JP2000219713A - Photocurable resin composition - Google Patents

Abstract

(A) A urethane (meth) acrylate obtained by reacting a polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, (B) a component other than the component (A), In one molecule (meta)
A photocurable resin composition containing a (meth) acrylate compound having at least one acryloyl group, (C) a photopolymerization initiator, and (D) a polyol compound. [Effect] This composition is composed of a transparent thermoplastic resin C
When used for bonding a CD lid and a CCD chip, it has excellent moisture and heat resistance and durability of adhesive strength against temperature change.
It is extremely useful in bonding a CD chip as compared with a conventional adhesive.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition useful for bonding a thermoplastic resin, for example, an electronic and optical component made of a thermoplastic resin, particularly a CCD lid and a CCD chip made of a transparent thermoplastic resin. About things.

[0002]

2. Description of the Related Art Conventionally, CCD [charge co.
Coupled device (charge coupled device)] To protect the chip from dust, moisture, etc., a thin film glass CCD lid [LID (cover)] has been used, but the glass lid is high in specific gravity and heavy. In addition, cracking often occurs during manufacturing, surface polishing, or mounting work on a CCD chip, and there is a problem that workability, workability, and productivity are lacking. In recent years, these glasses have high specific gravity, moldability,
For the purpose of improving the workability and the like, CCD lids made of a transparent thermoplastic resin have been known. Examples of the transparent thermoplastic resin include polymethyl methacrylate resin, which is generally called an acrylic resin, and various modified acrylic resins obtained by improving this from the viewpoint of water resistance and heat resistance, for example, the methyl group of polymethyl methacrylate is replaced with a cyclohexyl group or a norbornene group. And imidized acrylic resin. Further, there may be mentioned a copolymer of styrene and methyl methacrylate, a polycarbonate resin or a modified product thereof, a polystyrene resin, a polyarylate resin, a polyolefin, a norbornene-based resin, and a resin modified from these. In order to bond the CCD lid made of transparent thermoplastic resin and the CCD chip, it is also possible to use an epoxy-based adhesive to hold the CCD at a high temperature and bond it. However, from the viewpoint of productivity, a photo-curing adhesive was used. Adhesion has also attracted attention. However, when a CCD lid made of a transparent thermoplastic resin is bonded to a CCD chip having a different linear expansion coefficient from the CCD lid, there is a problem that the bonding surface is separated due to a slight difference in expansion coefficient due to a temperature change.

[0003]

The problem to be solved by the present invention is to provide an adhesive for thermoplastic resin, for example, an electronic / optical component made of thermoplastic resin, which is excellent in wet heat resistance and durability of adhesive force against temperature change. In particular, it is an object of the present invention to provide a photocurable resin composition useful as an adhesive for bonding a CCD lid and a CCD chip made of a transparent thermoplastic resin.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by the following specific photocurable resin composition.

That is, the present invention provides (A) a urethane (meth) acrylate obtained by reacting a polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, and (B) a component other than the component (A).
An object of the present invention is to provide a photocurable resin composition containing a (meth) acrylate compound having at least one (meth) acryloyl group in one molecule, a (C) photopolymerization initiator, and a (D) polyol compound.

[0006]

DETAILED DESCRIPTION OF THE INVENTION As described above, the urethane (meth) acrylate (hereinafter referred to as "urethane (meth) acrylate (A)") of the component (A) used in the present invention comprises a polyol compound, a polyisocyanate compound and a hydroxyl group. It is obtained by reacting a contained (meth) acrylate compound.

The polyol compounds used include polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, aliphatic hydrocarbons having two or more hydroxyl groups in the molecule, and oils having two or more hydroxyl groups in the molecule. A cyclic hydrocarbon, an unsaturated hydrocarbon having two or more hydroxyl groups in a molecule, and the like are used. These polyols can be used alone or in combination of two or more.

The above polyether polyols include aliphatic polyether polyols, alicyclic polyether polyols, and aromatic polyether polyols.

Here, examples of the aliphatic polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, pentaerythritol, dipentaerythritol, and trimethylol. Propane, ethylene oxide-added triol of trimethylolpropane, propylene oxide-added triol of trimethylolpropane, ethylene oxide and propylene oxide-added triol of trimethylolpropane, ethylene oxide-added tetraol of pentaerythritol, and ethylene oxide-added hexagon of dipentaerythritol Polyols such as alkylene oxide-added polyols such as Alcohols, or two or more kinds of polyether polyol obtained by ring-opening polymerization of ion-polymerizable cyclic compounds, and the like.

The ionic polymerizable cyclic compound includes:
For example, ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl ether, allyl glycidyl Examples thereof include cyclic ethers such as ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate. Specific combinations of the two or more ion-polymerizable cyclic compounds include tetrahydrofuran and ethylene oxide, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, ethylene oxide and propylene oxide, butene-1- Oxides and ethylene oxide, tetrahydrofuran, butene-1-oxide and ethylene oxide can be exemplified.

The above-mentioned ion-polymerizable cyclic compound is subjected to ring-opening copolymerization with a cyclic imine such as ethyleneimine, a cyclic lactonic acid such as β-propiolactone and glycolic lactide, or dimethylcyclopolysiloxane. Polyether polyols can also be used.

As the alicyclic polyether polyol,
Examples thereof include alkylene oxide-added diols of hydrogenated bisphenol A, alkylene oxide-added diols of hydrogenated bisphenol F, and alkylene oxide-added diols of 1,4-cyclohexanediol.

As the aromatic polyether polyol,
For example, alkylene oxide addition diols of bisphenol A, alkylene oxide addition diols of bisphenol F, alkylene oxide addition diols of hydroquinone, alkylene oxide addition diols of naphthohydroquinone, and alkylene oxide addition diols of anthrahydroquinone are exemplified.

As commercial products of the above polyether polyols, for example, aliphatic polyether polyols include:
PTMG650, PTMG1000, PTMG2000
(Mitsubishi Chemical Corporation), PPG1000, EXC
ENOL1020, EXENOL2020, EXCE
NOL3020, EXCENOL4020 (all manufactured by Asahi Glass Co., Ltd.), PEG1000, Unisafe DC11
00, Unisafe DC1800, Unisafe DCB11
00, Unisafe DCB1800 (all manufactured by NOF Corporation), PPTG1000, PPTG2000, P
PTG4000, PTG400, PTG650, PTG
2000, PTG3000, PTGL1000, PTG
L2000 (from Hodogaya Chemical Industry Co., Ltd.), Z-3
001-4, Z-3001-5, PBG2000, PB
G2000B (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), TMP
30, PNT4 glycol, EDA P4, EDA P
8 (above, manufactured by Nippon Emulsifier Co., Ltd.), Quadrol (produced by Asahi Denka Co., Ltd.), tone polyol 0200, tone polyol 0221, tone polyol 0301, tone polyol 0310, tone polyol 2201, tone polyol 2221 (above, union carbide) Company)
Is mentioned. As the aromatic polyether polyol, UNIOL DA400, DA700, DA1000, D
B400 (all manufactured by NOF Corporation) and the like.

The polyester polyol used for synthesizing the urethane (meth) acrylate (A) is as follows:
It is obtained by reacting a polyhydric alcohol with a polybasic acid. Here, as the polyhydric alcohol, ethylene glycol,
Polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,
1,2-bis (hydroxyethyl) cyclohexane,
2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolpropane, trimethylol Ethylene oxide adduct of propane, propylene oxide adduct of trimethylolpropane, adduct of ethylene oxide and propylene oxide of trimethylolpropane, sorbitol, pentaerythritol, dipentaerythritol, alkylene oxide addition polyol (for example,
TMP30, PNT4 glycol, EDA P4, ED
AP8 (all manufactured by Nippon Emulsifier Co., Ltd.), Quadrol (manufactured by Asahi Denka Co., Ltd.), tone polyol 0200, tone polyol 0221, tone polyol 0301, tone polyol 0310, tone polyol 2201,
Tone polyol 2221 (all manufactured by Union Carbide Co., Ltd.)]. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like. Commercial products of these polyester polyols include Clapol P1010 and Clapol P201.
0, PMIPA, PKA-A, PKA-A2, PNA-
2000 (all manufactured by Kuraray Co., Ltd.) and the like can be used.

The polycarbonate polyol used in the synthesis of the urethane (meth) acrylate (A) includes, for example, a polycarbonate diol represented by the formula (1).

[0017]

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(Wherein R ¹ and R ² represent a C2-20 alkylene group, a (poly) ethylene glycol residue, a (poly) propylene glycol residue or a (poly) tetramethylene glycol residue, and m is 1 Specific examples of R ¹ and R ² include 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol 1,1,7-heptanediol, 1,8
-Octanediol, 1,9-nonanediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and the like. As the polycarbonate polyol, as commercial products, DN-980, DN-981, DN-982,
DN-983 (Nippon Polyurethane Industry Co., Ltd.)
PC-8000 (manufactured by PPG), PNOC100
0, PNOC2000, PMC100, PMC2000
(Kuraray Co., Ltd.), Plaxel CD-20
5, CD-208, CD-210, CD-220, CD
-205PL, CD-208PL, CD-210PL,
CD-220PL, CD-205HL, CD-208H
L, CD-210HL, CD-220HL, CD-21
0T, CD-221T (Daicel Chemical Industries, Ltd.)
Manufactured) can be used.

As the polycaprolactone polyol used in the synthesis of the urethane (meth) acrylate (A), ε-caprolactone is used, for example, ethylene glycol, polyethylene glycol, propylene glycol,
Addition to diols such as polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol And polycaprolactone diol obtained by the reaction. These commercial products include Plaxel 205, 2
05AL, 212, 212AL, 220, 220AL
(Above, manufactured by Daicel Chemical Industries, Ltd.) and the like can be used.

The aliphatic hydrocarbon having two or more hydroxyl groups in the molecule used for the synthesis of the urethane (meth) acrylate (A) includes ethylene glycol, propylene glycol, tetramethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 2,2-diethyl-1,3-propane Diol, 3-methyl-1,5-pentanediol, 2-
Methyl-1,8-octanediol, hydroxy-terminated hydrogenated polybutadiene, glycerin, trimethylolpropane, pentaerythritol, sorbitol and the like.

The alicyclic hydrocarbon having two or more hydroxyl groups in the molecule used for the synthesis of urethane (meth) acrylate (A) includes, for example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2
-Bis (hydroxyethyl) cyclohexane, a dimethylol compound of dicyclopentadiene, and tricyclodecanedimethanol.

Examples of the unsaturated hydrocarbon having two or more hydroxyl groups in the molecule used in the synthesis of the urethane (meth) acrylate (A) include hydroxy-terminated polybutadiene and hydroxy-terminated polyisoprene.

Furthermore, urethane (meth) other than the above
Examples of the polyol used for the synthesis of the acrylate (A) include β-methyl-δ-valerolactone diol, castor oil-modified diol, terminal diol compound of polydimethylsiloxane, and polydimethylsiloxane carbitol-modified diol.

The number average molecular weight of these polyols is preferably from 50 to 15000 (number average molecular weight in terms of polystyrene by the GPC method, the same applies hereinafter), and particularly preferably from 100 to 100.
8000.

The polyisocyanate compound used in the synthesis of the urethane (meth) acrylate (A) is preferably a diisocyanate compound.
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate,
1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate,
4,4'-diphenylmethane diisocyanate, 3,
3'-dimethylphenylene diisocyanate, 4,4 '
-Biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
Bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyldiisocyanate, 4-
Examples include diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and tetramethyl xylylene diisocyanate. Of these, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate and the like are particularly preferred. These diisocyanates can be used alone or in combination of two or more.

Examples of the hydroxyl group-containing (meth) acrylate used in the synthesis of the urethane (meth) acrylate (A) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) ) Acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate,
Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, or (meth) acrylate represented by the following structural formula (2),

[0027]

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Wherein R ³ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 15, preferably 1 to 4. Further, alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, etc. And a compound obtained by an addition reaction of a glycidyl group-containing compound with (meth) acrylic acid. Of these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate and the like are preferred.

The method of synthesizing the urethane (meth) acrylate (A) is not particularly limited, and for example, the following (i) to (i)
This is performed according to the method of ii). (I) A method of reacting (b) a polyisocyanate and (c) a hydroxyl group-containing (meth) acrylate, followed by (a) a polyol. (Ii) A method in which (a) a polyol, (b) a polyisocyanate, and (c) a hydroxyl group-containing (meth) acrylate are charged at once and reacted. (Iii) A method in which (a) polyol and (b) polyisocyanate are reacted, and then (c) a hydroxyl group-containing (meth) acrylate is reacted.

In the synthesis of the urethane (meth) acrylate (A) used in the present invention, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-laurate are usually used.
Butyltin, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 1,4-diaza-2-methylbicyclo [2.2.2] octane and the like are mixed with a urethanation catalyst in a total amount of 100 wt. 0.01 to 1 part
The reaction is preferably carried out using parts by weight. The reaction temperature in this reaction is usually 0 to 90 ° C, preferably 10 to 80 ° C.
Perform at ° C.

The preferred number average molecular weight of the urethane (meth) acrylate (A) used in the present invention is from 400 to 200.
00, and particularly preferably 600 to 10,000.

The urethane (meth) acrylate of the component (A) contains the component (A) and the component (B) in the composition of the present invention from the viewpoint of the viscosity of the composition in consideration of adhesion to a substrate and handleability. 5 to 70 parts by weight, especially 10 to 100 parts by weight, based on the total weight of component (C) and component (D)
It is preferred to contain 60 parts by weight.

The (meth) acrylate compound having at least one (meth) acryloyl group in one molecule of the component (B) used in the present invention (hereinafter, also referred to as “(meth) acrylate compound (B)”) includes: Either a monofunctional compound having only one (meth) acryloyl group or a polyfunctional compound having two or more (meth) acryloyl groups may be used, and these may be used in an appropriate ratio.

Examples of the monofunctional compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate,
Isobutyl (meth) acrylate, t-butyl (meth)
Acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) Acrylate, decyl (meth) acrylate,
Isodecyl (meth) acrylate, undecyl (meth)
Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol mono (meth) acrylate, ethoxyethyl (meth)
Acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth)
Acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, Adamantyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, (meth) acryloylmorpholine,
2- (meth) acryloyloxyethyl phthalic acid, 2-
(Meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- ( (Meth) acryloyloxyethyl succinic acid, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, mono [2-
(Meth) acryloyloxyethyl] phosphate, mono [2- (meth) acryloyloxyethyl] diphenyl phosphate, mono [2- (meth) acryloyloxypropyl] phosphate, compounds represented by the following formulas (3) to (5) Can be mentioned.

[0035]

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Wherein R ⁴ represents an alkylene group having 2 to 6 carbon atoms or a hydroxyalkylene group, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. And p represents an integer of 0 to 20. ]

[0037]

Embedded image

[In the formula, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkylene group having 2 to ⁸ carbon atoms, and q represents an integer of 0 to 8. ]

[0039]

Embedded image

[Wherein, R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents an alkylene group having 2 to 8 carbon atoms, r represents an integer of 0 to 8, and R ¹¹ and R ¹² represent hydrogen atoms. And an alkyl group having 1 to 6 carbon atoms. ]

Of these monofunctional compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) ethyl ) Acrylate,
Isobornyl (meth) acrylate, (meth) acryloylmorpholine, and nonylphenyl EO-modified acrylate represented by the formula (3) are particularly preferred.

Commercially available monofunctional compounds of the (meth) acrylate compound (B) used in the present invention include Aronix M101, M102, M110, M111, M
113, M114, M117, M120, M152, M
154, M5300, M5400, M5500, M56
00 (all manufactured by Toagosei Co., Ltd.), KAYARADTC
-110S, R-128H, R629, R644 (all manufactured by Nippon Kayaku Co., Ltd.), HEA, HPA, 4HBA,
IPAA, AIB, SBAA, TBA, IAAA, HE
XA, CHA, NOAA, IOAA, INAA, LA,
TDA, MSAA, CAA, HDAA, LTA, ST
A, ISAA-1, ODAA, NDAA, IBXA, A
DAA, TCDA, 2-MTA, DMA, viscote
# 150, # 150D, # 155, # 158, # 16
0, # 190, # 190D, # 192, # 193, # 2
20, # 320, # 2311HP, # 2000, # 21
00, # 2150, # 2180, MTG (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK ester M-20G, M
-40G, M-90G, M-230G, CB-1, S
A, S, AMP-10G, AMP-20G, AMP-6
0G, AMP-90G, A-SA, NLA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), ACMO (produced by Kojin Co., Ltd.), light acrylate IA-A, LA, SA, BO-
A, EC-A, MTG-A, DPM-A, PO-A, P
-200A, THF-A, IB-XA, HOA-MS,
HOA-MPL, HOA-MPE, HOA-HH, IO
-A, BZ-A, NP-EA, NP-10EA, HOB
-A, FA-108, epoxy ester M-600A,
Light ester HOA, HOP-A, HO, HOP, H
OB, PM (Kyoeisha Chemical Co., Ltd.), FA-5
11, FA-512A, FA-513A (all manufactured by Hitachi Chemical Co., Ltd.), AR-100, MR-100, MR
-200, MR-260 (all manufactured by Daihachi Chemical Co., Ltd.),
JAMP-100, JAMP-514, JPA-514
(Above, manufactured by Johoku Chemical Co., Ltd.).

The (meth) acrylate compound (B)
As the polyfunctional compound used as, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di ( Meth) acrylates,
Neopentylglycol hydroxypivalate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth)
Acrylate, dipentaerythritol penta (meth)
Acrylate, dipentaerythritol hexa (meth)
Acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, trimethylolpropanepolyoxyethyl (meth) acrylate, trimethylolpropanetrioxypropyl (meth) acrylate, trimethylolpropanepolyoxyethyl (meth) acrylate, tris (2- (Hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tricyclodecanedimethano Distearate (meth) acrylate, bisphenol A Jiepokishiji (meth) acrylate, bisphenol F Jiepokishiji (meth) acrylate, bis [2- (meth) acryloyloxyethyl] phosphate, bis [2- (meth) acryloyloxy propyl]
Phosphate and tris [2- (meth) acryloyloxyethyl] phosphate.

Of these polyfunctional compounds, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (hydroxypentylate) di (meth) acrylate ) Acrylates are particularly preferred.

Commercially available polyfunctional compounds include SA
-1002, SA-2006, SA-2007, SA-
4100, SA-5001, SA-6000, SA-
7600, SA-8000, SA-9000 (all manufactured by Mitsubishi Chemical Corporation), VISCOAT # 195, # 195
D, # 214HP, # 215, # 215D, # 230,
# 230D, # 260, # 295, # 295D, # 30
0, # 310HP, # 310HG, # 312, # 335
HP, # 335D, # 360, GPT, # 400, V #
540, # 700, GPT (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD MANDA, R-52
6, NPGDA, PEG400DA, R-167, HX
-220, HX-620, R-551, R-712, R
-604, R-684, GPO-303, TMPTA,
THE-330, TPA-320, TPA-330, P
ET-30, RP-1040, T-1420, DPH
A, D-310, D-330, DPCA-20, DPC
A-30, DPCA-60, DPCA-120 (above,
Nippon Kayaku Co., Ltd.), Aronix M-210, M-
208, M-215, M-220, M-225, M-2
33, M-240, M-245, M-260, M-27
0, M-305, M-309, M-310, M-31
5, M-320, M-350, M-360, M-40
0, M-408, and M-450 (all of which are manufactured by Toagosei Co.
), SR-212, SR-213, SR-355 (all manufactured by Sartomer), SP-1506, SP-150
7, SP-1509, SP-1519-1, SP-15
63, SP-2500, VR60, VR77, VR90
(The above are manufactured by Showa Polymer Co., Ltd.), Light Ester P-2
M (above, manufactured by Kyoeisha Chemical Co., Ltd.), Viscote 3PA
(Manufactured by Osaka Organic Chemical Industry Co., Ltd.), EB-169, EB-
179, EB-3603, R-DX63182 (the above,
Daicel UCB Co., Ltd.).

The component (B) can be used to control the viscosity of the composition of the present invention and the Tg, refractive index and the like of the cured product within a desired range.

Component (B), (meth) acrylate, comprises component (A), component (B), component (C) and component (D).
Is preferably 20 to 90 parts by weight, particularly 30 to 80 parts by weight in the composition of the present invention, based on 100 parts by weight.

The photopolymerization initiator of the component (C) can be used without any particular limitation as long as it is used in a known photocurable resin composition. For example, 2,2-dimethoxy- 1,2-diphenylethan-1-one, 2-
Hydroxy-2-methyl-1-phenyl-propane-1
-One, 1-hydroxycyclohexylphenyl ketone, 3-methylacetophenone, 2,2-dimethoxy-
2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone,
Triphenylamine, carbazole, 3-methylacetophenone, benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-
Diaminobenzophenone, benzoin ethyl ether,
Benzoin propyl ether, Michler's ketone, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-
2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2,
4,6-trimethylbenzoylphenylphosphinate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis ( 2,6-dimethoxybenzoyl) -2,4
4-trimethylpentylphosphine oxide, methylbenzoyl formate, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] Propanone].

Among these photopolymerization initiators, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-
Hydroxy-2-methyl-1-phenyl-propane-1
-One, 1-hydroxycyclohexylphenyl ketone, 3-methylacetophenone, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholino-propan-1-one and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferred.

[0050] These commercial products include IRGACUR.
E184, 261, 369, 500, 651, 907,
CGI-403, 819, 1700, 1800, 185
0, DAROCUR953, 1116, 1173, 16
64, 2273, 2959, ZL1 3331 (or more,
Ciba Specialty Chemicals Co., Ltd.), Luc
irin TPO, LR8728, LR8893 (above, manufactured by BASF), Jubecryl P36 (manufactured by UCB), VICURE55 (manufactured by Akzo), ESACUR
E KIP100F, KIP150 (LAMBERTI
Kayakure ITX, QTX, DET
X, BMS (all manufactured by Nippon Kayaku Co., Ltd.) and the like.

These components (C) may be used alone or in combination of two or more.

In the composition of the present invention, the compounding amount of the component (C) is usually 0 parts by weight based on the total weight of the components (A), (B), (C) and (D) as 100 parts by weight. .1
To 20 parts by weight, preferably 0.5 to 15 parts by weight, particularly preferably 1 to 10 parts by weight. If the amount is less than 0.1 part by weight, curing will be insufficient.

The polyol of component (D) includes polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol,
An aliphatic hydrocarbon having two or more hydroxyl groups in a molecule, an alicyclic hydrocarbon having two or more hydroxyl groups in a molecule, an unsaturated hydrocarbon having two or more hydroxyl groups in a molecule, and the like are used. Specifically, all of those listed as the raw materials of the component (A) are used. These polyols can be used alone or in combination of two or more. The number average molecular weight of the polyol of the component (D) is 300 or more,
Furthermore, 300 to 20,000, especially 600 to 15,000
0 is preferred. Component (D) has the effect of improving the durability of the adhesive force of the composition of the present invention to changes in temperature.

In the composition of the present invention, the compounding amount of the component (D) is selected from the components (A), (B), (C) and (D) in view of sufficient adhesiveness and durability. 10 total weight
As 0 parts by weight, it is usually 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight.

In the composition of the present invention, in addition to the component (A), the component (B), the component (C), and the component (D), as the component (E), a radical other than a compound containing a (meth) acryloyl group is used. A polymerizable compound can be included. Such compounds include N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl acetate, vinyl propionate, styrene,
Examples thereof include divinylbenzene and unsaturated polyester. The unsaturated polyester is an ester of a dicarboxylic acid having a radical polymerizable unsaturated double bond and an alcohol, and examples of the dicarboxylic acid having a radical polymerizable unsaturated double bond include maleic anhydride, itaconic acid, and fumaric acid. And alcohols such as methanol, ethanol, n-propyl alcohol, is
o-propyl alcohol, n-butyl alcohol, is
o-butyl alcohol, sec-butyl alcohol, t
monohydric alcohols such as tert-butyl alcohol, n-hexanol, cyclohexanol and 2-ethylhexyl alcohol; (poly) ethylene glycols such as ethylene glycol, diethylene glycol and triethylene glycol; propylene glycol, dipropylene glycol, tripropylene glycol and the like (Poly) propylene glycols; dihydric alcohols such as 1,6-hexanediol; trihydric alcohols such as glycerin and trimethylolpropane.

In the composition of the present invention, epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, SB
S (styrene / butadiene / styrene block copolymer), hydrogenated SBS, SIS (styrene / isoprene / styrene block copolymer), petroleum resin, xylene resin, ketone resin, fluorine-based oligomer, silicone-based oligomer, polysulfide A system oligomer or the like can be blended.

Further, various paint additives other than those described above, for example, antioxidants, ultraviolet absorbers, light stabilizers, antioxidants, silane coupling agents, defoamers, leveling agents, antistatic agents, surfactants, and preservatives Stabilizer, thermal polymerization inhibitor, plasticizer,
A wettability improver and the like can be blended as needed.
For example, antioxidants include Irganox 24
5, 259, 565, 1010, 1035, 1076,
1081, 1098, 1222, and 1330 (all manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like.

Examples of the ultraviolet absorber include benzotriazole-based and triazine-based ultraviolet absorbers, and commercially available products include Tinuvin P, 234, 320 and 32.
6, 327, 328, 213, 400 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumisor
b 110, 130, 140, 220, 250, 30
0, 320, 340, 350, and 400 (all manufactured by Sumitomo Chemical Co., Ltd.).

As the light stabilizer, Tinuvin 14
4,292,622LD (all manufactured by Ciba Specialty Chemicals Co., Ltd.) SANOL LS440, LS77
0 (manufactured by Sankyo Co., Ltd.), Sumisorb TM-
061 (manufactured by Sumitomo Chemical Co., Ltd.), and when the total composition of the present invention is 100 parts by weight, 5 parts by weight or less can be added.

Examples of the anti-aging agent include phenol-based anti-aging agents, allylamine-based anti-aging agents, ketone amine-based anti-aging agents, and the like.
gene W, S, P, 3C, 6C, RD-G, FR,
AW (above, manufactured by Sumitomo Chemical Co., Ltd.) and the like.
Examples of the silane coupling agent include γ-mercaptopropylmethylmonomethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmonoethoxysilane, γ-mercaptopropyldiethoxysilane, γ
-Mercaptopropyltriethoxysilane, β-mercaptoethylmonoethoxysilane, β-mercaptoethyltriethoxysilane, β-mercaptoethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxylpropyltrimethoxysilane, γ-glycidoxylpropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane and the like. These commercially available products include Silaace S310, S311 and S3
20, S321, S330, S510, S520, S5
30, S610, S620, S710, S810 (all manufactured by Chisso Corporation), SH6062, AY43-06
2, SH6020, SZ6023, SZ6030, SH
6040, SH6076, SZ6083 (Toray,
Dow Corning Silicone Co., Ltd.), KBM40
3, KBM503, KBM602, KBM603, KB
M803, KBE903 (above, Shin-Etsu Silicone Co., Ltd.)
Manufactured).

As the defoaming agent, Floren AC-20 is used.
2, AC-300, AC-303, AC-326F, A
C-900, AC-1190, AC-2000 (or more,
Organic copolymers not containing Si or F atoms, examples of which are Floren AC-901 and AC-
950, AC-1140, AO-3, AO-4OH (all manufactured by Kyoeisha Yushi Co., Ltd.), FS1265, SH20
0, SH5500, SC5540, SC5570, F-
1. Silicon antifoaming agents such as SD5590 (all manufactured by Dow Corning Toray Silicone Co., Ltd.), Megafac F-142D, F-144D, F-178K, F-17
9, F-815 (above, Dainippon Ink and Chemicals, Inc.)
And other fluorine atom-containing defoamers.

As the leveling agent, polyflow No.
7, no. 38, no. 50E, S, 75, No. 7
5, no. 77, No. 90, no. 95, no. 30
0, No. 460, ATF, KL-245 (all manufactured by Kyoeisha Yushi Co., Ltd.) and the like. The amounts of these additives used can be determined as necessary within a range that does not impair the purpose of the composition of the present invention.

The composition of the present invention can be cured by irradiation with ultraviolet light, visible light, electron beam, or the like, as in the case of ordinary photocurable resin compositions. For example, the composition of the present invention is filled between the adherends so that the thickness of the adhesive layer becomes 10 to 100 μm, and 50 to 500
Irradiation at 0 mJ / cm ² easily cures and allows the adherends to adhere to each other.

The composition of the present invention can be used for bonding thermoplastic resin,
For example, it has excellent adhesiveness between the electronic and optical parts made of thermoplastic resin, especially CCD lid made of transparent thermoplastic resin and CCD chip, and excellent durability of adhesive force against temperature change. And is suitable as a photocurable adhesive.

[0065]

[Synthesis of Urethane Acrylate as Component (A)]

Synthesis Example 1 In a 1-liter separable flask equipped with a stirrer and a thermometer, 209 g of isophorone diisocyanate, 3,5
-Di-t-butyl-4-hydroxytoluene in 0.2
g, 0.8 g of di-n-butyltin dilaurate, stirred and cooled to 10 ° C. in a cold water bath under a dry air atmosphere, and then 109 g of 2-hydroxyethyl acrylate so that the contents were maintained at 10 to 35 ° C. Was added little by little over 1 hour to react. Thereafter, the hydroxyl value is 109.7 mgK.
OH / g polytetramethylene glycol (trade name: P
480 g of TMG1000, manufactured by Mitsubishi Chemical Corporation)
Stirring was continued at 40 to 60 ° C. for 5 hours to cause a reaction. Thereafter, the reaction product was taken out to obtain a urethane acrylate (A1) having a number average molecular weight of 1650.

Synthesis Example 2 Polyester diol having a hydroxyl value of 111.7 mgKOH / g (trade name: Kurapol P1010, manufactured by Kuraray Co., Ltd.) instead of polytetramethylene glycol of Synthesis Example 1
The same operation as in Synthesis Example 1 was performed except that 472 g was used, and a urethane acrylate having a number average molecular weight of 1530 (A
2) was obtained.

Synthesis Example 3 Polyether polyol having a hydroxyl value of 55.2 mg KOH / g (trade name: PTGL2000, Hodogaya Chemical Industry Co., Ltd.) was used in place of the polytetramethylene glycol of Synthesis Example 1.
The same operation as in Synthesis Example 1 was carried out, except that 956 g of the product was used, to obtain a urethane acrylate (A3) having a number average molecular weight of 2570.

Examples and Comparative Examples <Preparation of Photocurable Resin Composition> Each component having the composition shown in Table 1 was added to a reaction vessel equipped with a stirrer, followed by stirring and mixing. , And Comparative Examples 1 to 3 were prepared. Each component in Table 1 is as follows. (B)
Component B1 Isobornyl acrylate (commercial product: IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) B2 Phenoxyethyl acrylate (commercial product: Biscoat 192, manufactured by Osaka Organic Chemical Industry Co., Ltd.) B3 Nonylphenol EO-modified acrylate (commercial product: (Aronix M111, manufactured by Toagosei Co., Ltd.) B4 Hydroxypivalate neopentyl glycol diacrylate (commercially available: KAYARD MANDA, manufactured by Nippon Kayaku Co., Ltd.) (C) Component C1, 2,2-dimethoxy-1,2 -Diphenylethane-1-one (commercial product: Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) C2 2-hydroxy-2-methyl-1-phenyl-propan-1-one (commercial product: Darocur 1173, Ciba Special T-Chemicals Co., Ltd.) C3 1-Hydroxycyclohexylphenyl ketone (commercial product: Irga cure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) (D) Component D1 polytetramethylene glycol (trade name: PTMG1000, manufactured by Mitsubishi Chemical Co., Ltd.) D2 polytetra Methylene glycol (trade name: PTGL2000, manufactured by Hodogaya Chemical Industry Co., Ltd.) Next, the composition prepared as described above (Examples 1 to 3)
3 and Comparative Examples 1 to 3), the wet heat resistance and the durability of the adhesive force to temperature change of each composition were evaluated as follows.

(1) Moisture / heat resistance test Transparent thermoplastic resin (norbornene resin, ARTON F
(Manufactured by JSR Corporation)]
× 38.5mm × 0.8mm) and CCD chip (7.7mm ×
39.2 mm) and applied with a dispenser so that the coating thickness becomes about 30 μm, and the light amount is 30
A light of 00 mJ / cm ² was irradiated with a metal halide lamp to bond. After that, temperature 85 ° C, relative humidity 85% RH
When left in the constant temperature and humidity chamber for 48 hours and 96 hours,
When peeling between the CCD lid and the CCD chip was observed, the sample was judged to be poor in heat and humidity resistance, and was indicated by x in Table 1. Further, when no peeling was observed, the sample was judged to be excellent in wet heat resistance, and was indicated by a circle in Table 1.

(2) Durability test of adhesive strength against temperature change The CCD lid and the CCD chip were bonded in the same manner as in the wet heat resistance test. Using a thermal cycle tester [Tavaispec Co., Ltd., thermal shock tester TSV-40], -40
10 minutes after standing at 125 ° C for 25 minutes
Repeated 0 times. At this time, the case where peeling between the CCD lid and the CCD chip was observed was judged to be poor in the durability of the adhesive force with respect to the temperature change, and was indicated by x in Table 1. Further, when no peeling was observed, it was judged that the durability of the adhesive force against the temperature change was good, and the result was indicated by ○ in Table 1.

Table 1 shows the results of the above evaluations of the examples and comparative examples. From these results, all of Examples 1, 2, and 3 have good wet heat resistance and good durability of adhesive strength against temperature change, while Comparative Examples 1, 2, and 3 have good wet heat resistance and good adhesive strength against temperature change. Was poor in durability.

[0073]

[Table 1]

[0074]

As described above, the photocurable adhesive of the present invention comprises a CCD lid made of a transparent thermoplastic resin and a C lid.
Since it has excellent durability when used for bonding CD chips, it has a CCD lid made of transparent thermoplastic resin and a CC lid.
It is extremely useful in bonding D chips as compared with conventional adhesives.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hitomi Nomiyama 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (72) Inventor Takayoshi Tanabe 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Inside (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd.F-term (reference) 4J011 QA03 QA13 QA23 QA24 QB16 QB24 SA01 SA04 SA05 SA06 SA21 SA24 SA25 SA27 SA34 SA36 SA53 SA54 SA61 SA62 SA63 SA64 SA75 SA82 TA04 UA01 VA01 WA01 WA06 4J027 AC03 AC04 AG02 AG03 AG04 AG09 AG23 AG24 AG27 AJ08 BA01 BA02 BA07 BA08 BA10 BA12 BA13 BA16 BA19 BA20 BA26 BA28 CA06 CA10 CB10 CD09 4J040 FA011 FA012 FA291 HB02 KA01

Claims (3)

[Claims] (A) a urethane (meth) acrylate obtained by reacting a polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, and (B) one molecule other than the component (A) in one molecule. Meta)
A photocurable resin composition containing a (meth) acrylate compound having at least one acryloyl group, (C) a photopolymerization initiator, and (D) a polyol compound. 2. The photocurable resin composition according to claim 1, which is used for bonding a thermoplastic resin. 3. The method according to claim 1, which is used for bonding a CCD lid made of a transparent thermoplastic resin and a CCD chip.
The photocurable resin composition according to the above.