JPS59226013A - Uv-curable resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent moist heat resistance and high adhesivity to a UV-transmitting material, by compounding a specific (meth)acrylic component with specific amounts of gamma-glycidoxypropyl trimethoxysilane and a photopolymerization initiator. CONSTITUTION:100pts.wt. of a (meth)acrylic component composed of 40- 90pts.wt. of an epoxy (meth)acrylate (preferably having a molecular weight of 300-1,500) and 60-10pts.wt. of a (meth)acrylate monomer [e.g. benzyl (meth) acrylate] is compounded with 1-8pts.wt. of gamma-glycidoxypropyl trimethoxysilane and 1-10pts.wt. of a photopolymerization initiator (e.g. benzoin isobutyl ether). USE:Bonding of materials at least one of which is transparent to UV light, e.g. glass/glass, glass/metal, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ultraviolet curable resin composition, and more specifically, it has excellent adhesion to materials such as glass to glass, glass to metal, plastics to each other, and which has at least one surface that is transparent to ultraviolet light. The present invention relates to an ultraviolet curable resin composition having heat and humidity resistance.

Various acrylates and methacrylates are conventionally known as compounds that have the property of being polymerized in a short time when irradiated with ultraviolet rays in the presence of a photopolymerization initiator. These ultraviolet curable resins containing various acrylates and methacrylates as main components have the advantage that they can be bonded in a shorter time than conventional bonding methods when bonding ultraviolet transmitting materials such as glass. For this reason, ultraviolet curable resins are commonly used for adhering materials that have an ultraviolet transmitting material on at least one side, such as glass to glass or glass and different materials. However, when this ultraviolet curing resin is used to bond glass, etc., the initial bond has sufficient strength, but
One drawback is that the adhesive strength decreases under conditions such as moist heat, water, and hot water.

The present invention provides bonding of materials having an ultraviolet transmitting material on at least one side, such as glass/glass, glass/metal, etc.
An object of the present invention is to provide an ultraviolet curable resin composition that has good adhesion to materials and does not deteriorate its adhesive strength over time due to moist heat, water, or hot water.

This object of the present invention is achieved by incorporating a specific amount of γ-glycidoxyprobyltrimethoxysilane into a composition containing an acrylic and/or methacrylic component and a photopolymerization initiator.

That is, the present invention uses 40 to 90 parts by weight of epoxy acrylate and/or epoxy methacrylate, and 60 to 10 parts by weight of acrylic monomer and/or methacrylic monomer.
1 to 8 parts by weight of γ-glycidoxypropyltrimethoxysilane and 1 to 10 parts by weight of a photopolymerization initiator are blended into 100 parts by weight of the components consisting of parts by weight. .

Epoxy acrylate and/or used in the present invention
or epoxy methacrylate (hereinafter referred to as epoxy (meth)acrylate (Xu) (, t, molecular weight is 300 to 1
500 range is preferred). If the molecular weight is less than 300, the adhesive force with the adhesive material will decrease, and if the molecular weight exceeds 1,500, the viscosity of the composition will become high, making it difficult to use. The epoxy (meth)acrylate in the present invention is blended in a ratio of 40 to 90 parts by weight in 100 parts by weight of acrylic and/or methacrylic component (hereinafter referred to as (meth)acrylic component (1)). If it is less than 40 parts by weight, the adhesion to adhesive materials such as glass and moisture and heat resistance over time will decrease, and if it exceeds 90 parts by weight, the viscosity of the composition will become high and it will be difficult to use. ) Acrylate is a reaction product obtained by reacting various epoxy resins with various acrylic monomers and/or methacrylic monomers (hereinafter referred to as (meth)acrylic monomers).

The (meth)acrylic monomers used in the present invention are known ones, such as benzyl (meth)acrylate trimethylolpropane tri(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate. , g, etc. are exemplified. The (meth)acrylic monomer is blended in an amount of 60 to 10 parts by weight per 100 parts by weight of the (meth)acrylic component.

The amount of γ-glycidoxyprobyl trime 1 to xysilane used in the present invention is 1 to 1 to 10 parts by weight per 10 Qlum parts of the (meth)acrylic component and the (meth)acrylic monomer.
If the amount is less than 1 layer, the moisture and heat resistance over time will be low, and if it exceeds 8 layers, the heat and moisture resistance over time will be at a high level, but the heat resistance will decrease significantly, which is not preferable. .

In the present invention, the photopolymerization initiator is blended in an amount of 1 to 10 parts by weight based on the (meth)acrylic component. If the amount is less than 1 part by weight, desired curing will not occur, and if it exceeds 10 parts by weight, the curing rate will not increase significantly. Examples of the photopolymerization initiator used include benzoin isobutyl needle, benzoin ethyl ether, benzyl dimethyl ketal, benzophenone benzyl, 2,2-jethoxyacetophenone, and diethylthioxanthone.

Furthermore, in the present invention, in addition to the above-mentioned essential components,
Furthermore, to accelerate the reaction, a polymerization accelerator is added, up to 5 parts by weight per 100 parts by weight of the (meth)acrylic component, and a thermal polymerization inhibitor is added to improve thermal stability or storage stability.
They may be added in an amount of 5 parts by weight or less per 100 parts by weight of the acrylic component.

As the polymerization accelerator, metal soaps such as cobalt naphthenate and tertiary amines such as 2-dimethylaminoethanol, N,N-dimethylaniline, and p-dimethylaminobenzoic acid are used.

Further, as the thermal polymerization inhibitor, hydroquinone, p-benzoquinone, [-butylhydroquinone, etc.] are used.

Hereinafter, the present invention will be specifically explained based on Examples and Comparative Examples.

Applications 1 to 2 and Ratios 1 to 6 Compositions were prepared using the ingredients and blending amounts shown in Table 1 by thoroughly stirring until uniform. This composite acid product was sandwiched between two covering bodies, and the tensile shear strength at 23° C. after curing the composition was measured. Further, after curing, the tensile shear strength retention rate (%) after being left for two weeks at a temperature of 50° C. and a relative humidity of 95% was evaluated.

The results are shown in Table 1. Note that the aging object has a thickness of 5. Adhesion was performed using On+i glass and a steel plate with a thickness of 1.6 mm, with an adhesion area of 5×2511111. The composition was cured by irradiating it for 3 minutes at a distance of 20C1l using an 80w/cw metal halide lamp. Furthermore, the tensile speed trace in the measurement of tensile shear strength was set at 11 m 2 /min.

As shown in Table 1, Examples 1 and 2 in which γ-glycidoxypropyltrimethoxysilane was blended had a higher tensile strength than Comparative Examples 1 and 2 in which γ-glycidoxypropyltrimethoxysilane was not blended. Extremely high shear strength. Also,
Comparative Examples 3 to 6 using A riboester acrylate and urethane acrylate as part of the acrylate component,
The tensile shear strength is significantly inferior to that of Examples 1 and 2 in which epoxy acrylate was used as part of the Acrylay-I component. This shows that a composition containing epoxy acrylate as part of the acrylate component and containing γ-glycidoxypropyltrimethoxysilane has excellent moisture and heat resistance over time.

~East 3-8 and 7-8 Each composition was prepared using the ingredients and formulation m shown in Table 2,
The composition was placed between adherends and cured. 2 after curing
Tensile shear strength at 3°C and 100°C (kg/cd
) and tension under conditions of temperature 50°C and relative humidity 95%!
¥[i strength l0 (k (1/cd)) was measured and the results are shown in Figure 1 and Table 2. The adherend, adhesive area, curing conditions, and tensile speed were the same as in Example 1. And so.

Table 2 *7: Kyoeisha oils and fats (manufactured by Kikisha, (trade name) Epoxy Ester 3002M As shown in Table 2 and Figure 1, γ
- As the blending amount of glycidoxypropyl 1 to rimethoxysilane increases, the tensile shear strength at 100°C decreases, but the tensile strength under conditions of a temperature of 50°C and a relative humidity of 95% increases. From this, when considering both heat resistance and moist heat resistance over time, it is preferable that the amount of γ-glycidoxypropyltrimethoxysilane to be blended is about 1 to 8 parts by weight per 100 parts by weight of the (meth)acrylic component. I understand.

Example 8 and Comparative Examples 9 to 13 Compositions were prepared using the ingredients and amounts shown in Table 3,
The cured composition was sandwiched between adherends and cured. temperature 5
Tensile shear strength retention under conditions of 0°C and 95% relative humidity (
%) and storage stability at 23°C (normal temperature) were measured and the results are shown in Table 3. In addition, the adherend, adhesive area, curing conditions,
The tensile speed was the same as in Example 1.

In Table 6 and Table 3, the types of silane compounds were changed, and Comparative Examples 10 and 11, in which vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane were blended, were those in which no silane compound was blended. Comparative Example 1, which contained β-3,4 epoxycyclohexylethyltrimethoxysilane, was inferior to Comparative Example 9 in tensile shear strength after being left for two weeks at a temperature of 50°C and a relative humidity of 95%.
Sample No. 3 shows only the same tensile shear strength as Comparative Example 9. Furthermore, in Comparative Example 12 in which γ-mercaptopropyl trime-1 hexysilane was blended, although the tensile shear strength was slightly improved compared to Comparative Example 9, it gelled after one day and was inferior in storage stability. On the other hand, Example 8 in which γ-glycidoxypropyltrimethoxysilane was blended showed a significantly high tensile shear strength and excellent storage stability. From this, it can be seen that among the silane compounds, only the composition containing γ-glycidoxypropyltrimethoxysilane is excellent in heat-and-moisture resistance and storage stability over time.

As explained above, epoxy (meth)acrylate,
The ultraviolet curable resin composition of the present invention, which contains a (meth)acrylic monomer, a photopolymerization initiator, and γ-glycidoxypropyltrimethoxysilane in a specific ratio, not only exhibits high adhesion to adhesive materials, but also Because it has excellent moisture and heat resistance, heat resistance, and storage stability, it is suitable for adhering materials that have UV transmittance on at least one side, especially for adhering glass to glass, dissimilar materials such as glass and metal, and plastics. It is suitably used as an adhesive.

[Brief explanation of drawings]

Figure 1 shows the blending amount (heavy part) of γ-glycidoxypropyltrimethoxysilane and the tensile shear strength (kg/cnf
) is a graph showing the relationship between Patent Applicant Yokohama Rubber Co., Ltd. Agent Patent Attorney Tatsuo Ito Patent Attorney Tetsuya Ito

Claims (1)

[Claims] ■Phoxy acrylate and/or epoxy methacrylate 1 to 40 to 90 parts, acrylic 7-summer and/
Alternatively, 100 parts by weight of a component consisting of 60 to 10 type openings of methacrylic monomer are added to γ-glycidoxyprobyl!・21 to 8 parts by weight of dimethoxysila and 1 to 10 parts by weight of photopolymerization initiator
An ultraviolet curable resin composition characterized by containing parts by weight.