JP2003096185A - Photocurable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocationically curable resin composition giving an excellent conversion rate at a low temperature and giving a cured product excellent in adhesive strength and moisture permeation resistance. SOLUTION: The photocationically curable resin composition comprises (A) a cationically polymerizable compound, (B) a photocationic polymerization initiator and (C) an aliphatic thioether compound. A liquid crystal display or an electroluminescence display excellent in adhesive strength and moisture permeation resistance can be obtained with good productivity using a sealing material comprising the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocationic curable resin composition, its use, and more particularly to a sealing material for liquid crystal displays and a sealing material for electroluminescence displays. More specifically, it relates to a photocationic curable resin composition having excellent adhesiveness, moisture permeability resistance, and photocationic polymerizability at low temperatures, and uses thereof.

[0002]

BACKGROUND OF THE INVENTION In recent years, flat panel displays using various display elements have been developed and manufactured in the electronic and electrical industries. Most of these displays have a display element sealed in a cell made of a flat panel such as glass or plastic. Typical examples thereof include a liquid crystal (LC) display and an electroluminescence (EL) display.

A liquid crystal display usually has a glass substrate 2
The periphery of the sheet is sealed with a sealing material and pasted together, and the liquid crystal is sealed therein. Conventionally, the sealing material is
Thermosetting epoxy resins have been used. However, such a thermosetting epoxy resin needs to be heated and cured at a high temperature of 150 ° C. to 180 ° C. for about 2 hours, which causes a problem that productivity cannot be improved.

On the other hand, the EL display is excellent in high brightness, high efficiency, high-speed response, and the like, and is attracting attention as a next-generation flat panel display. EL elements include inorganic EL elements and organic EL elements. For example, the inorganic EL elements have been put to practical use in timepiece backlights and the like.
The organic EL element is superior to the inorganic EL element in terms of high brightness, high efficiency, high-speed response, and multicoloring, but it has low heat resistance and the heat resistance temperature is usually about 80 to 100 ° C. Therefore, in the seal of the organic EL display, there is a problem that even if a thermosetting epoxy resin is used as the sealing material, it cannot be sufficiently heat-cured.

In order to solve these problems, attempts have been made to develop a photo-curing type sealing material which can be cured at low temperature and at high speed. As the photo-curable sealant, there are usually a photo radical-curable sealant and a photocation-curable sealant. Acrylic resin is mainly used as a photo-radical curable sealant, and it has the advantage of being able to use various acrylate monomers and oligomers, but its moisture resistance is insufficient and it reduces volume shrinkage and adhesion. Further improvement of strength was needed.

On the other hand, an epoxy resin is mainly used as a photocationic curable sealant, and its adhesiveness is relatively good, but further improvement in photocurability such as photosensitivity and fast curability is required. It was being done. In particular, in the cationic photopolymerization, although the polymerization temperature can usually be set in a relatively low range, the conversion rate of the polymerizable compound is not improved because the polymerization temperature is low, and it is difficult to obtain excellent photosensitivity and fast curability. There was a problem. Therefore, in order to improve the conversion rate of the polymerizable compound in the photocationic polymerization, attempts have been made to blend a compound having a hydroxyl group, but in some cases it is not possible to obtain a high molecular weight polymer due to chain transfer by the hydroxyl group. there were.

Therefore, a photo-cationic polymerization which gives a cured product which is excellent in photo-curing property such as having high photo-curing property even in a relatively low temperature region, and which is also excellent in adhesiveness to a substrate and moisture resistance. The advent of mold resin compositions has been desired. Therefore, the present inventors have diligently studied to solve the above problems,
A resin composition composed of a cationically polymerizable compound, a photocationic initiator and an aliphatic thioether compound has excellent low-temperature curability, and the cured product has excellent adhesive strength and moisture resistance, and good production. It has been found to have properties. Further, the present inventors have found that such a photocationic curable resin composition can be suitably used for flat panels such as liquid crystal displays and electroluminescence displays, and have completed the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in polymerization conversion property at low temperature and has excellent adhesive strength and moisture permeation resistance. Another object of the present invention is to provide a photocationic curable resin composition which gives a cured product having good productivity.

Further, the present invention relates to a sealing material suitable for a flat panel such as a liquid crystal display and an electroluminescence display, a liquid crystal display and an electroluminescence display using the sealing material, a liquid crystal display using the sealing material, and an electroluminescence display. It is an object to provide a sealing method and a manufacturing method.

[0010]

SUMMARY OF THE INVENTION The photocationic curable resin composition according to the present invention is characterized by containing (A) a cationically polymerizable compound, (B) a photocationic initiator and (C) an aliphatic thioether compound. The aliphatic thioether compound (C) is preferably a compound represented by the following general formula (I).

[0011]

[Chemical 2]

[In the above general formula (I), R represents an alkyl group having 1 to 18 carbon atoms. ]. The cationically polymerizable compound (A) is preferably an epoxy compound and / or an oxetane compound. The aliphatic thioether compound (C) is preferably contained in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of the photocationic curable resin composition.

The cationic photo-curable resin composition may further contain (D) a fine particle inorganic filler. The photocationic curable resin composition may further contain (E) a silane coupling agent. The cationically polymerizable compound (A) is 5 to 99.8 parts by weight, the photocationic initiator (B) is 0.1 to 10 parts by weight, and the aliphatic thioether compound (C) is 0.01 to 5 parts by weight. The amount of the fine particle inorganic filler (D) is 0 to 70 parts by weight, and the amount of the silane coupling agent (E) is 0 to 10 parts by weight (however, the amount is based on 100 parts by weight of the cationic photocurable resin composition. ) Is preferable.

The liquid crystal display sealing material according to the present invention is characterized by comprising the above-mentioned photocationic curable resin composition. The sealing method according to the present invention is a method for sealing a liquid crystal display in which opposing substrates of a liquid crystal display are bonded to each other with a sealing material, wherein the sealing material for liquid crystal display is used as the sealing material.

The method for manufacturing a liquid crystal display according to the present invention is a method for manufacturing a liquid crystal display, including a step of laminating opposing substrates of the liquid crystal display with a sealing material, wherein the sealing material for liquid crystal display is used as the sealing material. It has a feature. The liquid crystal display according to the present invention is characterized in that the sealing material for adhering the opposing substrates of the liquid crystal display is the sealing material for the liquid crystal display.

The electroluminescent display sealing material according to the present invention is characterized by comprising the above-mentioned photocationic curable resin composition. The sealing method according to the present invention is characterized in that the sealing material for an electroluminescent display is used as a sealing material in a sealing method for an electroluminescent display, in which opposing substrates of the electroluminescent display are bonded with a sealing material.

A method for manufacturing an electroluminescent display according to the present invention is a method for manufacturing an electroluminescent display, which comprises a step of laminating opposing substrates of the electroluminescent display with a sealing material, wherein the sealing material for electroluminescent display is used as a sealing material. It is characterized by using.

The electroluminescent display according to the present invention is characterized in that the sealing material for adhering the opposing substrates of the electroluminescent display is the sealing material for the electroluminescent display.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below. [(A) Cationic Polymerizable Compound] Examples of the cationic polymerizable compound (A) in the present invention include epoxy compounds and oxetane compounds.

Specific examples of the epoxy compound include phenyl glycidyl ether and butyl glycidyl ether as compounds having one epoxy group, and hexanediol diglycidyl ether and tetraethylene as compounds having two or more epoxy groups. Examples thereof include glycol diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and novolac type epoxy compound.

Examples of the compound having an alicyclic epoxy group also include compounds represented by the following general formulas (1) and (2).

[0022]

[Chemical 3]

The oxetane compound is represented by the following general formula (3)

[0024]

[Chemical 4]

Any compound having at least one oxetane ring represented by can be used.
For example, a compound containing preferably 1 to 15 oxetane rings, more preferably a compound containing 1 to 10 and particularly preferably a compound containing 1 to 4 are mentioned. <Compound having one oxetane ring> One oxetane ring
The following general formula (4)

[0026]

[Chemical 5]

Examples thereof include compounds represented by In the general formula (4), Z, R ¹ and R ² mean the following atoms or substituents. Z is an oxygen atom or a sulfur atom.
R ¹ is an alkyl group having 1 to 6 carbon atoms such as hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group and butyl group; trifluoromethyl group, perfluoromethyl group, perfluoroethyl group, perfluoro A fluoroalkyl group having 1 to 6 carbon atoms such as propyl group; an aryl group having 6 to 18 carbon atoms such as phenyl group and naphthyl group, a furyl group or a thienyl group.

R ² is a hydrogen atom, a methyl group, an ethyl group,
Alkyl groups having 1 to 6 carbon atoms such as propyl group, butyl group, pentyl group and hexyl group; 1-propenyl group, 2
-Propenyl group, 2-methyl-1-propenyl group, 2-
An alkenyl group having 2 to 6 carbon atoms such as methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group; benzyl group, fluorobenzyl group, methoxybenzyl group, phenethyl group, styryl Group, substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms such as cinnamyl group and ethoxybenzyl group; group having other aromatic ring such as aryloxyalkyl group such as phenoxymethyl group and phenoxyethyl group; ethylcarbonyl Group, propylcarbonyl group, butylcarbonyl group, etc., with 2 to 2 carbon atoms
6 alkylcarbonyl groups; an ethoxycarbonyl group,
An alkoxycarbonyl group having 2 to 6 carbon atoms such as propoxycarbonyl group and butoxycarbonyl group; 2 to 2 carbon atoms such as ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, pentylcarbamoyl group
6 N-alkylcarbamoyl groups.

Substituents other than the above may be used as long as the effects of the present invention are not impaired. More specific examples of the compound having one oxetane ring include 3-ethyl-3
-Hydroxymethyl oxetane, 3- (meth) allyloxymethyl-3-ethyl oxetane, (3-ethyl-3
-Oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy)
Methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1
-(3-Ethyl-3-oxetanylmethoxy) ethyl]
Phenyl ether, isobutoxymethyl (3-ethyl-
3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3)
-Oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) Ether, dicyclopentenylethyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2- Tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-
Ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl)
Ether, 2-hydroxypropyl (3-ethyl-3-
Oxetanylmethyl) ether, butoxyethyl (3-
Ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl)
Ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-
3-oxetanylmethyl) ether and the like can be mentioned.

Examples of the compound having two oxetane rings include compounds represented by the following general formulas (5) and (6).

[0031]

[Chemical 6]

In the general formulas (5) and (6), R ¹
Is a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or another alkyl group having 1 to 6 carbon atoms, like the general formula (4); a trifluoromethyl group, 1 to 1 carbon atoms such as perfluoromethyl group, perfluoroethyl group, perfluoropropyl group
6 fluoroalkyl groups; aryl groups having 6 to 18 carbon atoms such as phenyl group and naphthyl group; furyl group or thienyl group. R ^{1 s} in the general formulas (5) and (6) may be the same or different.

In the general formula (5), R ³ is a linear or branched alkylene group having 1 to 20 carbon atoms such as ethylene group, propylene group, butylene group, poly (ethyleneoxy) group, poly ( A linear or branched poly (alkyleneoxy) group having 1 to 120 carbon atoms, such as a propyleneoxy) group, a propenylene group, a methylpropenylene group,
A linear or branched unsaturated hydrocarbon group such as butenylene group, carbonyl group, alkylene group containing carbonyl group,
An alkylene group containing a carbamoyl group in the middle of the molecular chain.

Further, the R ³ is represented by the following general formula (7),
It may be a polyvalent group selected from the groups represented by (8), (9) and (10).

[0035]

[Chemical 7]

In the general formula (7), R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a methoxy group, an ethoxy group or a propoxy group. 1 to 4 carbon atoms such as butoxy group
Represents an alkoxy group, a halogen atom such as chlorine atom or bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkylcarboxyl group, a carboxyl group, or a carbamoyl group, and X is an integer of 1 to 4.

[0037]

[Chemical 8]

In the above general formula (8), R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a methoxy group, an ethoxy group or a propoxy group. 1 to 4 carbon atoms such as butoxy group
Represents an alkoxy group, a halogen atom such as chlorine atom or bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkylcarboxyl group, a carboxyl group, or a carbamoyl group, and X is an integer of 1 to 4.

[0039]

[Chemical 9]

In the general formula (9), R ⁵ is an oxygen atom, a sulfur atom, a methylene group, —NH—, —SO—, —
_{SO 2 -, - C (CF} 3) 2 - or -C (CH _{3) 2} - a. General formula (10) is the following substituent.

[0041]

[Chemical 10]

In the above general formula (10), R ⁶ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a phenyl group or a naphthyl group having a carbon number of 6 to 18 aryl groups, y is 0-20
It is an integer of 0. R ⁷ is an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and butyl group, and an aryl group having 6 to 18 carbon atoms such as phenyl group and naphthyl group.

R ⁷ may also be a group represented by the following general formula (11).

[0044]

[Chemical 11]

In the general formula (11), R ⁸ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a carbon atom having a carbon number of 6 to such as a phenyl group or a naphthyl group. 18 aryl groups. Z is 0 to 10
It is an integer of 0. <Compound having two oxetane rings> As a more specific compound having two oxetane rings, the following formula (12):
Examples thereof include compounds represented by (13).

[0046]

[Chemical 12]

Further, examples of the compound having two oxetane rings include 3,7-bis (3-oxetanyl) -5-oxa-nonane and 1,4-bis [(3-ethyl-3-oxetanylmethoxy) ) Methyl] benzene,
1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,2-bis [(3-ethyl-3
-Oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-
3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-)
3-oxetanylmethyl) ether, tricyclodecanediyldimethylene bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-
Oxetanylmethoxy) methyl] butane, 1,6-bis [(3-ethyl-3-oxetanylmethoxy) methyl]
Hexane, polyethylene glycol bis (3-ethyl-
3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl)
Ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-) 3-oxetanylmethyl) ether, E
O-modified bisphenol F bis (3-ethyl-3-oxetanylmethyl) ether and the like can be mentioned.

<Compound having three or more oxetane rings>
Examples of the compound having 3 or more oxetane rings include compounds represented by the following formulas (14), (21) and (22).

[0049]

[Chemical 13]

In the general formula (14), R ¹ is the number of carbon atoms such as hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group, as in the general formula (4). Number of carbon atoms of 1 to 6 alkyl groups, trifluoromethyl group, perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, etc. Number of carbon atoms of 1 to 6 fluoroalkyl groups, phenyl group, naphthyl group, etc. 6 to 18 aryl group, furyl group or thienyl group. R ^{1 s} in the general formula (14) may be the same or different.

R ⁹ represents an organic group having a valence of 3 to 10, for example, a branched or linear alkylene group having 1 to 30 carbon atoms such as groups represented by the following formulas (15) to (17). A branched poly (alkyleneoxy) group such as a group represented by the following formula (18) or a linear or branched polysiloxane-containing group represented by the following formula (19) or formula (20).

In the formula (14), j represents an integer of 3 to 10 which is equal to the valence of R ⁹ .

[0053]

[Chemical 14]

In the above formula (15), R ¹⁰ is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.

[0055]

[Chemical 15]

In the above formula (18), L is an integer of 1 to 10 and may be the same or different.

[0057]

[Chemical 16]

Specific examples of the compound having three or more oxetane rings include compounds represented by the following formula (21) and general formula (22).

[0059]

[Chemical 17]

The compound represented by the general formula (22) is 1 to
It has 10 oxetane rings and is as follows.

[0061]

[Chemical 18]

In the general formula (22), R ¹ is the same as in the general formula (4), and is the number of carbon atoms such as hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. Number of carbon atoms of 1 to 6 alkyl groups, trifluoromethyl group, perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, etc. Number of carbon atoms of 1 to 6 fluoroalkyl groups, phenyl group, naphthyl group, etc. 6 to 18 aryl group, furyl group or thienyl group. R ^{1 s} in the general formula (22) may be the same or different.

[0063] R ⁸ are as for formula (11) R ⁸ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an aryl group having 6 to 18 carbon atoms such as a hexyl group.
Z is an integer of 0-100. At this time, R ⁸ may be the same or different. R ¹¹ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group or a trialkylsilyl group having 3 to 12 carbon atoms (the alkyl groups in the trialkylsilyl group are the same as each other. Or may be different, for example, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, etc.).

R represents an integer of 1 to 10. As the compound having three or more oxetane rings, more specifically,
Trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether,
Pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, diether Pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, etc. Is mentioned.

(High molecular weight compound) Further, as the compound (A) having an oxetane ring, in addition to the above-mentioned examples, a high molecular weight of polystyrene conversion number average molecular weight of about 1000 to 5000 measured by gel permeation chromatography is used. The compound which has is also mentioned. Examples of such compounds include compounds represented by the following general formulas (23), (24), and (25).

[0066]

[Chemical 19]

(Here, p is an integer of 20 to 200.)

[0068]

[Chemical 20]

(Here, q is an integer of 15 to 200.)

[0070]

[Chemical 21]

(Here, s is an integer of 20 to 200.) These compounds having an oxetane ring can be used alone or in combination of two or more.
The content ratio of the cationically polymerizable compound (A) in the resin composition of the present invention is such that the photocationic curable resin composition 10 is used.
0 part by weight is preferably 5 to 99.8 parts by weight, more preferably 5 to 99.6 parts by weight, further preferably 10 to 90 parts by weight, and particularly preferably 30 to 90 parts by weight.
It is desirable that the amount is, by weight, most preferably 50 to 90 parts by weight.

When the amount of the cationically polymerizable compound (A) is 30 parts by weight or more, the photosensitivity and the quick-curing property are excellent, which is preferable. As other cationically polymerizable compounds, for example, oxolane compounds, cyclic acetal compounds, cyclic lactone compounds, thiirane compounds, thietane compounds, spiro orthoester compounds, vinyl ether compounds, ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds, Examples thereof include vinyl compounds.

These may be used alone or in combination of two or more. [(B) Photocationic Initiator] The photocationic initiator (B) of the present invention is not particularly limited as long as it is a compound that initiates cationic polymerization of the resin of the component (A) by light, and any of them can be used. You can

Preferred examples of the photocationic initiator include:
An onium salt having a structure represented by the following general formula (26) can be given. This onium salt reacts with light,
It is a compound that releases a Lewis acid. During ^{_{[R 12 a R 13 b R}} 14 c R 15 d W] m + [MX n + m] m- (26) above wherein the cation is an onium ion, W is
S, Se, Te, P, As, Sb, Bi, O, I, B
r, Cl, or N≡N, R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are the same or different organic groups, and are a, b, c.
And d are each an integer of 0 to 3, and (a + b +
c + d) is equal to ((valence of W) + m).

M is a metal or metalloid which constitutes the central atom of the halogenated complex [MX _{n + m} ], for example,
B, P, As, Sb, Fe, Sn, Bi, Al, Ca,
In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is, for example, a halogen atom such as F, Cl or Br, m is the net charge of the halide complex ion,
n is the valence of M. Specific examples of the onium ion in the general formula (26) include diphenyliodonium,
4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl)
Iodonium, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4
-(Diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, η5-
2,4- (Cyclopentagenyl) [1,2,3,4,
5,6-η- (Methylethyl) benzene] -iron (1+)
Etc.

Specific examples of the anion in the general formula (26) include tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate and hexachloroantimonate. Further, in the formula (26), a perchlorate ion, a trifluoromethanesulfonate ion, a toluenesulfonate ion, a trinitrotoluenesulfonate ion or the like may be used as the anion instead of the halogenated complex [MX _{n + m} ]. Good.

Further, in the general formula (26), the anion may be an aromatic anion instead of the halogenated complex [MX _{n + m} ]. Specifically, for example, tetra (fluorophenyl) borate, tetra (difluorophenyl) borate, tetra (trifluorophenyl) borate, tetra (tetrafluorophenyl) borate, tetra (pentafluorophenyl) borate, tetra (perfluorophenyl) ) Borate, tetra (trifluoromethylphenyl) borate, tetra (di (trifluoromethyl) phenyl) borate and the like can be mentioned.

These photocationic initiators may be used alone or in combination of two or more. The content ratio of the photocationic initiator (B) in the resin composition of the present invention is the photocationic curable resin composition 10.
In 0 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.3 to 4 parts by weight, particularly preferably 0.3 to 3 parts by weight.
It is desirable that the amount is parts by weight. When the content ratio of the photocationic initiator (B) is 0.1 part by weight or more, the cured state of the resin composition becomes good, which is preferable, and from the viewpoint of preventing the photocationic initiator from being eluted after curing, 10 It is preferably less than or equal to parts by weight.

[(C) Aliphatic Thioether Compound] The photocationic curable resin composition according to the present invention contains an aliphatic thioether compound (C). As such an aliphatic thioether compound (C), for example, a compound represented by the following general formula (I) is preferable.

[0080]

[Chemical formula 22]

However, in the general formula (I), R is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 6 to 18 carbon atoms. Photocationic initiator (B) of the cationically polymerizable compound (A)
When an aliphatic thioether compound (C) having such a substituent is used together in the polymerization using
For example, preferably 0 to 100 ° C., more preferably 2
The conversion of the cationically polymerizable compound at 0 to 100 ° C. is improved, and the cured product thereof can exhibit excellent adhesive strength and moisture permeation resistance.

These aliphatic thioether compounds (C)
Can be used alone or in combination of two or more. The content ratio of such an aliphatic thioether compound (C) is such that the photocationic curable resin composition 10
The amount is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and particularly preferably 0.1 to 3 parts by weight, relative to 0 parts by weight.

When the aliphatic thioether compound (C) is used in such a range, the conversion can be further improved and the curability can be further improved. [(D) Fine Particle Inorganic Filler] The resin composition of the present invention preferably contains a fine particle inorganic filler (D). The fine particle inorganic filler has an average diameter of primary particles of 0.005.
It is an inorganic filler of 10 μm.

Specifically, silica, talc, alumina,
Plums, calcium carbonate and the like can be mentioned. As the fine particle inorganic filler, both untreated surface-treated one and surface-treated one can be used. As surface-treated fine particle inorganic filler,
Examples thereof include methoxy group-based, trimethylsilyl group-based, octylsilyl group-based, and fine particle inorganic fillers surface-treated with silicone oil.

These fine particle inorganic fillers (D) are 1
They may be used alone or in combination of two or more. The content ratio of the fine particle inorganic filler (D) in the resin composition of the present invention is preferably 0 to 70 parts by weight,
It is more preferably 0.1 to 70 parts by weight, and particularly preferably 1 to 30 parts by weight.

When the fine particle inorganic filler is added within such a range, the moisture permeation resistance, the adhesive strength, the thixotropic property and the like are improved. [(E) Silane Coupling Agent] The photocationic curable resin composition according to the present invention may contain a silane coupling agent (E), if necessary. Examples of the silane coupling agent (E) include silane compounds having a reactive group such as an epoxy group, a carboxyl group, a methacryloyl group and an isocyanate group.

Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane,
Vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ
-Glycidoxypropyltrimethoxylan, β-
(3,4-epoxycyclohexyl) ethyltrimethoxylan and the like.

These silane coupling agents (E) are
They may be used alone or in combination of two or more. The amount of silane coupling agent (E) used is
It is preferably 0 to 10 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the photocationic curable resin composition.
0 parts by weight, particularly preferably 0.3 to 8 parts by weight is desirable.

It is preferable to add such a silane coupling agent (E) within the above range because the adhesive strength is improved. Therefore, the photocationic curable resin composition according to the present invention,
5 to 99.8 parts by weight of the cationically polymerizable compound (A), 0.1 to 10 parts by weight of the photocationic initiator (B), and 0.01 to 10 parts by weight of the aliphatic thioether compound (C).
5 parts by weight, the fine particle inorganic filler (D) is 0 to 70 parts by weight, and the silane coupling agent (E) is 0 to 1 parts.
Amount of 0 parts by weight (however, cationic photo-curable resin composition 1
The amount based on 00 parts by weight is shown. ) Is preferable.

When the fine particle inorganic filler (D) and the silane coupling agent (E) are used in combination,
5 to 99.6 parts by weight of the cationically polymerizable compound (A), 0.1 to 10 parts by weight of the photocationic initiator (B), and 0.01 to 10 parts by weight of the aliphatic thioether compound (C).
5 parts by weight, the fine particle inorganic filler (D) is 0.1 to 7
It is preferable that 0 part by weight and the silane coupling agent (E) are contained in an amount of 0.1 to 10 parts by weight (however, the amount is based on 100 parts by weight of the cationic photocurable resin composition).

[Other Components] The resin composition of the present invention comprises:
Other components such as a resin component, a filler, a modifier, a stabilizer, and an antioxidant can be contained within a range that does not impair the effects of the present invention. <Other resin component> As the other resin component,
For example, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, silicon-based oligomer, polysulfide. Examples include system oligomers.

These may be used alone or in combination of two or more. <Filler> Examples of the filler include glass beads, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, propylene polymer particles, and the like.

These may be used alone or in combination of two or more. <Modifier> Examples of the modifier include a polymerization initiation aid, an antioxidant, a leveling agent, a wettability improver, a surfactant, a plasticizer, and an ultraviolet absorber. These may be used alone or in combination of two or more.

<Antioxidant> Examples of the antioxidant include phenol compounds. Specifically, phenol compounds include hydroquinone, resorcin, 2,6-
Di-tert-butyl-P-cresol, 4,4′-thiobis- (6-tert-butyl-3-methylphenol), 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-ethylphenol, 1,1,3-tris (2-methyl-4hydroxy-5) -Tert-butylphenyl) butane, n-octadecyl-3- (3,5-di-tert-butyl-4-
Hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethyleneglycolbis [3- (3-tert-butyl-4)
-Hydroxy-5-methylphenyl) propionate]
Etc.

These may be used alone or in combination of two or more. [Preparation of Photocationic Curable Resin Composition] The photocationic curable resin composition according to the present invention is prepared so that the respective compositions are uniformly mixed. In the viscosity range of 0.01 to 300 Pa · s, the coating work can be performed more efficiently, and the mixing stability of each composition is good. The viscosity range is more preferably 0.1 to 100 Pa · s.

The viscosity may be adjusted by adding a resin compounding ratio and other components. When the viscosity is high, kneading may be performed by a conventional method using a triple roll or the like. [Sealing Material, Sealing Method, Manufacturing Method, Liquid Crystal Display and Electroluminescent Display] The sealing material according to the present invention comprises the above-mentioned photocationic curable resin composition.

Since such a sealing material has a high degree of polymerization conversion of the cationically polymerizable compound, is excellent in productivity, and is excellent in adhesive strength and moisture permeation resistance, it is a sealing material for a liquid crystal display or a sealing material for an electroluminescent display. Is suitable as The method of sealing a display using a sealing material made of such a cationic photocurable resin composition is as follows.

First, the sealing material for a liquid crystal display or the sealing material for an electroluminescent display according to the present invention is applied to a liquid crystal display substrate or an electroluminescent display substrate, respectively. The application method is not limited as long as the sealing material can be applied uniformly. For example, it may be carried out by a known method such as screen printing or a method of applying using a dispenser.

After the sealing material according to the present invention is applied on the base material of the display, the display base material is attached and irradiated with light to cure the applied sealing material. Any light source can be used here as long as it can be cured within a predetermined working time. Usually UV light,
More specifically, a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be given as a material that can be irradiated with light in the visible light range.

Usually, when the irradiation light amount is too small, the irradiation light amount can be appropriately selected within a range in which the uncured portion of the resin composition does not remain or a range in which adhesion failure does not occur, but it is usually 500 to 3000 mJ. / Cm ² . There is no particular upper limit of the irradiation amount, but if it is excessive, unnecessary energy is wasted and productivity is reduced, which is not preferable.

In this way, the opposing substrates in the liquid crystal display or the electroluminescence display can be attached by the sealing material according to the present invention. Such a liquid crystal display or electroluminescent display sealing method is a sealing method which provides a liquid crystal display or an electroluminescent display excellent in productivity with high polymerization conversion of a cationically polymerizable compound, adhesive strength, and excellent in moisture permeation resistance. is there.

Further, the method for manufacturing a liquid crystal display or an electroluminescent display according to the present invention is a method in which opposing substrates in the liquid crystal display or the electroluminescent display are bonded with the sealing material of the present invention. Furthermore, the liquid crystal display according to the present invention uses the sealing material according to the present invention as a seal for laminating opposing substrates of a liquid crystal display, and the electroluminescent display according to the present invention uses the sealing material according to the present invention as an electro-luminescent material. It is used as a sealing material to bond the opposing substrates of a luminescent display.

[0103]

The cationic photo-curable resin composition according to the present invention has an excellent conversion rate at low temperature, and the cured product has excellent adhesive strength and moisture permeation resistance. The sealing material made of the composition can provide a liquid crystal display or an electroluminescent display having excellent adhesive strength and moisture resistance with good productivity.

[0104]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. <Measurement Method> The conversion rate was calculated from the absorption reduction rate of the epoxy group or oxetane ring in the IR spectrum (conversion rate) of the obtained resin composition and cured product, which was evaluated as follows. (Adhesive strength) The adhesive strength is such that two glass plates are sandwiched with a resin composition (thickness 100 μm), irradiated with light, and bonded, and the two glass plates are peeled off, and the pulling speed is 2 mm / It was measured at min.

(Film Moisture Permeability) A resin composition film (thickness 100 μm, photocured in accordance with JIS Z0208).
The moisture permeability of m) was measured under the conditions of 40 ° C. and 90% RH. <Raw material> (Cationic polymerizable compound (A)) Epoxy compound a-1: Bisphenol F diglycidyl ether oxetane compound a-2: 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (light Cationic initiator (B)) Photoinitiator b-1: a compound represented by the following formula.

[0106]

[Chemical formula 23]

(Aliphatic Thioether Compound (C)) Thioether Compound c-1: Dilaurylthiodipropionate (Fine Particle Inorganic Filler (D)) Fine Particle Silica d-1: Untreated Surface with Average Diameter of Primary Particles of 12 nm , Fine particle silica.

[0108]

Example 1 (Preparation of Resin Composition) According to the compounding recipe shown in Table 1, a compound (A) having an oxetane ring was used as a component (a).
-1 (bisphenol F diglycidyl ether 96.
9 parts by weight, 3 parts by weight of photoinitiator b-1 (formula (26)) as the photocationic initiator (B) component, and c-1 (dilauryl thiodipropionate) as the aliphatic thioether (C) component. A transparent liquid composition was obtained by mixing 0.1 part by weight and stirring for 1 hour.

(Light curing) 3000 with a metal halide lamp
It was cured by irradiation with light of mJ / cm ² . The evaluation results are shown in Table 2.

[0110]

Example 2 Except that the components having the composition shown in Table 1 were used,
A resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0111]

Comparative Examples 1 to 3 Resin compositions were prepared and evaluated in the same manner as in Example 1 except that the components having the compositions shown in Table 1 were used. The results are shown in Table 2.

[0112]

[Table 1]

[0113]

[Table 2]

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 C08L 63/00 71/02 71/02 C09K 3/10 C09K 3/10 Z (72) Inventor Imon Shuhei 580-32, Nagaura, Sodegaura, Chiba Prefecture Mitsui Chemicals Co., Ltd. (72) Inventor Yasushi Mizuta Chiba Prefecture, 580-32, Nagaura, Sodegaura City Mitsui Chemicals Co., Ltd. (72) Inventor, Yoshio Kikuta Chiba Prefecture 580-32 Nagaura, Sodegaura City Mitsui Chemicals Co., Ltd. (72) Inventor Toshiaki Hozuka Toshiaki Hozu 580-32 Nagaura, Sodegaura City, Chiba F-Term (Reference) Mitsui Chemicals Co., Ltd. 4H017 AA04 AB17 AC04 AC08 AC17 AD06 AE05 4J002 CD011 CD051 CD061 CH031 CN011 CN031 CP031 DE148 DE238 DJ018 DJ048 DJ058 EB116 EV067 EV296 EW176 EX019 EX039 EX069 EX079 EY006 EZ006 FB098 FD018 FD206 FD207 FD349 GP00 4J005 AA07 AA11 BA00 BB04 4J07 FA09 AD01 AB03 AB03 AB01 AB03

Claims (15)

[Claims] 1. A photocationic curable resin composition comprising (A) a cationically polymerizable compound, (B) a photocationic initiator and (C) an aliphatic thioether compound. 2. The aliphatic thioether compound (C)
Is a compound represented by the following general formula (I), wherein the photocationic curable resin composition according to claim 1; [However, in the general formula (I), R represents a carbon atom number of 1 to 1.
18 alkyl groups are shown. ]. 3. The photocationic curable resin composition according to claim 1, wherein the cationically polymerizable compound (A) is an epoxy compound and / or an oxetane compound. 4. The aliphatic thioether compound (C)
Is contained in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of the cationic photocurable resin composition. 4. The cationic photocurable resin composition according to claim 1, wherein object. 5. The cationic photo-curable resin composition according to claim 1, wherein the cationic photo-curable resin composition further contains (D) a fine particle inorganic filler. 6. The cationic photo-curable resin composition according to claim 1, wherein the cationic photo-curable resin composition further contains (E) a silane coupling agent. 7. The cationically polymerizable compound (A) is 5 to
99.8 parts by weight, 0.1 to 10 parts by weight of the photocationic initiator (B), 0.01 to 5 parts by weight of the aliphatic thioether compound (C), and 0 to 0 parts of the fine particle inorganic filler (D). 70 parts by weight, and the silane coupling agent (E) are contained in an amount of 0 to 10 parts by weight (however, the amount is based on 100 parts by weight of the photocationic curable resin composition). The photocationic curable resin composition according to any one of 1 to 6. 8. A sealing material for a liquid crystal display, which comprises the photocationic curable resin composition according to claim 1. 9. A sealing method for a liquid crystal display, which comprises bonding opposing substrates of a liquid crystal display with a sealing material, wherein the sealing material for liquid crystal display according to claim 8 is used as the sealing material. 10. A liquid crystal display manufacturing method including a step of laminating opposing substrates of a liquid crystal display with a sealing material, wherein the sealing material for liquid crystal display according to claim 8 is used as the sealing material. Display manufacturing method. 11. A liquid crystal display, wherein the sealing material for adhering opposite substrates of the liquid crystal display is the sealing material for a liquid crystal display according to claim 8. 12. A sealing material for an electroluminescence display, comprising the photocationic curable resin composition according to claim 1. 13. A sealing method for an electroluminescent display, which comprises adhering opposite substrates of an electroluminescent display with a sealing material, wherein the sealing material for electroluminescent display according to claim 12 is used as the sealing material. Method. 14. In a method for manufacturing an electroluminescent display, which includes a step of adhering opposite substrates of the electroluminescent display with a sealing material, the sealing material for an electroluminescent display according to claim 12 is used as the sealing material. And a method for manufacturing an electroluminescent display. 15. A sealing material for adhering opposite substrates of an electroluminescent display together.
An electroluminescent display comprising the sealing material for an electroluminescent display described in 1.