JPS6222875A - Adhesive - Google Patents

Abstract

PURPOSE:To provide an adhesive having excellent thermal resistance, water resistance, moist heat resistance, etc., and suitable for use in bonding plastics rubbers and glass, etc., which comprises at least one compd. selected from particular substituted 1,3-butadiene derivatives and their (co)polymers. CONSTITUTION:An adhesive comprising at least one compd. Selected from substituted 1,3-butadiene derivatives of the formula (wherein each X is H or SiR1R2R3, provided that at least one X is SiR1R2R3; R1, R2 and R3 are each independently halogen, lower alkoxy or lower alkyl, provided that R1, R2 and R3 are not simultaneously lower alkyl) and their (co)polymers. Examples of the compd. of the formula include 1-[trimethoxy]silyl-1,3-butadiene and 1-[methoxydimethyl]silyl-1,3-butadiene. The (co)polymer can be obtd. by subjecting the compd. of the formula to radical, anionic or cationic polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel adhesive suitable for plastics, rubber, glass, etc.

Conventional resins for adhesives can be categorized as follows: - Thermosetting sesame oil such as formaldehyde resin, epoxy resin, and unsaturated polyester resin. ■Thermoplastic resins such as vinyl acetate resins, methyl methacrylate resins, polyimide resins, and cyanoacrylate resins, which are polymers with a glass transition point above room temperature and which need to be heated above this temperature. ■Elastomers with a glass transition point below room temperature, such as natural rubber and styrene-butadiene rubber. (2) Examples include composite resins that are a combination of the above resins.

The present invention relates to an adhesive that is novel in terms of the above classification and its chemical structure.

That is, the present invention is represented by the structural formula [1] (X represents a hydrogen atom or S 1RIRzRs, and one of X is always S
tR+RtRi. Further, R1, R1゜R3 represents a halogen, a lower alkoxy group or a lower alkyl group, and R3
, R2 and R1 are lower alkyl groups at the same time. ) ItA-1,3-butadiene derivative, homopolymer (n) of structural formula (1) and copolymer CII of structural formula (1) [)
The present invention relates to a novel adhesive comprising one or more compounds selected from the following.

The substituted-1,3-butadiene derivatives of the present invention include 1
-[trimethoxy]silyl-1,3-butadiene, 1-
[Methoxydimethyl]silyl-1,3-butadiene, 1
- (Dimethoxymethyl]silyl-1,3-butadiene, 1-[trichloro]silyl-1,3-butadiene, and 1-[dimethylchloro]silyl-1,3-butadiene.

Also, 2-[trimethoxy]silyl-1,3-butadiene, 2-[methoxydimethyl]silyl-1,3-butadiene, 2-[dimethoxymethyl]silyl-L3-butadiene, 2-[trichloro]silyl-1,3-butadiene and 2-[dimethylchloro]silyl-1,3-butadiene, etc. Furthermore, the homopolymer (II) of the structural formula (T) of the present invention can be prepared using the structural formula (1 ) can be easily produced by radical polymerization, anionic polymerization, and cationic polymerization.

Furthermore, the copolymer (1) of the structural formula [I] of the present invention can be obtained by radical polymerization, anionic polymerization, and cationic polymerization of the compound of the structural formula (1) and various monomers, for example, as disclosed in Japanese Patent Application No. 60-10308. By doing so, it can be easily manufactured.

The performance of the adhesive of the present invention is excellent in heat resistance, water resistance, and heat and humidity resistance.

In addition, since the adhesive of the present invention has a reactive silyl group, a diene structure and/or a polydiene structure, etc. due to its chemical structure,
Suitable for adhesion between various base materials.

In other words, adhesives between base materials such as leather, paper, wood, felt, woven fabric, thermoplastic resins, thermosetting resins, rubber, tiles, glass, metals, and ceramics, especially thermoplastic resins that are relatively difficult to adhere to. , effective for adhesion between thermosetting resins, rubber and glass.

Furthermore, the adhesive of the present invention can be used not only as an adhesive itself, but also with other polymers, curing agents such as amines, melamine, peroxides, and boron compounds, and reaction accelerators such as divinylbenzene and hexamethylenetetramine. It can also be used as an adhesive composition containing additives such as calcium carbonate and a solvent.

Furthermore, when the adhesive of the present invention is used, a new bonding method can be employed.

For example, copolymer CII of structural formula (1) in the present invention
Adhesives consisting of By performing various treatments such as adding a curing agent such as a polymerization initiator and a reaction accelerator such as a polyfunctional monomer, this glass transition point can be freely changed, and a so-called hardening phenomenon is observed.

Therefore, by these treatments, copolymer C of structural formula (T)
I[[] can also be used as a so-called adhesive by using it as an adhesive and changing the glass transition point over time.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 8.0 mg of 2-1-1/methoxysilyl-1,3-butadiene polymer (containing 15% by weight of monomer) produced by radical bulk polymerization was placed on a polymethyl methacrylate plate.
．． After coating on an area of Qxl, 0cn (), it was attached to silicone rubber and bonded by heating at 70°C in an oven for 24 hours.

The shear adhesive strength of this polymethyl methacrylate plate/silicone rubber bonded body was 2.0 kg/cnt.

Further, this adhesive was subjected to a moisture resistance test in which it was left in a moisture permeability tester at 70° C. and a relative humidity of 95% for 7 days to examine its adhesion state, and no peeling phenomenon was observed, indicating sufficient adhesive strength.

Examples 2 to 5 In the same manner as in Example 1, various bonded bodies of temporary glass/silicon rubber, polymethyl methacrylate plate/glass plate, aluminum plate/silicon rubber and polymethacrylate plate, and polyethylene plate/polyethylene plate were made. When a shear adhesive strength test and a moisture resistance test were conducted, all adhesive bodies showed sufficient adhesive strength.

Example 6 2-triisopropoxysilyl-1,3-butadiene/methyl methacrylate/butyl acrylate copolymer radically copolymerized in toluene solution (polymerization charge weight ratio 7/
100g of 30% toluene solution of 1/2), Nippon Gosei KK
12 mg of an adhesive composition consisting of ethyl acetate-toluene 40% solution) 6'Og and 0.5 g of benzoyl peroxide was applied to an area of 1.0 x 1, QcJ on a methyl methacrylate board, and then applied with toluene. When the odor became weak, it was attached to silicone rubber, and the methyl methacrylate/silicone rubber bond was subjected to a shear adhesion test and a moisture resistance test in the same manner as in Example 1. Indicated.

Example 7 A 30% toluene solution of the 2-triisopropoxysilyl-1,3-butadiene/methyl methacrylate/butyl acrylate copolymer (polymerization charge weight ratio ?/1/2) of Example 6 was placed on release paper. After coating, it was vacuum dried at 60° C. for 30 minutes to form a film with a thickness of 60 μm.

This coating had a tanky feel to the touch.

Further, this film was transferred to a glass cloth nonwoven fabric to make an adhesive product.

After cutting this adhesive product into a size of 2.5cm x 8cm,
Peel off the release paper and place it on a 5 mm thick plywood board with a contact area of 2°5 cf.
When the glass cloth nonwoven fabric/plywood was adhered to a size of 1I x 2.5 cm, the glass cloth nonwoven fabric/plywood adhered to each other without shifting.

Furthermore, after 15 minutes, the glass cloth nonwoven fabric or plywood of the glass cloth nonwoven fabric 7 plywood could be easily peeled off by hand in parallel with the adhesive surface.

However, when this glass cloth nonwoven fabric/plywood was left in an atmosphere of 40°C and 95% relative humidity for 4 hours, it could not be easily peeled off by hand, and the 2-triisopropoxysilyl-1,3-butadiene/methyl methacrylate copolymer It turns out that the combination can be used as an adhesive.

Claims (1)

[Claims] There are ▲ mathematical formulas, chemical formulas, tables, etc. represented by the structural formula [ I ] ▼ [ I ] (X represents a hydrogen atom or SiR_1R_2R_3,
One of X is always SiR_1R_2R_3. Also, R
_1, R_2, and R_3 represent a halogen, a lower alkoxy group, or a lower alkyl group, except when R_1, R_2, and R_3 are lower alkyl groups at the same time. ) An adhesive comprising one or more compounds selected from substituted-1,3-butadiene derivatives, homopolymers [II] of structural formula [I], and copolymers [III] of structural formula [I].