JPS63283918A - Integrally molded product of glass/resin - Google Patents

Abstract

PURPOSE:To improve adhesion strength (peel strength), by a method wherein an adhesive agent layer is formed of an adhesive agent obtained by adding silane coupling agent mainly composed of polyamide containing tertiary amine within a main chain and containing an epoxy group, in a molded product which has been integrated through a glass part and adhesive agent layer. CONSTITUTION:An adhesive agent layer is formed of an adhesive agent obtained by adding silane coupling agent mainly composed of polyamide possessing tertiary amine within a main chain and containing an epoxy group, in a molded product composed of a glass part and a synthetic resin part coating the glass part partly and integrated through the glass part and adhesive agent layer at the time of injection molding. Hydrogen of amide bond in nylon 6/66/8/12/11/612/610 and copolymer of those are replaced with an alkoxymethyl group such as metchoxy/ethoxy/butoxy methyl group as the polyamide containing the tertiary amine. Although an addition quantity of the silane coupling agent varies according to kinds of the polyamide and silane coupling agent, normally it is decided to be 1-40 pts. wt. polyamide per 100 pts. wt. of silane coupling agent.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention consists of a glass part and a synthetic resin part that partially covers the glass part, the synthetic resin part is formed by injection molding, and the glass part This relates to the amount of glass and resin integrally molded in a structure in which the glass and resin are integrated through an adhesive layer. This invention is particularly effective for molded products that are exposed to harsh operating environments (outside air), such as automobile glass plate weather strips and tail lamps.

<Prior Art> Here, a weather strip with a glass plate will be explained as an example, but the present invention is not limited to this.

Nowadays, as shown in Figures 1 and 2, from the viewpoint of ease of assembly, sealability, and weight reduction (thinner wall thickness), a glass plate (glass part) 1 and a weather strip (synthetic resin part) 3 are assembled.
A weather strip with a glass plate is known in which the weather strip is integrated with an adhesive layer 5 during injection molding (JP-A-54-100022 and JP-A-56-998).
17・Refer to Publication No. 57-1111, etc.).

<Problems to be solved by the invention> The above adhesive layer can be used under severe usage environments.
In particular, when attempting to obtain high adhesive strength (peel strength) in a high-temperature atmosphere, it was necessary to form a primer layer on the adhesion site of the glass part. For this reason, a two-coat method was used to treat the adhesion area of the glass portion prior to injection molding, which increased the number of production steps.

Means for Solving the Problems> In order to solve the above problems, the present inventors made earnest efforts in development, and as a result, they were able to come up with the amount of glass and resin integrally molded with the following structure.

It consists of a glass part and a synthetic resin part that partially covers the glass part, the synthetic resin part is formed by injection molding, and is integrated with the glass part through an adhesive layer during injection molding. The molded article is characterized in that the adhesive layer is formed of an adhesive whose main ingredient is polyamide having a tertiary amine in its main chain, to which a silane coupling agent containing an epoxy group is added.

<Embodiment> (a) The glass plate (glass part) is usually one that has not been subjected to any special surface treatment such as a single layer of brimmer or a ceramic coat layer on the adhesion part, but when more durability is required. If this is the case, use one that has undergone these surface treatments.

(b) The weather strip (synthetic resin part) is formed by injection molding. Specifically, as shown in FIG. 2, the glass plate 1 with the adhesive layer 5 formed thereon is set in a mold 7.8, and a synthetic resin □ material is poured into the formed cavity 9 through the gate 10. Inject by injection. As the material, a soft formulation of vinyl chloride resin, ABS resin, polyamide, etc. is usually used. From the viewpoint of adhesion, it is presumed that the halogen group-containing polymer such as vinyl chloride resin ionically bonds with the nitrogen of the tertiary amine contained in the polyamide adhesive forming the adhesive layer described below.

(C) The adhesive constituting the adhesive layer has a polyamide having a tertiary amine as a main ingredient, and a silane coupling agent containing an epoxy group is added thereto. The amount of the silane coupling agent added varies depending on the type of polyamide and the silane coupling agent, but is usually 1 to 40 parts by weight of the latter per 100 parts by weight of the former! (preferably 2 to 30 parts by weight) This adhesive is used as a solution type using the following solvent, and the method of applying it to the adhering area of the glass plate is dipping, brushing, and spraying. This is done using a coating method such as

■For the polyamide containing the above tertiary amine, the hydrogen of the amide bond in nylon 6/66Φ8/12/11/612/610 and their copolymers is replaced with an alkoxymethyl group such as methoxy, ethoxy, or butoxymethyl group. Substituted (degree of substitution: 5 to 50%) represented by the following chemical formula: (where R is an alkyl group) or where the nitrogen of the amide bond is composed of the nitrogen of a nitrogen-containing heterocycle such as a piperazine ring or a pyridine ring. For example, those represented by the following chemical formula: (where R: alkylene) can be mentioned, and these can be used alone or in combination.

In the case of the former alkoxymethyl-substituted polyamide, citric acid, itaconic acid,
Geltar acid, adipic acid, azelaic acid, succinic acid,
Organic acids such as glycolic acid, crotonic acid, lactic acid, and maleic acid are added in an amount of 0.1 to 5 parts by weight per 100 parts by weight of polyamide, and from the viewpoint of heat resistance, the melting point of these polyamides is 80%. Use something above ℃.

■As the silane coupling agent containing the above epoxy group; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, β- Examples include (3,4-epoxycyclohexyl)-engineered methyltrimethoxysilane.

■As the above-mentioned solvent, lower alcohol, phenol, formic acid, etc. can be used as a sole solvent, but the lower alcohol is used as the main solvent, and water, halogenated hydrocarbons, and even aromatic hydrocarbons are suitably added within the range of 50% by volume. Specific examples of alcohols that may be mixed solvents include methanol, ethanol, isopropyl alcohol, etc. Specific examples of halogenated hydrocarbons include methyl chloride, chloroform, carbon tetrachloride, trichloroethane, trichloroethylene, etc. Specific examples of aromatic hydrocarbons include toluene and xylene.

<Operations and Effects of the Invention> As described above, the glass/resin integral molding amount of the present invention consists of a glass part and a synthetic resin part that partially covers the glass part, and the synthetic resin part is formed by injection molding. , and in a molded product configured to be integrated with the glass part via an adhesive layer during injection molding, the adhesive layer is mainly made of polyamide having a tertiary amine in the main chain and contains an epoxy group. By being formed with an adhesive containing a silane coupling agent, the adhesive layer (
Even with just one coat (1 coat), it exhibits high adhesive strength and peel strength even under harsh usage conditions (especially under high temperature atmosphere).

Therefore, when injection molding a glass/resin unit, only one coat is required for surface treatment of the adhering part of the glass part to form an adhesive layer. There is no need for two coats to form the glass and resin, so the number of molding steps for integral molding of glass and resin can be reduced overall. Furthermore, when a single layer of brimer is formed, the adhesive durability (adhesive strength after weathering test) is significantly improved compared to the conventional two-coat method.

<Example> Test examples conducted to confirm the effects of the present invention will be described below.

Each adhesive shown in Table 1 was applied to each glass shown in Table 2 (1
00x150x3.5mm) on the surface to be coated, pre-dry it, and apply it to the mold cavity (10mm).
Then, each vinyl chloride resin material having the formulation shown in Table 3 was injected into the cavity by injection.

Here, the molding conditions are: material temperature: 190°C, cylinder temperature: 190°C, injection pressure: 50kgf/C1', mold temperature: 30°C, mold clamping pressure: 100kgf/am''. A 180° peel test (80°C atmosphere) was conducted for Examples and Comparative Examples.However, Examples 7 to
9 is data obtained by conducting a 180° C. peel test (23° C. atmosphere) after conducting a weather resistance test (Quezaometer; black panel temperature 63° C.) for the indicated time.

The test results are shown in Table 2.0 Each of the examples of the present invention showed a high adhesive strength with adherend failure of 80 to 100%, whereas the comparative examples all showed a high adhesive strength of vinyl chloride resin. Interfacial peeling occurred at the glass or glass part. In addition, Example 7~
From the results of the adhesive strength after the weathering test in Section 9, when glass treated with ceramic coating (Example 8) or brimer treatment (Example 9) was used, the adhesive durability in a high-temperature atmosphere was lower than that of untreated glass (Example 9). It can be seen that this is significantly improved compared to Example 7).

′! A dispersion consisting of a copolymer shown in Table J1 (n5m7 and 10 in Table 2*) 18-XDI, trimethylolpropane, γ-glycidoxypurvyltrimethoxysilane, and carbon black ultraviolet absorber.

Table 3

[Brief explanation of drawings]

Fig. 1 is a perspective view of a weatherstrip with a glass plate, which is an example of an integrated glass/resin molded product to which the present invention can be applied, and Fig. 2 is a partial cross-sectional view of a mold for forming a weatherstrip with a glass plate of M1 diagram ( (when setting the glass plate, before material injection). 1...Glass plate (glass part), 3...Weather strip (synthetic resin part), 5...Adhesive layer. Patent application Toyoda Gosei Co., Ltd.

Claims (1)

[Claims] Consisting of a glass part and a synthetic resin part that partially covers the glass part, the synthetic resin part is formed by injection molding,
and in a molded article having a structure in which the glass part and the adhesive layer are integrated during injection molding, the adhesive layer is mainly made of polyamide having a tertiary amine in the main chain and contains an epoxy group. A glass/resin integrally molded product characterized by being formed with an adhesive containing a silane coupling agent.