JPH1180314A - Photosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosetting resin composition curable even in a thick form using light having longer wavelength compared with conventional resin composition and giving a cured product having excellent adhesivity by including an epoxy resin, a specific silicon compound and an onium salt. SOLUTION: This composition contains (A) an epoxy resin (bisphenol A epoxy resin, etc.), (B) a silicon compound having Si-Si bond [containing the recurring unit expressed by the formula I (R is H, an alkyl or an aryl), e.g. a polysilane expressed by the formula II ((n) is >=10)] and (C) an onium salt selected from sulfonium salts expressed by the formula III, iodonium salts expressed by the formula IV and diazonium salts expressed by the formula Ar-N2 <+> X<-> (Ar is an alkyl or an ary; X is a component exhibiting acidity by photodecomposition and is a halide or sulfolate of B, P, Sb or As).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photocurable resin composition.

[0002]

2. Description of the Related Art In recent years, there has been an interest in photocurable resin compositions because of their excellent energy saving and workability. Conventionally, a photocurable resin composition containing an acrylic resin has been generally used. However, acrylic resins have a problem that heat resistance and moisture resistance are not sufficient.

For this reason, photocurable resin compositions containing epoxy resins having excellent heat resistance, mechanical properties and moisture resistance have been studied. In this case, since the epoxy resin itself does not cause a photoreaction, the following method is used to provide photocurability.

(1) An epoxy resin is modified with a photofunctional group such as an acrylic group. However, when the epoxy resin is modified, there is a disadvantage that the original performance of the epoxy resin is lost.

(2) An onium salt (for example, a sulfonium salt, an iodonium salt or a diazonium salt) which generates an acid by photolysis is added to an epoxy resin. But,
These onium salts have an absorption below 300 nm and cannot effectively absorb the strongest light of 365 nm among the bright lines of a mercury lamp usually used as a light source. The onium salt can be decomposed by 254 nm light, but the absorption derived from the benzene ring of the epoxy resin itself is also 300 nm.
Due to the following, it is difficult to effectively decompose the onium salt added to the epoxy resin. Furthermore, even when such an epoxy resin composition is used for bonding a transparent substrate, it is difficult to obtain sufficient adhesive strength by photocuring because the transparent substrate itself often has an absorption of 300 nm or less. It is. It has been reported that aromatic compounds such as anthracene and perylene act as sensitizers, but the effect of promoting photodecomposition of onium salts is insufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photocurable resin composition which can be photocured even with a thick film using light having a longer wavelength than conventional ones, and which gives a cured product having excellent adhesion. To provide things.

[0007]

The photocurable resin composition of the present invention comprises (a) an epoxy resin, (b) a silicon compound having a Si--Si bond, and (c) an onium salt. .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The epoxy resin that is the main component (component (a)) of the photocurable resin composition of the present invention is not particularly limited. For example,
Bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin,
Alicyclic epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanate and hydantoin epoxy,
Hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin such as propylene glycol-diglycidyl ether and pentaerythritol-polyglycidyl ether, epoxy obtained by reacting aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin Resin, a spiro ring-containing epoxy resin, a diglycidyl ether type epoxy resin which is a reaction product of an ortho-allylphenol novolak compound and epichlorohydrin, a diallyl bisphenol compound having an allyl group at the ortho position of each hydroxyl group of bisphenol A and epichlorohydrin, and A glycidyl ether type epoxy resin which is a reaction product of the above can be used.

In the present invention, the component (b) Si—Si
Examples of the silicon compound having a bond include a polysilane having a repeating unit represented by the following general formula (I).

[0010]

Embedded image (However, R represents hydrogen or a substituted or unsubstituted alkyl group or aryl group, which may be the same or different. The alkyl group or aryl group may contain an element such as oxygen, nitrogen, sulfur, and halogen. .) Specific examples of the polysilane contained in the general formula (I) are shown below. Note that n and m in each chemical formula are integers of 10 or more. However, if n + m exceeds 10,000, the solubility deteriorates. Therefore, n + m is preferably 10,000 or less.

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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In the present invention, the onium salt of the component (c) is a sulfonium salt represented by the following general formula (IIA):
It is selected from the group consisting of an iodonium salt represented by (IIB) and a diazonium salt represented by (IIC).

[0017]

Embedded image (However, Ar represents a substituted or unsubstituted alkyl group or aryl group, which may be the same or different. The alkyl group or the aryl group may contain an element such as oxygen, nitrogen, sulfur, and halogen. X Is a component showing acidity by photolysis, and represents a halide or sulfolate of B, P, Sb or As.) Specific examples of onium salts are shown below.

[0018]

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[0019]

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[0020]

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[0021]

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The components contained in the photocurable resin composition of the present invention have the following effects. The silicon compound (b) absorbs at 300 to 400 nm, and effectively absorbs and excites the strongest light of 365 nm among the emission lines of a mercury lamp. The excited silicon compound accelerates the decomposition of the onium salt of the component (c) by photoexcited electron transfer. The acid generated by the decomposition of the onium salt acts as a curing catalyst for the epoxy resin. Therefore, the photocurable resin composition of the present invention can be photocured even with a thick film using light having a longer wavelength than before. In addition, the cured product obtained by light curing has excellent mechanical properties. Incidentally, the resin composition of the present invention may be cured by heating after photocuring.

The silicon compound (b) is preferably used in an amount of 0.001 to 50 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the epoxy resin. 0.
If the amount is less than 001 parts by weight, photocuring of the epoxy resin becomes insufficient. If the amount exceeds 50 parts by weight, there arises a problem that the mechanical strength of the cured product decreases.

The onium salt of the component (c) is an epoxy resin 1
It is preferably used in the range of 0.001 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, based on 00 parts by weight. 0.
If the amount is less than 001 parts by weight, photocuring of the epoxy resin becomes insufficient. If the amount exceeds 20 parts by weight, problems such as a decrease in mechanical strength and coloring of the cured product occur.

The photocurable resin composition of the present invention may contain other organic components for improving properties. Also,
Depending on the purpose, a compound having a cationic polymerizable substituent such as lactone, cyclic imine, or cyclic imide, or a compound having a polymerizable unsaturated group such as acryl, methacryl, or vinyl group may be added. Further, the photocurable resin composition may be used by being mixed with an inorganic filler such as silica.

[0026]

【Example】

Example 1 100 parts by weight of Epicoat 828 (Epibis type epoxy resin manufactured by Shell Chemical Co., Ltd.), polysilane [1-34] 3
A resin composition was prepared by mixing parts by weight and 2 parts by weight of a sulfonium salt [2-3], and this was coated on a glass substrate by a bar coater to form a 200 μm thick film. A high-pressure mercury lamp of 500 W was set at a position 5 cm above the film, and the film was cured by irradiating ultraviolet rays. In this case, a cured film could be obtained in 30 seconds.

Further, borosilicate crown glass BK7
(Manufactured by Shot Co., Ltd.) and applying the above resin composition
It was sandwiched between another borosilicate crown glass via a 00 μm spacer. UV light from a high-pressure mercury lamp
Irradiated for minutes. As a result, the two glasses could be bonded with a sufficient bonding strength.

Comparative Example 1 100 parts by weight of Epikote 828 (Epibis type epoxy resin manufactured by Shell Chemical Co., Ltd.) and a sulfonium salt [2
-3] 2 parts by weight were mixed to prepare a resin composition, which was applied on a glass substrate with a bar coater to form a 200 μm thick film. A high-pressure mercury lamp of 500 W was set at a position 5 cm above the film, and the film was cured by irradiating ultraviolet rays. In this case, it took 180 seconds to obtain a cured film.

In addition, borosilicate crown glass BK7
(Manufactured by Shot Co., Ltd.) and applying the above resin composition
It was sandwiched between another borosilicate crown glass via a 00 μm spacer. UV light from a high-pressure mercury lamp
Irradiation was performed for 0 minutes, but the adhesion was insufficient and the two glasses were easily peeled off.

Example 2 100 parts by weight of Epicoat 828 (Epibis type epoxy resin manufactured by Shell Chemical Co., Ltd.), polysilane [1-30] 4
A resin composition was prepared by mixing parts by weight and 3 parts by weight of a sulfonium salt [2-23], and this was coated on a glass substrate by a bar coater to form a film having a thickness of 200 μm. A high-pressure mercury lamp of 500 W was set at a position 5 cm above the film, and the film was cured by irradiating ultraviolet rays. In this case, 30
A cured film could be obtained in seconds.

Example 3 100 parts by weight of Epicoat 828 (Epibis type epoxy resin manufactured by Shell Chemical Co., Ltd.) and polysilane [1-30] 4
A resin composition was prepared by mixing parts by weight and 2 parts by weight of an iodonium salt [2-29], and this was coated on a glass substrate with a bar coater to form a 200 μm thick film. A high-pressure mercury lamp of 500 W was set at a position 5 cm above the film, and the film was cured by irradiating ultraviolet rays. In this case, 20
A cured film could be obtained in seconds. Further, the cured film was cured by heating at 100 ° C. for 10 minutes. The measured surface hardness was 5H.

The above resin composition was applied on a glass substrate with a bar coater to form a film having a thickness of 200 μm.
Selective nitrogen laser light (50 mW,
334 nm) for photocuring. In this case, a cured film could be obtained in 30 seconds. When this was washed away with ethanol, only the exposed portions remained, and patterning was possible.

Example 4 Resin was prepared by mixing 100 parts by weight of celloxide 2021 (manufactured by Daicel Chemical Industries, alicyclic epoxy resin), 3 parts by weight of polysilane [1-34], and 2 parts by weight of sulfonium salt [2-3]. A composition was prepared and applied to a glass substrate with a bar coater to form a film having a thickness of 100 μm. A high-pressure mercury lamp of 500 W was set at a position 5 cm above the film, and the film was cured by irradiating ultraviolet rays. In this case, a cured film could be obtained in 10 seconds.

Example 5 100 parts by weight of Epicoat 828 (Epibis type epoxy resin manufactured by Shell Chemical Co., Ltd.) and polysilane [1-35] 4
A resin composition was prepared by mixing parts by weight and 2 parts by weight of a sulfonium salt [2-24], and this was coated on a glass substrate by a bar coater to form a film having a thickness of 200 μm. A high-pressure mercury lamp of 500 W was set at a position 5 cm above the film, and the film was cured by irradiating ultraviolet rays. In this case, 20
A cured film could be obtained in seconds.

Example 6 Epicoat 828 (Epibis type epoxy resin manufactured by Shell Chemical Co., Ltd.) 100 parts by weight of epibis type epoxy resin (Epicoat 828 manufactured by Shell Chemical Co., Ltd.), 4 parts by weight of polysilane [1-30], and iodonium Salt [2-3
5] A resin composition was prepared by mixing 2 parts by weight, and this was applied on a glass substrate with a bar coater to form a 200 μm thick film. A high-pressure mercury lamp of 500 W was set at a position 5 cm above the film, and the film was cured by irradiating ultraviolet rays.
In this case, a cured film could be obtained in 20 seconds.

Example 7 A resin was prepared by mixing 100 parts by weight of celloxide 2021 (manufactured by Daicel Chemical Industries, alicyclic epoxy resin), 3 parts by weight of polysilane [1-34], and 2 parts by weight of sulfonium salt [2-12]. A composition was prepared and applied to a glass substrate with a bar coater to form a film having a thickness of 100 μm. A high-pressure mercury lamp of 500 W was set at a position 5 cm above the film, and the film was cured by irradiating ultraviolet rays. In this case, a cured film could be obtained in 30 seconds.

Example 8 70 parts by weight of Epikote 828 (Epibis type epoxy resin manufactured by Shell Chemical Co., Ltd.), 30 parts by weight of Epicoat 1001 (Epibis type epoxy resin manufactured by Shell Chemical Co., Ltd.)
A resin composition was prepared by mixing 4 parts by weight of polysilane [1-30] and 2 parts by weight of iodonium salt [2-29], and the resin composition was applied on borosilicate crown glass BK7 (manufactured by Schott) and 100 μm in thickness. And another borosilicate crown glass. This was irradiated with ultraviolet light from a high-pressure mercury lamp for 1 minute to photo-cur, and
It was cured by heating at 00 ° C for 30 minutes. As a result, the two glasses could be bonded with a sufficient bonding strength. The cured product did not have cracks due to shrinkage and was excellent in transparency.

[0038]

As described in detail above, the photocurable resin composition of the present invention can be photocured even in a thick film using light having a longer wavelength than in the past, and has a superior adhesive property. Is obtained.

Claims (1)

[Claims] 1. An epoxy resin, (b) Si-Si
A photocurable resin composition comprising a silicon compound having a bond and (c) an onium salt.