JPH08311130A - Photocurable resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition containing a specific resin, a specific diacrylate and a specific photopolymerization initiator as essential components, excellent in flexibility, heat resistance and alkali resistance, and useful in an electronic material field. CONSTITUTION: A photocurable resin composition contains (A) a vinylester resin of formula I (R<1> is H, methyl; R<2> is a divalent organic group; n is 0, 1) (e.g. a resin of formula II), (B) a tricyclodecanedimethylol diacrylate of formula III (R<3> is H, methyl) (e.g. a compound of formula IV), and (C) a photopolymrization initiator (e.g. biacetylacetophenone) as essential components. The components A, B and C are preferably used in amounts of 95-5 pts.wt., 5-95 pts.wt., and 3-15 pts.wt. (based on 100 pts.wt. of the total amount of the components A and B), respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photocurable resin composition having excellent flexibility, water resistance and alkali resistance.

[0002]

2. Description of the Related Art In recent years, demands for energy saving, high productivity, and no pollution have increased, and attention has been paid to a process of curing a resin by light. On the other hand, applications using the photocurable resin composition are not only used as paints, inks, and adhesives for conventional plastics, paper, wood, inorganic materials, etc., but also semiconductors, electronic material fields represented by liquid crystals, and optical fibers, It has been further expanded to the field of optoelectronics represented by optical lenses and the like, as well as the medical field.

[0003]

However, since the photocurable resin composition generally has a high crosslink density, it is poor in flexibility, and because of the nature of the coating film, it has to be applied to a substrate, Since it contains a certain functional group, it was inferior in water resistance and alkali resistance. In order to improve this, attempts have been made to impart flexibility by using a photopolymerizable component of a long-chain unsaturated compound system, but in recent years due to expansion of applications, etc., there is a demand for water resistance and alkali resistance. Was not happy.

The present invention has been made in view of the above circumstances and drawbacks, and an object thereof is to provide a photocurable resin composition excellent in flexibility, water resistance and alkali resistance.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that the resin composition described below can achieve the above object and completed the present invention. Is.

That is, the present invention provides (A) a vinyl ester resin represented by the following general formula,

[0007]

Embedded image (However, in the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is 2
A valent organic group, n is an integer of 0 or 1 respectively) (B) tricyclodecane dimethylol diacrylate represented by the following general formula and

[0008]

[Chemical 4]

(In the formula, R ³ represents a hydrogen atom or a methyl group.) (C) A photocurable resin composition comprising a photopolymerization initiator as an essential component.

Hereinafter, the present invention will be described in detail.

As the vinyl ester resin (A) used in the present invention, those represented by the above general formula 3 can be used. R ² of this vinyl ester resin has 1 to 18 carbon atoms, preferably 2 to 12 carbon atoms. Specific examples of the vinyl ester resin include, for example,

[0012]

Embedded image

[0013]

[Chemical 6]

[0014]

[Chemical 7] Etc., and these can be used alone or in combination.

As the (B) tricyclodecane dimethylol diacrylate used in the present invention, the one represented by the above chemical formula 4 can be used. As a specific example of this tricyclodecane dimethylol diacrylate,
For example,

[0016]

Embedded image

[0017]

[Chemical 9] Etc., and these can be used alone or in combination. The mixing ratio is preferably 5 to 95 parts by weight with respect to 95 to 5 parts by weight of the vinyl ester resin (A). If the content is less than 5 parts by weight, the viscosity of the photocurable composition is high and the coating property is poor, and if it exceeds 95 parts by weight, the effect of improving the water resistance due to the use of the component (A) is small and not preferable. . In addition to this tricyclodecane dimethylol diacrylate, other photopolymerizable monomers, for example,
Isobornyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate , Trimethylolpropane trimethacrylate,
Trimethylol ethane trimethacrylate, tetramethylol methane tetraacrylate, etc. may be appropriately added within the range of 5 to 95 parts by weight.

Examples of the (C) photopolymerization initiator used in the present invention include biacetylacetophenone, benzophenone, benzyl, benzoyl isobutyl ether, benzyl dimethyl ketal, (1-hydroxycyclohexyl).
Phenyl ketone, (1-hydroxy-1-methylethyl) phenyl ketone, p-isopropyl-α-hydroxyisopropylphenone, diethylthioxanthone, ethylanthraquinone, bis (diethylamino) benzophenone, and the like, which may be used alone or in combination. Can be used. The mixing ratio of this photopolymerization initiator is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the resin component [(A) + (B)]. If the amount is less than 1 part by weight, the photocurability is not improved, and if it exceeds 20 parts by weight, the adhesion is poor and the moisture resistance is not preferable. In addition to the photopolymerization initiator, a photosensitizer can be appropriately used in combination.
In this case, 1 to 20 parts by weight of the photopolymerization initiator for each
It is desirable to use 1 to 5 parts by weight.

The photocurable resin composition of the present invention comprises (A) a vinyl ester resin, (B) tricyclodecane dimethylol diacrylate and (C) a photopolymerization initiator as essential components, but for the purpose of the present invention. In the range that does not conflict,
If necessary, a thermal polymerization inhibitor, a surfactant, an adhesive, a thixotropic agent, a filler, a pigment and the like can be added and blended.

The photocurable resin composition of the present invention is produced by mixing (A) vinyl ester resin, (B) tricyclodecane dimethanol diacrylate, (C) photopolymerization initiator and other compounds and dissolving them. can do. The photocurable resin composition thus produced can be used for various purposes.

[0021]

The photocurable resin composition of the present invention provides a coating film excellent in flexibility, water resistance and alkali resistance by using a specific vinyl ester resin and a specific tricyclodecane dimethylol diacrylate. We were able to.

[0022]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, "part" means "part by weight".

Examples 1 to 2 Based on the composition ratios shown in Table 1, vinyl ester resin, tricyclodecane dimethylol diacrylate,
A photopolymerization initiator and others were mixed and dissolved to produce a photocurable resin composition.

Comparative Examples 1 to 3 Compounds were prepared based on the compositional composition ratios shown in Table 1, mixed and dissolved to prepare photocurable resin compositions.

The photocurable resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were coated on an iron substrate treated with # 400 sandpaper to a film thickness of 30 to 35 μm and 2 kW (80 W).
/ Cm ² ) A high pressure mercury lamp was used for irradiation for 15 seconds at an irradiation distance of 15 cm to obtain a coating film. The coating film was tested for flexibility, water resistance and alkali resistance, and the results are shown in Table 1. The photocurable resin composition of the present invention was excellent in various properties, and the effects of the present invention could be confirmed.

[0026]

[Table 1] * 1: Evaluation was made after immersion in tap water at 25 ° C for 10 days. ○ mark: good, × mark: bad * 2: Evaluation was made after immersion in 3% NaOH aqueous solution at 25 ° C for 12 hours. ○ mark: good, × mark: bad.

[0027]

As is clear from the above description and Table 1, the photocurable resin composition of the present invention is excellent in flexibility, water resistance and alkali resistance, and is excellent in the fields of electronic materials, optoelectronics, etc. It can be used in a wide range of fields.

Claims (1)

[Claims] 1. A vinyl ester resin represented by the following general formula: (However, in the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is 2
A valent organic group, n is an integer of 0 or 1 respectively) (B) Tricyclodecane dimethylol diacrylate represented by the following general formula and (However, in the formula, R ³ represents a hydrogen atom or a methyl group.) (C) A photocurable resin composition comprising a photopolymerization initiator as an essential component.