare with free radical system, above-mentioned alicyclic epoxy compound has excellent surface cure; But along with polymeric carries out, the speed of reaction of such material reduces, and inner solidified nature is insufficient, has the so-called problem that can not be solidified rerum natura fully.In addition, the kind of spendable compound is few, is difficult to control the rerum natura of resulting cured article.On the other hand, though compare with above-mentioned alicyclic epoxy compound, the kind of the Racemic glycidol fundamental mode epoxy compounds of widespread use in thermofixation is abundant, but its when carrying out cation photocuring reactivity insufficient, therefore must use in-problem SbF in security ₆Or AsF ₆Etc. special initiator, perhaps adopt the method share with thermofixation etc.In contrast, because oxetane compound initiation reaction speed when being used for cationic photopolymerization separately is slow but reaction of propagation speed is fast, therefore known oxetane compound and epoxy compounds are share so that polymerization velocity increases.But, compare with existing free radical system, even light solidified still is insufficient in this case, must higher sensitivityization.In addition, though known vinyl ether compound has higher cationically polymerizable, compare with above-mentioned epoxy or trimethylene oxide, the cured film that obtains is closed in this compounds homopolymerization has cure shrinkage big, the problem that descends with the tackiness of base material.

Therefore, by in above-mentioned alicyclic epoxy compound, also using vinyl ether compound, carried out the polymerizability of a lot of trials, and kept tackiness (for example, patent documentation 2 and 3) with the raising epoxy compounds.And further the trial composition that will contain this combination is used for such as stereolithography with composition (patent documentation 4) or CD with external coating (EC) agent (patent documentation 5), ink-jet recording with ultra-violet solidified composition specific end use such as (patent documentations 6).But, adopting aforesaid way in epoxy compounds, to share simply in the composition that vinyl ether compound obtains, though the reactivity of epoxy compounds can increase really, but the reactivity of vinyl ether compound reduces greatly, and the result can not obtain sufficient cured film rerum natura on the contrary.In order to improve this deficiency, (patent documentation 4,5) used multi-functional vinyl ether compound, but its effect still is insufficient in the above-mentioned research.

On the other hand, carried out following research: in containing the cationic composition of epoxy compounds, use such as aliphatic category polyvalent alcohol (patent documentation 7,8) or the conduct of phenolic compound hydroxy-containing compounds such as (patent documentations 9,10) be composition arbitrarily, improves solidified nature with this.But be to use under the situation of aliphatic category polyvalent alcohol,, have the problem of cured film fragilityization though improved the reactivity of epoxy compounds.In addition, though phenolic compound discloses the first rank phenol aldehyde type phenolic compound that dihydroxy-benzene, trihydroxybenzene etc. have the phenolic compound of 1 or 2 phenol aromatic nucleus and have methylol in molecule, but its solidified nature is all insufficient, when particularly using first rank novolac type phenol resin, there is the slow problem that reduces of hardness of cured film.

In addition, though also disclose the technology of adding phenolic compound in the patent documentation 11, though but this moment since the effect of phenolic compound performance free radical inhibitors or antioxidant thereby can prolonged preservation contain the cationic composition of unstable initiator can not expect to increase at the light solidified this respect of composition.

Patent documentation 1: No. 3794576 specification sheets of United States Patent (USP)

Patent documentation 2: the spy opens flat 6-298911 communique

Patent documentation 3: the spy opens flat 9-328634 communique

Patent documentation 4: No. 2667934 communique of Japanese Patent

Patent documentation 5: the spy opens flat 4-120182 communique

Patent documentation 6: the spy opens flat 9-183928 communique

Patent documentation 7: No. 1266325 communique of Japanese Patent

Patent documentation 8: special table 2001-527143 communique

Patent documentation 9: special table 2002-509982 communique

Patent documentation 10: No. 3251188 communique of Japanese Patent

Patent documentation 11: the spy opens the 2002-69269 communique

Non-patent literature 1: just great work " industry of カ チ オ Application hardening technique launches " the MATERIAL STAGE that waits of angle Gang, technical intelligence association, on May 10th, 2002, the 2nd volume, No. 2, P.39-92

Summary of the invention

The object of the present invention is to provide the cationic photosensitive composite, and the photosensitive coated material, jetted ink, flat-panel monitor (FPD) sealing agents such as tackiness agent, particularly organic EL that contain said composition, and the photocuring thing of above-mentioned substance.Described cationic photosensitive composite has excellent light solidified (surface cure, inside solidification), is not subjected to the overslaugh of the oxygen in the atmosphere, and the photocuring thing of said composition shows good tackiness for various base materials such as resin, metal, glass.

In order to address the above problem, the present inventor studies intensively, and finds that following photosensitive composite can solve above-mentioned problem, thereby has finished the present invention.Described photosensitive composite is to contain specific epoxy compounds, specific multinuclear phenolic compound and the photosensitive composite of cationic photopolymerization initiator, and described photosensitive composite is further to contain the vinyl ether compound with hydroxyl or the photosensitive composite of oxetane compound therein.

Promptly, the invention provides following photosensitive composite, it is characterized in that it contains the epoxy compounds (a) of 30wt%～90wt%, the multinuclear phenolic compound (b) of 0.1wt%～40wt%, the energy line susceptibility cationic polymerization initiators (c) of 0.1wt%～10wt%; In the molecule of described epoxy compounds (a), have at least 2 epoxy group(ing); Described multinuclear phenolic compound (b) contains 3～5 phenol aromatic nucleus, the ortho position of each hydroxyl of described multinuclear phenolic compound (b) not by methylol, contain alkyl, contain more than or equal to any one group in the cycloalkyl of 4 carbon atoms and replace more than or equal to 4 carbon atoms, and described multinuclear phenolic compound (b) has at least 2 do not have the phenol aromatic nucleus that replace at least one ortho position of its hydroxyl.In addition, the invention provides following photosensitive composite, it is characterized in that, in above-mentioned photosensitive composite, further contain the hydroxy-containing compounds (d) of 1wt%～60wt%; Have at least 1 hydroxyl in the molecule of described hydroxy-containing compounds (d), also have at least a group at least 1 vinyl ether group and the oxetanyl.

Description of drawings

[Fig. 1] is the diagrammatic cross-section of representational OLED element portion.

[Fig. 2] OLED display device diagrammatic cross-section partly for having special sealed structure.

Nomenclature

1 substrate

2 hole injecting electrodes

3 hole transporting layers

4 luminescent layers

5 electron injection electrodes

6 sealing materials

7 tackiness agents (layer)

Embodiment

Hereinafter the present invention is carried out specific description.

Among the present invention, in order to realize excellent light solidified, it is important using the epoxy compounds (a) that has at least 2 epoxy group(ing) in the molecule.As this compound, get final product so long as satisfy the epoxy compounds of above-mentioned requirements, there is no particular limitation, for example can enumerate glycidyl ether type epoxy compounds, alicyclic epoxy compound etc.

Object lesson as glycidyl ether type epoxy compounds, can enumerate the bisphenol type epoxy compound, Bisphenol F type epoxy compounds, phenol phenolic epoxy compound, cresols phenolic epoxy compound, Hydrogenated Bisphenol A type epoxy compounds, the diglycidylether of the oxirane affixture of dihydroxyphenyl propane, the diglycidylether of the oxirane affixture of Bisphenol F, the diglycidylether of the oxirane affixture of Hydrogenated Bisphenol A, ethylene glycol diglycidylether, propylene glycol diglycidylether, neopentylglycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, TriMethylolPropane(TMP) diglycidylether and/or trihydroxymethylpropanyltri diglycidyl ether, tetramethylolmethane triglycidyl ether and/or tetramethylolmethane four glycidyl ethers, Sorbitol Powder seven glycidyl ethers and/or Sorbitol Powder six glycidyl ethers, resorcinol diglycidyl ether, Dicyclopentadiene (DCPD)-phenol add-on type glycidyl ether, methylene radical two (2, the 7-dihydroxy naphthlene) four glycidyl ethers, 1,6-dihydroxy naphthlene diglycidylether etc.

Object lesson as the alicyclic epoxy compound, can enumerate 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 4-epoxy) hexanaphthene--dioxane, two (3,4-epoxycyclohexyl methyl) adipic acid ester, titanium dioxide vinyl cyclohexene, 4 vinyl epoxy cyclohexane, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy group(ing)-6-methylcyclohexanecarboxylic acid ester, methylene radical two (3, the 4-epoxy-cyclohexane), the Dicyclopentadiene (DCPD) diepoxide, ethylene glycol-two (3,4-epoxycyclohexyl methyl) ether, two (3,4-epoxy-cyclohexane carboxylic acid) second diester, two (3,4-epoxy-cyclohexane carboxylic acid) propylene diester, epoxy hexahydrobenzene dioctyl phthalate dioctyl ester, epoxy hexahydrobenzene dioctyl phthalate two-2-ethylhexyl, 1,4-cyclohexanedimethanol-two (3, the 4-epoxycyclohexane carboxylate) etc.

As 2 officials energy alicyclic epoxy compound, can use CELLOXIDE 2021,2080,3000 (Daicel chemical industry society system); UVR-6110,6105,6128, ERLX-4360 (DowChemical Japan society system), as 3 officials can or more polyfunctional multifunctional alicyclic epoxy compound, can use EPOLEAD GT300, GT400 (Daicel chemical industry society system) etc.

Wherein, because the alicyclic epoxy compound is excellent on aspect the cationic polymerization, so be preferred.Can use separately a kind these have the compound of epoxy group(ing), at least 2 kinds that also can make up these compounds with epoxy group(ing) are used.

Multinuclear phenolic compound of the present invention (b) contains a plurality of phenol aromatic nucleus.Wherein said phenol aromatic nucleus refers to the aromatic nucleus with phenol hydroxyl.Among the present invention, the phenol hydroxyl plays an important role in photo-crosslinking, has only by using this multinuclear phenolic compound with phenol hydroxyl, just can obtain the photosensitive composite that demonstrates excellent light solidified of the present invention.

In addition, in the multinuclear phenolic compound (b), on any one ortho position of its all hydroxyls, do not have methylol.That is, multinuclear phenolic compound (b) does not comprise the multinuclear phenolic compound that has methylol in molecule that is commonly referred to as resole.Though methylol has the reactivity with epoxy group(ing), because the formed key of result of reaction is unstable under acidic condition, the hardness of the film that obtains after the curing has the problem of reduction as time passes, so be not preferred.Further, multinuclear phenolic compound (b) is characterised in that, it does not have the alkyl or cycloalkyl that contains more than or equal to 4 carbon atoms on the ortho position, especially, multinuclear phenolic compound (b) does not comprise the phenolic compound that usually is called as free radical inhibitors or antioxidant, and described phenolic compound for example is the hindered phenolic of sterically hindered phenol etc. with bulky tertiary butyl.This is because the phenol hydroxyl of multinuclear phenolic compound (b) is relevant with the direct sunshine curing reaction, and bulky substituting group is the hindering factor of this reaction, thus such substituting group to be substituted on the ortho position of phenol hydroxyl be unfavorable.

Further, for multinuclear phenolic compound (b), necessary condition is as follows: it contains 3～5 phenol aromatic nucleus, and at least 2 phenol aromatic nucleus in its molecule do not have replacement at least one ortho position of its hydroxyl.If multinuclear phenolic compound (b) only has 1～2 phenol aromatic nucleus, then in photocuring reaction, can not form crosslinking structure effectively; In addition, if its phenol aromatic nucleus more than or equal to 6, then produces and the irrelevant phenol hydroxyl of crosslinking reaction, solidified nature and cured film rerum natura there is detrimentally affect.

As this multinuclear phenolic compound, can enumerate the various multinuclear phenolic compounds shown in for example following general formula (5)～(13), further can enumerate the various multinuclear phenolic compounds shown in for example following general formula (1), (3) and as the multinuclear phenolic compound with 3～5 phenol aromatic nucleus of the Friedel-Crafts of low-molecular-weight chain polyhutadiene and phenol reaction affixture etc.;

(in the above-mentioned general formula, R ₁The expression carbonatoms is 1～5 alkyl or alkoxyl group, the R in the different phenyl ring ₁Can be identical or different, in addition, the R of the p in each phenyl ring ₁Can be identical or different.P is 0～4 integer, and the p in the different phenyl ring can be identical or different, and q is 1～3 integer, and the q in the different phenyl ring can be identical or different.p+q≤5。But, R ₁Carbonatoms be 4 or 5 o'clock, R ₁Not on the ortho position of the hydroxyl on the phenyl ring);

(in the general formula (8), except R ₂Carbonatoms be beyond 1～3, identical with general formula (5).P is identical with general formula (5) with q);

(in the general formula (9), B is for being selected from a kind of group in the group shown in following general formula (10), (11) and (12), R ₁Identical with p) with general formula (5);

(in the above-mentioned general formula, R ₃, p is identical with general formula (5) with q);

(R in the general formula (1) represents that carbonatoms is that 1～5 alkyl, carbonatoms are that 5～10 cycloalkyl, carbonatoms are 1～5 alkoxyl group, halogen atom, hydroxyl, aryl or aralkyl, a plurality of R in general formula difference fully also can be identical, m is 0～3 integer, and n is 1～3 integer);

(in the general formula (3), n represents 1～3 integer).

Wherein, preferably, also preferably can obtain the multinuclear phenolic compound (g) that is equivalent to the addition compound shown in the above-mentioned general formula (3) of the cured article that water absorbability is low, water tolerance is excellent with the intermiscibility of epoxy compounds (a), the vinyl ether that contains hydroxyl or trimethylene oxide and reactive excellent with the multinuclear phenolic compound (e) shown in the above-mentioned general formula (1).

In multinuclear phenolic compound (e), m is preferably 1～3, and more preferably 1.In addition, m is 1～3 o'clock, the contraposition of substituent group R preferred combination hydroxyl on phenyl ring.Wherein to be preferably carbonatoms be that 1～5 alkyl, alkoxyl group, carbonatoms are 5～10 cycloalkyl, aryl, aralkyl to R.For example, be 1～5 alkyl as carbonatoms, can enumerate methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl, sec-butyl, tert-pentyl etc.It as carbonatoms 5～10 cycloalkyl, as preferred example, can enumerate carbonatoms and be 6 cyclohexyl, be 1～5 alkoxyl group as carbonatoms, for example can enumerate, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, tert.-butoxy, sec-butoxy etc., as aryl, can enumerate for example phenyl, naphthyl, xenyl etc., as aralkyl, can enumerate for example benzyl, α-Jia Jibianji, α, d-dimethyl benzyl etc.

For example, can be by the phenol (R fortified phenol) or the phenol that will have the substituted radical of representing with R, utilize known synthetic method, promptly in the presence of acid catalysts such as hydrochloric acid, oxalic acid, tosic acid, with formaldehyde, Paraformaldehyde 96, formalin etc. at 0 ℃～150 ℃ following stoichiometric numbers hour by tens of hours, obtain representing multinuclear phenolic compound (e) more than or equal to the condenses of 0 integer as n.At this moment, though the amount of by product is also relevant with reaction conditions, generally can recently control the amount that generates as by product by the consumption of determining employed R fortified phenol or phenol and formaldehyde with the various multinuclear phenolic compounds (f) shown in the following general formula (2).

(in the general formula (2), R represents that carbonatoms is that 1～5 alkyl, carbonatoms are that 5～10 cycloalkyl, carbonatoms are 1～5 alkoxyl group, halogen atom, hydroxyl, aryl or aralkyl, a plurality of R in general formula difference fully also can be identical, m is 0～3 integer, n be 0 or more than or equal to 4 integer).

For example, if, then containing the content of the phenolic compound of 2 phenol aromatic nucleus greatly more than formaldehyde, the R fortified phenol increases, opposite, if the R fortified phenol is less than formaldehyde greatly, the content that then contains the multinuclear phenolic compound (f) of 6 or more a plurality of phenol aromatic nucleus increases.When the content of multinuclear phenolic compound (e) composition in the condenses that obtains is very few, can remove unreacting material and multinuclear phenolic compound (f) by methods such as distillation or reprecipitations.

Among the present invention, with respect to its multinuclear phenolic compound (e) and total amount (f), the ratio of multinuclear phenolic compound (e) is preferably greater than and equals 40wt%, more preferably greater than equaling 50wt%, further is preferably greater than and equals 60wt%.The content of multinuclear phenolic compound (e) is during less than 40wt%, and for example, when the amount of the phenolic compound that contains 2 phenol aromatic nucleus of the n=0 in the general formula (2) was too much, the light solidified of photosensitive composite reduced, and can not obtain sufficient luminous sensitivity.On the other hand, be equivalent to n in the general formula (2) more than or equal to the amount of the multinuclear phenolic compound (f) of 4 condenses when too much, even after photocuring reaction finishes, also remaining unreacted phenol hydroxyl, exist the film of its cured article can not show sufficient water tolerance, or because photostabilization is not enough thereby demonstrate significant xanthochromic problem, so be not preferred.

As commercially available product, for example, new molecular weight distribution concentrated resol: PAPS (ProductName: the organic material industry of rising sun society system) be suitable as multinuclear phenolic compound of the present invention (e) and use.

As the object lesson that synthesizes the middle R fortified phenol that uses of multinuclear phenolic compound (e), can enumerate phenol, p-cresol, meta-cresol, p-ethyl phenol, m-ethylphenol, the n-propyl phenol, between propylphenol, australol, NSC 2209, p-tert-butylphenol, between tert.-butyl phenol, to sec-butyl phenol, between sec-butyl phenol, Pentaphen, between tert.-amyl phenol, p-phenyl phenol, between phenylphenol, to cumylphenol, right-(α-Jia Jibianji) phenol, between-(α-Jia Jibianji) phenol, to cyclohexylphenol, p methoxy phenol, meta-methoxy phenol, para-chlorophenol, m-Chlorophenol, pyrocatechol, Resorcinol, Resorcinol etc.

On the other hand, can pass through at BF ₃Making Dicyclopentadiene (DCPD) and phenol carry out Friedel-Crafts under the existence Deng acid catalyst reacts and obtains multinuclear phenolic compound (g).At this moment, can recently control the amount of the various multinuclear phenolic compounds (h) shown in the following general formula (4) that produces as by product by the consumption of determining employed Dicyclopentadiene (DCPD) and phenol.

(in the general formula (4), n represent 0 or more than or equal to 4 integer).

Among the present invention, with respect to multinuclear phenolic compound (g) and total amount (h), the ratio of multinuclear phenolic compound (g) is preferably greater than and equals 40wt%, more preferably greater than equaling 50wt%, further is preferably greater than and equals 60wt%.The content of multinuclear phenolic compound (e) is during less than 40wt%, and for example, when the amount of the phenolic compound that contains 2 phenol aromatic nucleus of the n=0 in the general formula (4) was too much, the light solidified of photosensitive composite reduced, and can not obtain sufficient luminous sensitivity.On the other hand, be equivalent to n in the general formula (4) more than or equal to the amount of the multinuclear phenolic compound (h) of 4 affixture when too much, the solvability of photosensitive composite in other composition is not enough, simultaneously, even after photocuring reaction finishes, also remaining unreacted phenol hydroxyl, damage the water tolerance of the film of its cured article, further, the problems such as sufficient membrane property after generation can not obtain solidifying are not so be preferred.

As commercially available product, for example, the DPP-6125 in day special phenol resins DPP of the stone series (Nippon Oil(Nippon Mitsubishi Oil) chemistry society system) is suitable as multinuclear phenolic compound (g) and uses.

As the multinuclear phenolic compound (b) that uses among the present invention, can use a kind in the above-mentioned various multinuclear phenolic compound separately, or at least 2 kinds of making up in the above-mentioned various multinuclear phenolic compound use.

The energy line susceptibility cationic polymerization initiators (c) that uses among the present invention refers to and can produce the compound that shines the material that causes cationoid polymerisation by energy line, produces lewis acidic salt as particularly preferably being by irradiation.Particularly, can enumerate lewis acidic diazonium salt, lewis acidic salt compounded of iodine, lewis acidic sulfonium salt etc., these are to be respectively aromatic series diazonium, aromatic series iodine, aromatic matte by cationic moiety, and anionicsite is BF ₄ ^-, PF ₆ ^-, SbF ₆ ^-, [BX ₄] ^-(wherein, X replaced by at least 2 fluorine or trifluoromethyl phenyl) waits and the salt of formation.Particularly, can enumerate the phenyl diazonium salt of tetrafluoride boron, the diphenyl iodnium of phosphorus hexafluoride, the diphenyl iodnium of antimony hexafluoride, three-4-aminomethyl phenyl sulfonium salt of arsenic hexafluoride, three-4-aminomethyl phenyl sulfonium salt of tetrafluoride antimony, the diphenyl iodnium of four (pentafluorophenyl group) boron, the mixture of aluminium acetylacetonate salt and adjacent nitrobenzyl silyl ether, phenyl thiopyridines salt, phosphorus hexafluoride propadiene-iron chelate etc., can use CD-1012 (trade(brand)name: SARTOMER society system), PCI-019, PCI-021 (trade(brand)name: Japanese chemical drug society system), Optomer SP-150, Optomer SP-170 (trade(brand)name: rising sun electrification society system), UVI-6990 (trade(brand)name: Dow Chemical society system), CPI-100P, CPI-100A (trade(brand)name: San-Apro society system), TEPBI-S (trade(brand)name: Japanese catalyst society system), (trade(brand)name: Rhodia society system) etc., these can use separately also can make up at least 2 kinds of uses to R HODORSIL PHOTOINITIATOR 2074.

Among the present invention, further, can obtain the light solidified with more excellent solidified nature, tackiness and water-proof cured article can be provided by using hydroxy-containing compounds (d).As this hydroxy-containing compounds (d), it is to have at least 1 hydroxyl in the molecule and have the vinyl ether of cationically polymerizable or the compound of at least a kind of group in the oxetanyl, importantly has hydroxyl and above-mentioned cationically polymerizable group in 1 molecule simultaneously.This has pointed out, and the photo-crosslinking mechanism of photosensitive composite of the present invention is with general that use and with various not hydroxyls and to have the multi-functional vinyl ether of a plurality of polymerisation reactivity functional group different with the mechanism of the system of oxetane compound in the past.Promptly, wherein, same with above-mentioned multinuclear phenolic compound, it is important making hydroxyl participate in photocuring reaction directly, when hydroxyl is participated in photocuring reaction directly, photocuring reaction and the cationic photopolymerization that is caused by vinyl ether or oxetanyl react simultaneously, thus in above-mentioned multinuclear phenolic compound further and use these compounds, can show the solidified nature that is difficult to the excellence that obtains so far.Compare with polyfunctional vinyl ether, trimethylene oxide, though there are the significantly reduced problem of solidified nature in vinyl ether, the trimethylene oxide of the simple function that only has a polymerisation reactivity functional group in the past, if but it is the compound that contains hydroxyl of the present invention, even monofunctional compound also can provide the photosensitive composite with fully high solidified nature.

As used vinyl ether compound wherein, can enumerate the hydroxyethyl vinyl ether with hydroxyl, hydroxy butyl vinyl ether, the cyclohexanedimethanol mono vinyl ether, the cyclohexanediol mono vinyl ether, 9-hydroxyl nonyl vinyl ether, the propylene glycol mono vinyl ether, the neopentyl glycol mono vinyl ether, the glycerine divinyl ether, the glycerine mono vinyl ether, the TriMethylolPropane(TMP) divinyl ether, the TriMethylolPropane(TMP) mono vinyl ether, the tetramethylolmethane mono vinyl ether, the tetramethylolmethane divinyl ether, the tetramethylolmethane trivinyl ether, the Diethylene Glycol mono vinyl ether, the triethylene glycol mono vinyl ether, the TEG mono vinyl ether, three ring decanediol mono vinyl ethers, tristane dimethanol mono vinyl ether etc.

In addition, as the oxetane compound that uses among the present invention, can enumerate the compound shown in the following general formula (14) with hydroxyl.

(in the general formula (14), R ₄Be hydrogen atom; The alkyl of C1～6 such as methyl, ethyl, propyl group or butyl; The fluoroalkyl of C1～6; Allyl group; Aryl; Furyl or thienyl.R ₅The alkylidene group of C1～6 such as expression methylene radical, ethylidene, propylidene or butylidene; And on above-mentioned alkylidene group bonding alkylidene oxides such as the oxidation ethylidene of ether, oxypropylene, oxybutylene).

Wherein, as R ₄Be preferably low alkyl group, be preferably ethyl especially.In addition as R ₅Be preferably methylene radical.

Can use these hydroxy-containing compounds separately, also can make up at least 2 kinds of these hydroxy-containing compounds and use.

In photosensitive composite of the present invention, can will share by adding other polymerization starter and the polymerization starter of the present invention (c) that thermogenesis causes the material of cationoid polymerisation.As the object lesson of other polymerization starter, can enumerate 4,4-two (diethylamine) benzophenone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 9,10-diethoxy anthracene, 9,10-dibutoxy anthracene etc.

In photosensitive composite of the present invention, can share not containing the polyfunctional vinyl ether of hydroxyl or the hydroxy-containing compounds (d) of trimethylene oxide and the present application.As this vinyl ether, for example can enumerate ethylene glycol bisthioglycolate vinyl ether, butyleneglycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane tris vinyl ether, tetramethylolmethane tetrem alkene ether, glycerine trivinyl ether, triethylene glycol divinyl ether, Diethylene Glycol divinyl ether etc.In addition, as this trimethylene oxide, can enumerate 1,4-two ([(3-ethyl trimethylene oxide-3-yl) methoxyl group] methyl) benzene, two [1-ethyl (3-trimethylene oxide)] methyl ether, 1,3-two [(3-ethyl trimethylene oxide-3-yl) methoxyl group] benzene, 4,4-two [(3-ethyl trimethylene oxide-3-yl) methoxyl group] biphenyl, phenol phenolic aldehyde trimethylene oxide, oxetanyl silsesquioxane etc.

Other, the film rerum natura not to solidified nature, curing the time has in the dysgenic degree, can add other compound that shows cationically polymerizable.As these compounds, for example can enumerate, the low-molecular-weight epoxy compounds of use except above-mentioned can be enumerated annular lactone compound, cyclic acetal compound, cyclic thioether compound, spiro orthoester compound etc. in addition as thinner.Can use in the past di-alcoholss such as the so-called polyoxyethylene glycol such as ethylene glycol, propylene glycol, Diethylene Glycol and triethylene glycol that uses and polypropylene glycol in addition; Polyalcohols such as glycerine, TriMethylolPropane(TMP), tetramethylolmethane.

In the photosensitive composite of the present invention, further according to necessity, in order to promote solidified nature (raising sensitivity), can add free-radical polymerised compounds such as (methyl) acrylate monomer class or oligopolymer class and (methyl) vinyl acrylate and optical free radical initiator etc. for energy line.Wherein, particularly have vinyl and acrylate-based vinyl acrylate compound in 1 molecule simultaneously, because viscosity is low and have cationically polymerizable, so when keeping high sensitivity, can reduce viscosity, it is effective thinner when therefore, being used for the ink-jet purposes.Other can also add defoamer, flow agent, stopper, wax class, antioxidant, non-reactive polymer, particulate inorganic filler, silane coupling agent, photostabilizer, UV light absorber, static inhibitor, slip(ping)agent etc.

Wherein, in order to reduce water vapour permeability especially, the interpolation of particulate inorganic filler and silane coupling agent is effective.As this particulate inorganic filler, it is that the median size of primary particle is the inorganic filler of 0.005 μ m～10 μ m, specifically can enumerate silica, aluminum oxide, talcum, lime carbonate, mica etc.For the particulate inorganic filler, can use the untreated and surface treated particulate inorganic filler in surface simultaneously, as surface treated particulate inorganic filler, for example can enumerate, methoxyization, trimethyl silylization, the silylated particulate inorganic filler of octyl group or carried out surface-treated particulate inorganic filler with silicone oil, can use a kind of these particulate inorganic filler separately, at least 2 kinds that also can make up these particulate inorganic fillers are used.In addition; as silane coupling agent; it is the alkoxysilane compound containing trialkylsilyl group in molecular structure with epoxy group(ing), carboxyl, methacryloyl isoreactivity group; specifically can enumerate γ-glycidoxypropyltrime,hoxysilane, trimethoxysilyl M-nitro benzoic acid, γ-iso-butylene acyl-oxygen base propyl trimethoxy silicane, vinyltrimethoxy silane, vinyltriacetoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane etc.Can use a kind of these silane coupling agent separately, at least 2 kinds that also can make up these silane coupling agents are used.

Then, the composition ratio to each composition in the photosensitive composite of the present invention's use describes.And following part is the expression weight part all.

In the photosensitive composite, the hydroxyl concentration of phenol hydroxyl concentration of multinuclear phenolic compound (b) (being defined as the hydroxyl value in mole number * 1 molecule of polynary phenoloid (b)) and hydroxy-containing compounds (d) (being defined as the hydroxyl value in mole number * 1 molecule of hydroxy-containing compounds (d)) and, preferably smaller or equal to the epoxy group(ing) concentration of epoxy compounds (a) (being defined as the epoxy radix in mole number * 1 molecule of epoxy compounds (a)), more preferably the functional group concentration with respect to epoxy group(ing) is 1, and it is smaller or equal to 0.8.This be because, if compared with the epoxy group(ing) concentration in the photosensitive composite, phenol hydroxyl concentration and hydroxyl concentration are excessive, the wetting ability of the film after then solidifying is too high, cause that water tolerance is not enough or cured film fragilityization etc. takes place, thereby the cured film characteristic is insufficient.As the cooperation ratio of reality, though also relevant with the molecular weight of compound separately, the compound (a) that usually has at least 2 epoxy group(ing) in 1 molecule is 30wt%～90wt%, is preferably 60wt%～90wt%.Multinuclear phenolic compound (b) is 0.1wt%～40wt%, is preferably 0.5wt%～20wt%.Hydroxy-containing compounds (d) is 1wt%～60wt%, is preferably 10wt%～40wt%.Wherein, when in multinuclear phenolic compound (b), also using hydroxy-containing compounds (d), though cooperate ratio not limit especially to it, even but the few amount of multinuclear phenolic compound, its additive effect is also very big, so setting both total amounts is 100 o'clock, preferred multinuclear phenolic compound is 1～50, and hydroxy-containing compounds is 50～99.

The content of the energy line susceptibility cationic polymerization initiators (c) in the photosensitive composite of the present invention is preferably 0.1wt%～10wt%, more preferably 0.2wt%～5wt%.During greater than 10wt%, owing to used the initiator of excessive costliness, so undesirable economically, moreover, also because light penetration reduces, the curing of film bottom is insufficient, so undesirable.In addition, during less than 0.1wt%, the active cation amount of substance that produces by the energy line irradiation is not enough, can not obtain sufficient solidified nature.

The content of the above-mentioned particulate inorganic filler that uses according to necessity is 0wt%～70wt% in cationically polymerizable photosensitive composite of the present invention, is preferably 0.1wt%～60wt%.In addition, similarly in cationically polymerizable photosensitive composite of the present invention, the content of silane coupling agent is 0wt%～10wt%, is preferably 0.1wt%～10wt%.

Owing to have excellent solidified nature and for the tackiness of the excellence of various base materials, photosensitive composite of the present invention is useful as the photosensitivity tackiness agent.Especially, because polymerisation conversion height by the energy line irradiation, its productivity excellence, and wet fastness is also excellent, is suitable so conduct not only requires good tackiness also to require the FPD sealing agent of the liquid-crystal display of high reliability, organic EL (OLED) indicating meter, Electronic Paper etc.Wherein, because the OLED indicating meter is most preferred application examples with the demanding anti-water vapour permeability of sealing agent so the sealing agent that the present invention relates to is used as such sealing agent.

Hereinafter, see figures.1.and.2 photosensitive composite of the present invention is described as the application examples of OLED indicating meter with sealing agent.

Fig. 1 is the sectional view of representational OLED element portion.Among Fig. 1, hole injecting electrode 2 is formed on the substrate 1, and its top is formed with hole transporting layer 3 and luminescent layer 4, further forms electron injection electrode 5 thereon.Then; around the laminate that forms by above-mentioned hole transporting layer 3 and luminescent layer 4 and electron injection electrode 5, form sealing material 6; from the outer protection element; the sealing material fits together by adhesive coating 7 and hole injecting electrode 2, has used the sealing agent that contains cationically polymerizable photosensitive composite of the present invention in the described adhesive coating 7.

As substrate 1, can use transparent or semitransparent glass; Or resins such as polycarbonate, poly-terephthalic acid second diester, cyclic olefin base polymer etc., also can use the pliable and tough substrate after these material filmizations.

Hole injecting electrode 2 is formed by the conducting material with transparency, can use ITO, the ATO (SnO of doping Sb ₂), AZO (ZnO of doped with Al) etc.

Material as hole transporting layer 3, the preferred hole degree of excursion height that uses, the organic materials transparent and film-forming properties is good, for example, can use TPD (N, N-phenylbenzene-N, N-two (3-aminomethyl phenyl)-1,1-phenylbenzene-4, the 4-diamines) triphenylamine derivative such as, also has porphines in addition, tetraphenylporphines copper, phthalocyanine, copper phthalocyanine, porphyrin compound, N, N, N, N-four (p-methylphenyl)-Ursol D and N, N, N, N-tetraphenyl-4, aromatic nitrile bases such as 4-benzidine and N-phenyl carbazole, stilbene compounds, triazole derivative oxadiazole derivative, imdazole derivatives, the polyaryl alkane derivatives, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, the amino chalcone derivative oxazole derivative that replaces, the styryl anthracene derivant, fluorenone derivatives, hydrazone derivative, the silazane derivative, the polysilanes amino benzenes derivates, organic materialss such as poly-3 methyl thiophene.

As luminescent layer 4, preferably, can use oxine aluminium (Alq3) as such raw material by in visible field, having fluorescence and the good fluor of film-forming properties forms; Be-benzoquinoline phenol (BeBq ₂); 2,5-two (5,7-two tert-pentyls-2-benzoxazolyl)-1,3,4-thiadiazoles, 4,4-two [5,7-two (2-methyl-2-butyl)-2-benzoxazolyl] Stilbene, 2,5-two ([5-α, α '-dimethyl benzyl]-2-benzoxazolyl) thiophene, 2,5-two (5-methyl-2-benzoxazolyl) thiophene, 2-[2-(4-chloro-phenyl-) vinyl] and naphtho-[1, Benzooxazole kinds such as 2-d] oxazole; 2,2-(right-phenylene two vinylidenes)-benzothiazoles such as bisbenzothiazole; 2-[2-[4-(2-benzimidazolyl-) phenyl] vinyl] benzoglyoxaline, 2-[2-(4-carboxyl phenyl) vinyl] benzimidazoles such as benzoglyoxaline; Oxine metalloid inner complexs such as three (oxine) aluminium, oxine lithium, three (oxine) indium, two (5-chloro-oxine) calcium; Table indole dione two lithiums metal chelating combination oxynoid compounds such as (dilithium epindolidione); 1,4-two (2-methyl styrene base) benzene, 1,4-(3-vinyl toluene base) benzene, 1,4-two (3-ethyl styrene base) benzene, 1, styryl benzene-like compounds such as 4-two (2-methyl styrene base) 2-methylbenzene; 2,5-two (4-vinyl toluene base) pyrazine, 2,5-two (4-ethyl styrene base) pyrazine, 2, diphenylethyllene pyrazines derivatives such as 5-two [2-(4-xenyl) vinyl] pyrazine; And benzene-naphthalene diimide derivative, perylene derivative, oxadiazole derivative, aldazine derivative, cyclopentadiene derivant, styryl sulfonamide derivatives, coumarin derivatives etc.Further can use anthracene, salicylate, pyrene, coronene etc.

As electron injection electrode 5, can enumerate metals such as Al, In, Mg, Ti; Mg such as Mg-Ag, Mg-In alloy; Al alloys such as Al-Li, Al-Sr, Al-Ba etc.Wherein, because alloy working functions such as Al-Mg or Al-Li-Mg are low, and corrosion resistance excellent, so be particularly preferred.

As sealing material 6, use the material of water vapor barrier excellences such as stainless steel or glass usually, use the sealing agent contain cationoid polymerisation rerum natura composition of the present invention, the substrate that is formed with hole injecting electrode of sealing material and subtend is fitted.

Fig. 2 is the OLED display element portion sectional view that is formed by other sealed structure of the present invention.The formation method of this structure is as follows, after forming hole injecting electrode 2, hole transporting layer 3, luminescent layer 4 and electron injection electrode 5 on the substrate 1 successively, the sealing agent that use contains cationically polymerizable photosensitive composite of the present invention forms adhesive coating 7, then, and applying sealing material 6.When using flexible material as sealing material 6, the thorough seal by this solid film is special effective means.

As the method that on substrate 1, forms multilayered structure, can utilize resistive heating vapour deposition, ion beam sputtering and can wait in ink jet method, the print process that normal pressure forms and carry out as known method; Described multilayered structure is by the positive hole of lamination injecting electrode 2, positive hole transfer layer 3, luminescent layer 4, electron injection electrode 5 obtain successively.Then, as the method for sealing agent of the present invention being coated multilayered structure,, do not limit especially so long as the method that sealing agent can be coated with equably gets final product, for example can enumerate, based on the method for print processes such as silk screen printing, flexographic printing or use method that dispersion machine is coated with etc.

Behind 7 applying sealing materials 6 on the adhesive coating that sealing agent of the present invention forms, be cured as energy line from sealing material 6 one sides or substrate 1 one side irradiates lights.Wherein as operable light source, so long as the light source that can be cured in the operating time of regulation gets final product, do not limit especially, usually, it can be the light source of the light of irradiation ultraviolet radiation, visible wavelength, for example, Cooper-Hewitt lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, xenon lamp, metal halide lamp, electrodeless discharge lamp etc.Among the present invention, provide the FPD that uses the tackiness agent that contains above-mentioned photosensitive composite to make as mentioned above, wherein, particularly provide the OLED indicating meter of manufacturing like this as sealing agent.

In addition, utilize photosensitive composite of the present invention, because can be at air high speed ground cured film, so be used as for requiring not heat the coated material that carries out on high speed solidified resin molding, the substrate etc. suitably.As such example, can enumerate and be used to form the used coated material that prevents reflectance coating among FPD etc., for coating on base material, be cured the back and form the film have smaller or equal to 1.4 specific refractory power, the porous matter particulate that photosensitive composite of the present invention is contained have the space.

As this porous matter particulate, can enumerate median size is the silicon oxide particle of 5nm～1 μ m, is preferably the silicon oxide particle of the median size with 5nm～100nm especially.Particularly, can enumerate Aerosil (Japanese Aerosil society system), Snowtex PS (producing chemical society system daily) etc., Aerosil is an aerosil hydrophilic or that carried out surface-hydrophobicized processing, and SnowtexPS is that silicon oxide particle becomes the peart necklace shaped silica sol of straight chain shape banded.

When using these porous matter particulates,, can add 10 weight parts～70 weight parts, preferably use homogeneous in composition such as homogenizer to disperse these porous matter particulates for the photosensitive composite of 100 weight parts.In this coated material composition, according to necessity can and with tetraalkoxysilanes such as above-mentioned silane coupling agent (bonding the organoalkoxysilane of organic group), tetraethoxysilanes.

With the coating-forming agent that so obtains, on transparent base material, for example at resin base material such as polymethylmethacrylate, polycarbonate, polystyrene, triacetyl cellulose or to form thickness on inorganic materials such as glass be the reflectance coating that prevents of 10nm～1 μ m.When on base material, being coated with,, use nick version coating method, rolling method, flowing-type coating method, spin-coating method, die head coating method, cast reprint method, spraying method etc. especially owing to be necessary to form thin film with higher precision.

When using composition of the present invention in addition, though maximum being characterised in that by shining above-mentioned active ray, can make the film hardening of coating at high speed, can be according to necessity also with being heating and curing.That is, though composition of the present invention does not contain solvent etc. in essence, when having carried out dilution in order to carry out the viscosity adjustment, and when using porous matter particulate with the state of colloidal sol, composition can contain solvent.At this moment,, can before carrying out rayed, heat, under 50 ℃～150 ℃, carry out several minutes heating usually for prior solvent flashing composition.Similarly can promote to solidify after the exposure in addition by heating.

Further, by tinting material being made an addition in the composition of the present invention, can make photosensitive jetted ink.Photosensitive composite of the present invention has the feature that is easier to reduce viscosity, also has excellent light solidified, by mixing with the appropriate colouring agent, can be used as photosensitive jetted ink suitably.

As the tinting material that uses among the present invention, can use the various pigment of pigment dyestuff and/or mineral dye.Particularly, can enumerate white pigments such as titanium oxide, zinc white, white lead, lithopone and weisspiessglanz; Black pigments such as nigrosine, iron oxide black and carbon black; Yellow ultramarines such as chrome yellow, iron oxide yellow, organic yellow (100,50,30 etc.), titan yellow, diarylide yellow (benzine yellow) and permanent yellow; Molybdenum bright red, orange pigmentss such as solid orange, forging and smelting fast orange (vulcan fast orange), indanthrene brilliant orange forever; Ferric oxide, permanent brown pigments such as brown, coupling palm fibre; Red pigments such as oxidation is red, cadmium red, crimson antimony, permanent red, rhodamine reds, sodium alizarinsulfonate, thioindigo red, PV fuchsin, monolight fast red, quinoline a word used for translation ketone red pigment; Violet pigments such as cobalt violet, manganese violet, Fast violet, methyl violet color lake, indanthrene brilliant violet, dioxazine violet; Ultramarine, general Shandong soil indigo plant, cobalt blue, alkali blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, indanthrene blue, blue pigments such as indigo; Veridians such as chrome green, chromic oxide, bud green, naphthol green, green gold, acid green color lake, Victoria Green WPB color lake, phthalocyanine green, many chlorine bromine copper phthalocyanine; Other various high-visibility pigments, metallic powdery pigment, filler pigment etc.The content of these pigment is 1wt%～50wt% in the composition among the present invention, is preferably 5wt%～25wt%.

For above-mentioned pigment, according to necessity, can use pigment dispersing agent, pigment dispersing agent as the present invention's use, for example can enumerate higher fatty acid salt, alkyl-sulphate, alkyl sulfate, alkylsulfonate, sulfosuccinate, naphthalenesulfonate, alkylphosphonic, polyoxyalkylene alkyl ether phosphoric acid salt, polyoxy alkylidene alkyl phenyl ether, glyceryl ester, sorbitan ester, the agent of poly suboxygen ethylidene fatty amide isoreactivity; Be selected from segmented copolymer, unregulated polymer that at least 2 kinds of monomers in vinylbenzene, styrene derivatives, vinyl naphthalene radical derivative, vinylformic acid, acrylic acid derivative, toxilic acid, maleic acid derivatives, methylene-succinic acid, derivatives from itaconic acid, fumaric acid, the fumaric acid derivatives form; And the salt of above-mentioned substance.

As the dispersing of pigments method, for example can use various dispersion machines such as ball mill, sand mill, attritor, Rolled machine, agitator, Henschel mixer, colloidal mill, ultrasonic homogenizer, iron shot shredder, wet shotcrete technology mill, coating rocker.In order to remove the coarse particle composition of pigment dispersion, can use separating centrifuge or strainer in addition.

Though the median size of the pigment particles in the pigment ink is selected in aspects such as the stability from printing ink, image color, reflecting feel, photostabilization, preferably consider suitably to select particle diameter from raising gloss, raising texture aspect.

As mentioned above, photosensitive composite of the present invention utilizes its feature, can be used for above-mentioned various uses suitably.

Embodiment

The present invention will be described based on embodiment." part " in embodiment and the comparative example refers to weight part, and % refers to wt%.

And, carry out for the light solidified of photosensitive composite and the evaluation of physical property of cured film with following method.

The evaluation of physical property of＜light solidified and cured film 〉

Tack-free exposure (TFED): the exposure of the minimum of surface cure, the desired necessity of viscosity diminishes is obtained by referring to touch the observation overlay film in the exposure back.

Water tolerance: will impregnated in the water after 24 hours with tack-free exposure solidified overlay film, the state on visual inspection surface, the surface is judged to be when not coarse well.

Tackiness: for the cured film on the base material that is formed at preparation, carry out chessboard grid tape stripping (crosscut) test, carry out the mensuration of survival rate (in 100 grids 100 grids do not peel off fully and when remaining, be made as 100/100).

Flexible: in the cured film of having carried out forming on 2 oriented polypropylene of surface-treated (OPP) film, carry out the pliability tests of 180 degree, with generate being made as of crackle etc. *, be made as zero with unconverted.

Transformation efficiency:, calculate reactivity from each decrement that absorbs of uviolizing front and back epoxy group(ing), vinyl and try to achieve transformation efficiency by FT-IR.

[embodiment 1]

Get 100 parts 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate is as the compound that has at least 2 ester ring type epoxy group(ing) in the molecule (a); 6 parts para-tertiary butyl phenol phenolic resin (PAPS series: the organic material industry of rising sun society system), contain the phenolic compound of 50wt% in this para-tertiary butyl phenol phenolic resin with 3～5 phenol aromatic nucleus as multinuclear phenolic compound (b); The TEPBI-S of 2 parts salt compounded of iodine type (trade(brand)name: Japanese catalyst society system),, obtain photosensitive composite with the above-mentioned substance thorough mixing as energy line susceptibility cationic polymers initiator (c).Use metering bar coater this photosensitive composite to be coated on the various base materials such as glass, aluminium, OPP film, PET, and the thickness that makes film is 4 μ m, then, expose with 400W high pressure mercury vapour lamp exposure machine (Sen special light sources society system), the evaluation of light solidified of filming and cured film rerum natura, the result is as shown in table 1.

[embodiment 2]

As embodiment 1, wherein, the hydroxyethyl vinyl ether by 14 parts of further uses carries out the modulation of photosensitive composite as hydroxy-containing compounds (d), carries out the light solidified of film and the evaluation of cured film rerum natura, and the result is as shown in table 1.

[embodiment 3]

As embodiment 2, wherein, UVI-6990 by using 4 parts sulfonium salt type (about 50% propylene carbonate solution: Dow Chemical Japan society system) substitute 2 parts TEPBI-S as composition (c), use 18 parts 4-hydroxybutyl vinyl ether to substitute 14 parts hydroxyethyl vinyl ether as composition (d), carry out the modulation of photosensitive composite, carry out the light solidified of film and the evaluation of cured film rerum natura, the result is as shown in table 1.

[embodiment 4]

By with 70 parts 3,4-epoxycyclohexyl methyl-3,4-epoxy cyclohexane carboxylic-acid ester as composition (a), 4 parts PAPS type para-tertiary butyl phenol phenolic resin as composition (b), 24 parts hydroxy butyl vinyl ether as composition (d) thorough mixing, behind the modulation photosensitive composite, operate with embodiment 1 identically, carry out the light solidified of film and the evaluation of cured film rerum natura, the result is as shown in table 1.

[embodiment 5]

As embodiment 3, wherein, substitute 6 parts PAPS type para-tertiary butyl phenol phenolic resin as composition (b) by the DPP-6125 as the Dicyclopentadiene (DCPD) phenol resins (Nippon Oil(Nippon Mitsubishi Oil) chemistry society system) that uses 9 parts, carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[embodiment 6]

As embodiment 3, wherein, two [1-ethyl (3-oxetanyl)] methyl ether by 6 parts of further uses (the synthetic society in East Asia system) carries out the modulation of photosensitive composite, carries out the evaluation of light solidified and cured film rerum natura, and the result is as shown in table 1.

[embodiment 7]

In the photosensitive composite that obtains at embodiment 3, further use 9 parts 1,4-butyleneglycol divinyl ether carries out the modulation of photosensitive composite, carries out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[embodiment 8]

As embodiment 3, wherein, substitute 18 parts 4-hydroxybutyl vinyl ether as composition (d), carry out the modulation of photosensitive composite by the cyclohexanedimethanol mono vinyl ether that uses 15 parts, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[embodiment 9]

As embodiment 3, wherein, replace 18 parts 4-hydroxybutyl vinyl ether as composition (d), carry out the modulation of photosensitive composite by the 3-ethyl-3-hydroxymethyl trimethylene oxide that uses 18 parts, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[embodiment 10]

As embodiment 3, wherein, substitute 18 parts 4-hydroxybutyl vinyl ether as composition (d) by the 4-hydroxybutyl vinyl ether that uses 3-ethyl-3-hydroxymethyl trimethylene oxide of 9 parts and 9 parts, carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[embodiment 11]

As embodiment 3, wherein, (trade(brand)name: big Japanese ink industry society system) carry out the modulation of photosensitive composite as composition (a), carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1 for epoxy resin ICLONHP7200 by 10 parts of further uses.

[comparative example 1]

To only contain 100 parts 3,4-epoxycyclohexyl methyl-3, after 4-epoxy cyclohexane carboxylic-acid ester is modulated as the photosensitive composite of composition (c) as the UVI-6990 of composition (a) and 4 parts, similarly operate with the foregoing description 1, carry out the light solidified of photosensitive composite and the evaluation of cured film rerum natura, the result is as shown in table 1.

[comparative example 2]

As embodiment 3, wherein, do not use the multinuclear phenolic compound of composition (b) to carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 3]

As embodiment 9, wherein, do not use the multinuclear phenolic compound of composition (b) to carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 4]

As embodiment 10, wherein, do not use the multinuclear phenolic compound of composition (b) to carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 5]

As embodiment 1, wherein, substitute the multinuclear phenolic compound of 6 parts composition (b) by the tetramethylolmethane (polyvalent alcohol) that uses 6 parts, carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 6]

As embodiment 1, wherein, substitute the multinuclear phenolic compound of 6 parts composition (b), carry out the modulation of photosensitive composite by the butyleneglycol divinyl ether (vinyl ether that does not have hydroxyl) that uses 40 parts, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 7]

In embodiment 1, by using 6 parts to be that the CRG-951 (clear and polymer society system) of first rank novolac type phenol resin substitutes 6 parts of PAPS type para-tertiary butyl phenol phenolic resins as composition (b), carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 8]

As embodiment 3, wherein, by using 6 parts to be that the CRG-951 (clear and polymer society system) of first rank novolac type phenol resin substitutes 6 parts of PAPS type para-tertiary butyl phenol phenolic resins as composition (b), carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 9]

As embodiment 3, wherein, by use 6 parts four-[methylene radical-3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester] methane (with the pure pharmaceutical worker of light industry society system) substitutes 6 parts of PAPS type para-tertiary butyl phenol phenolic resins as composition (b), carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 10]

As embodiment 3, wherein, use 6 parts 2,2-methylene radical two (4-tert.-butyl phenol), it is the multinuclear phenolic compound that contains 2 phenol aromatic nucleus, substitutes 6 parts of PAPS type para-tertiary butyl phenol phenolic resins as composition (b) with this, carries out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 11]

As embodiment 3, wherein, use 6 parts para-tertiary butyl phenol phenolic resin, wherein, have the content height of the multinuclear phenolic compound of at least 6 phenol aromatic nucleus, and the content that contains the multinuclear phenolic compound of 3～5 phenol aromatic nucleus is 25%, substitute 6 parts of PAPS type para-tertiary butyl phenol phenolic resins with this para-tertiary butyl phenol phenolic resin as composition (b), carry out the modulation of photosensitive composite, carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

[comparative example 12]

As embodiment 3, wherein, substitute 6 parts of para-tertiary butyl phenol phenolic resins, carry out the modulation of photosensitive composite as composition (b) by using 70 parts para-tertiary butyl phenol phenolic resin (being equivalent to 56wt%), carry out the evaluation of light solidified and cured film rerum natura, the result is as shown in table 1.

By The above results as can be known, by the photosensitive composite shown in the energy line irradiation embodiment, these photosensitive composites all show excellent light solidified, water tolerance and with the tackiness of various substrates, particularly for the composition that contains hydroxy-containing compounds (d) (embodiment 2～11), transformation efficiency and flexible aspect on excellent.Comparative example 1～4th is equivalent to remove from embodiment 1,3,9,10 respectively the photosensitive composite of multinuclear phenolic compound (b), thus the value of TFED uprise, the solidified nature variation, tackiness also becomes bad simultaneously.In comparative example 5, attempt using polyvalent alcohol to substitute multinuclear phenolic compound (b), but do not obtain desired performance.In addition, in comparative example 7,8, use is the first rank novolac type phenol resin of heat-curing resin when substituting multinuclear phenolic compound of the present invention, and it is not enough to solidify rerum natura, and the phenomenon that viscosity is recovered occurs through for some time solidified surface, so undesirable.Be the different example of composition (b) in addition, as the multinuclear phenolic compound, in comparative example 9, use has the phenol antioxidant of the tertiary butyl at the ortho position, in comparative example 10, only use the multinuclear phenolic compound that contains 2 phenol aromatic nucleus, in comparative example 11, use has the high and content of multinuclear phenolic compound that contains 3～5 phenol aromatic nucleus of at least 6 the content of multinuclear phenolic compound of phenol aromatic nucleus less than the para-tertiary butyl phenol phenolic resin of 40wt%, all can not obtain satisfied performance under these situations.In addition, in comparative example 12, even use multinuclear phenolic compound of the present invention, but when its usage quantity was 56wt%, owing to surpass 40wt%, thereby tackiness and water tolerance reduced.

Hereinafter, to photosensitive composite of the present invention is described as the photosensitivity jetted ink.

[embodiment 12]

As embodiment 4, wherein, modulate photosensitive composite by the triethylene glycol divinyl ether of 9 parts of further uses.In said composition, with 5 parts titanium oxide pigments CR-50 (the former industry of stone society system) as pigment, 1.5 the aliphatics modification class dispersion agent Solsperse 32000 (Zeneca society system) of part is as pigment dispersing agent, 1 part 2,4-diethyl thioxanthone (Japanese chemical drug society system) is as photosensitizers, use sand mill to disperse 4 hours, the composition that obtains is filtered with the membrane filter pressurization obtain the energy-line solidifying type jetted ink.Measure the viscosity of the printing ink obtain with E type viscometer (25 ℃), found that the viscosity of the printing ink that obtains is lower, be 25mPas.Use this printing ink on various base materials such as glass, aluminium, OPP film, PET, to print with ink-jet printer with piezoelectric type China ink head, then, by UV irradiation equipment (1 metal halide lamp: output rating 120W) carry out the curing of printing ink, carry out the evaluation of its light solidity and cured film rerum natura.The result is as shown in table 2.

[embodiment 13]

As embodiment 12, wherein, use 9 parts 2-(2-vinyloxy group oxyethyl group) ethyl propylene acid esters to substitute 9 parts triethylene glycol divinyl ether, below operation similarly obtain the energy-line solidifying type jetted ink.Measure with E type viscometer (25 ℃), the viscosity of printing ink is 25mPas.Similarly this printing ink is printed on various base materials such as glass, aluminium, OPP film, PET with the ink-jet printer with piezoelectric type China ink head, then, carry out the curing of printing ink by UV irradiation equipment (the same), carry out the evaluation of its light solidity and cured film rerum natura.The result is as shown in table 2.

Shown in embodiment 12,13, photosensitive composite of the present invention is low owing to viscosity, and has excellent light solidified, water tolerance, tackiness, flexibility simultaneously, so be used in the photosensitivity jetted ink suitably.

Then, illustrate that evaluation photosensitive composite of the present invention is as the embodiment of OLED indicating meter with the characteristic of sealing agent.

[embodiment 14]

After using the photosensitive composite of knife coater coating embodiment 3,, be 3000mJ/cm in exposure by using 400W high pressure mercury vapour lamp exposure machine (Sen special light sources society system) ²Condition under carry out rayed and obtain the cured film that thickness is 100 μ m.To the film that so obtains, use the steam permeability detector according to JISK7129A: L80-5000 type (LYSSY society system), under the condition of 40 ℃ * 90%RH, to measure, vapor transfer rate is 5g/m ²24hr.In addition, photosensitive composite of the present invention is put into 30mm * 5mm, thickness is between the SUS/ glass of 10 μ m, similarly, is 500mJ/cm in exposure ²Condition under carry out after rayed adheres, by RTC-1210A tension test instrument ((strain) A﹠amp; D society system) be that 5mm/min measures with the draw speed, adhesion strength is 15MPa, shows good adhesion strength.

[embodiment 15]

As embodiment 14, wherein, use the photosensitive composite of embodiment 5 to come the photoresist of alternate embodiment 3, vapor transfer rate, the adhesion strength of mensuration are respectively 3g/m ²24hr, 13MPa.

[embodiment 16]

As embodiment 14, wherein, use the photosensitive composite of embodiment 8 to come the photoresist of alternate embodiment 3, vapor transfer rate, the adhesion strength of mensuration are respectively 3g/m ²24hr, 13MPa.

[comparative example 13]

As embodiment 14, wherein, use the photosensitive composite of comparative example 2 to come the photoresist of alternate embodiment 3, vapor transfer rate, the adhesion strength of mensuration are respectively 45g/m ²24hr, 5MPa.

As from the foregoing, the cationically polymerizable photosensitive composite of the present invention shown in the foregoing description 14～16 not only has excellent light solidified, water tolerance, flexibility and higher tackiness, further also has low water vapour permeability.In contrast, utilize shown in the comparative example 13 do not contain the composition of multinuclear phenolic compound of the present invention (b) time, adhesion strength is low, and Water Vapour Permeability is big, is unsuitable when the sealing agent.In the manufacturing of OLED indicating meter, using the fit operation of sealing material of sealing agent is the important procedure of reliability of the OLED indicating meter of decision manufacturing.Therefore, the photosensitive composite that shows excellent evaluation characteristic in the present embodiment can be used as the FPD sealing agent suitably, is specially adapted to the OLED indicating meter to low rate of perviousness special requirement.

At last, to photosensitive composite of the present invention is prevented that as forming reflectance coating from describing with the embodiment of coated material.

[embodiment 17]

In the photosensitive composite of 60 parts embodiment 4, further add 40 parts R812 (goods name: Japanese Aerosil society system), wherein R812 has carried out the aerosil that hydrophobization is handled to the surface, and the methyl ethyl ketone (with the pure pharmaceutical worker's industry of light) that adds 100 parts as solvent, is prevented the photosensitive composite that reflectance coating is used by the homogenizer thorough mixing.Said composition is coated on Delaglas (trade(brand)name: Chemicals society of Asahi Chemical Industry system) on the substrate of Xing Chenging by spin coater (Mikasa society system), described Delaglas is that to have the PMMA resin of black pigment and make the thickness of film be 0.1 μ m, carries out uviolizing then.Then, under 80 ℃, heat that removing in 1 minute desolvates obtains the measuring reflectance sample.Use ultraviolet visible spectrophotometer (V-550: Japanese beam split society system) measure the absolute specular reflection spectrum of this sample.Measurement result is as follows, and reflectivity is extremely low at the 620nm place, is 0.8%.

Table 1

	Tack-free exposure (TFED)	Water tolerance	Tackiness	Flexible	Transformation efficiency
							Epoxy group(ing)	Vinyl
					Embodiment 1	30mJ/cm 2			Well	100/100	×	60％	-
Embodiment 2	＜20mJ/cm 2	Well	100/100	○			98％	98％
					Embodiment 3	30mJ/cm 2			Well	100/100	○	98％	98％
Embodiment 4	30mJ/cm 2	Well	100/100	○			98％	98％
					Embodiment 5	30mJ/cm 2			Well	100/100	○	98％	98％
Embodiment 6	＜20mJ/cm 2	Well	100/100	○			98％	98％
					Embodiment 7	＜20mJ/cm 2			Well	100/100	○	98％	98％
Embodiment 8	30mJ/cm 2	Well	100/100	○			98％	98％
					Embodiment 9	30mJ/cm 2			Well	100/100	○	98％	98％
Embodiment 10	30mJ/cm 2	Well	100/100	○			98％	98％
					Embodiment 11	30mJ/cm 2			Well	100/100	○	98％	98％
Comparative example 1	100mJ/cm 2	Surface irregularity bleaches	100/100 wettability bad (OPP)	×			65％	-
					Comparative example 2	100mJ/cm 2			Well	100/100 wettability bad (OPP)	○	98％	-
Comparative example 3	60mJ/cm 2	Well	0/100 wettability bad (OPP)	○			98％	-
					Comparative example 4	60mJ/cm 2			Well	0/100 wettability bad (OPP)	○	98％	-
Comparative example 5	60mJ/cm 2	Surface irregularity bleaches	100/100	○			85％	-
					Comparative example 6	100mJ/cm 2			Surface irregularity bleaches	0/100 wettability bad (OPP)	○	73％	65％
Comparative example 7	30mJ/cm 2	Surface irregularity bleaches	0/100	×			55％	-
					Comparative example 8	60mJ/cm 2Viscosity reappears			Part surface is coarse	-	○	88％	85％
Comparative example 9	60mJ/cm 2	Part surface is coarse	100/100 (glass, Al) 0/100 (PET, OPP)	○			80％	80％
					Comparative example 10	80mJ/cm 2			Part surface is coarse	100/100	○	85％	83％
Comparative example 11	60mJ/cm 2	Part surface is coarse	100/100	○			90％	93％
					Comparative example 12	60mJ/cm 2			Part surface is coarse	0/100	×	80％	82％

Table 2

	Tack-free exposure (TFED)	Water tolerance	Tackiness	Flexible	Transformation efficiency
							Epoxy group(ing)	Vinyl
					Embodiment 12	30mJ/cm 2			Well	100/100	○	95％	93％
Embodiment 13	20mJ/cm 2	Well	100/100	○			95％	92％

Utilizability on the industry

Photosensitive composite of the present invention, because the curing in atmosphere is excellent, and its solidfied material is excellent for adherence, curing resistance to water and the flexibility of various base materials, so can be used for suitably the flat-panel monitor (FPD) of photosensitive coating material, ink-jet printing ink, sticker, particularly organic EL etc. with in the fields such as sealant.

Claims (12)

1. photosensitive composite is characterized in that, it contains the epoxy compounds (a) of 30wt%～90wt%, the multinuclear phenolic compound (b) of 0.1wt%～40wt%, the energy line susceptibility cationic polymerization initiators (c) of 0.1wt%～10wt%; In the molecule of described epoxy compounds (a), have at least 2 epoxy group(ing); Described multinuclear phenolic compound (b) contains 3～5 phenol aromatic nucleus, wherein the ortho position of each hydroxyl not by methylol, contain alkyl, contain more than or equal to any one group in the cycloalkyl of 4 carbon atoms and replace more than or equal to 4 carbon atoms, and described multinuclear phenolic compound (b) has at least 2 do not have the phenol aromatic nucleus that replace at least one ortho position of its hydroxyl.

2. photosensitive composite as claimed in claim 1, it further contains the hydroxy-containing compounds (d) of 1wt%～60wt%; Have at least 1 hydroxyl in the molecule of described hydroxy-containing compounds (d), also have at least a group at least 1 vinyl ether group and the oxetanyl.

3. photosensitive composite as claimed in claim 1 or 2, wherein, the epoxy group(ing) that described epoxy compounds (a) is had is the ester ring type epoxy group(ing).

4. as any described photosensitive composite of claim 1～3, wherein, described multinuclear phenolic compound (b) contains the various multinuclear phenolic compounds (e) shown in the following general formula (1), further contain the various multinuclear phenolic compounds (f) shown in the following general formula (2), and with respect to multinuclear phenolic compound (e) and total amount (f), the ratio of multinuclear phenolic compound (e) is more than or equal to 40wt%;

R in the general formula (1) represents that carbonatoms is that 1～5 alkyl, carbonatoms are that 5～10 cycloalkyl, carbonatoms are 1～5 alkoxyl group, halogen atom, hydroxyl, aryl or aralkyl, a plurality of R in the general formula (1) are different or identical mutually, m is 0～3 integer, and n is 1～3 integer;

In the general formula (2), R represents that carbonatoms is that 1～5 alkyl, carbonatoms are that 5～10 cycloalkyl, carbonatoms are 1～5 alkoxyl group, halogen atom, hydroxyl, aryl or aralkyl, a plurality of R in the general formula (2) are different or identical mutually, m is 0～3 integer, and n is 0 or more than or equal to 4 integer.

5. as any described photosensitive composite of claim 1～3, wherein, described multinuclear phenolic compound (b) contains the various multinuclear phenolic compounds (g) shown in the following general formula (3), further contain the various multinuclear phenolic compounds (h) shown in the following general formula (4), and with respect to multinuclear phenolic compound (g) and total amount (h), the ratio of multinuclear phenolic compound (g) is more than or equal to 40wt%;

N in the general formula (3) represents 1～3 integer;

N in the general formula (4) represents 0 or more than or equal to 4 integer.

6. cured article, it is by to any described photosensitive composite irradiation active ray as claim 1～5, further as required postradiation composition is heated to obtain.

7. photosensitivity tackiness agent, it contains any described photosensitive composite just like claim 1～5.

8. photosensitivity coated material, it contains any described photosensitive composite just like claim 1～5.

9. photosensitivity jetted ink, it contains any described photosensitive composite and tinting material just like claim 1～5.

10. cured article, it is by to any described photosensitive material irradiation active ray as claim 7～9, further as required postradiation material is heated to obtain.

11. flat-panel monitor, it is to use photosensitivity tackiness agent as claimed in claim 7 to make as sealing agent.

12. flat-panel monitor as claimed in claim 11, wherein, described flat-panel monitor is an organic electroluminescence display.

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