JPH0749516B2 - Polyphenylene oxide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyphenylene oxide resin composition having excellent adhesiveness to various base materials.

[Prior Art] It has been conventionally considered extremely difficult to firmly adhere a polyphenylene oxide resin to another substrate.

[Problems to be Solved by the Invention] As a result of intensive studies to solve the above problems, the present inventors have found that a polyphenylene oxide resin is blended with a specific organic silicon compound and organic titanate esters. The inventors have found that the product has excellent adhesiveness to various base materials and have completed the present invention.

An object of the present invention is to provide a polyphenylene oxide resin composition having excellent adhesion to various base materials.

[Means for Solving Problems and Actions Thereof] The objectives are (A) 100 parts by weight of polyphenylene oxide resin, (B) general formula R ¹ aSi (OR ² ) ₄ -a (wherein R ¹ and R ² are Polyphenylene oxide resin consisting of 1 to 1000 parts by weight of an organosilane or a partial hydrolyzate thereof represented by a valent organic group, a is 0 or 1, and 0.01 to 2000 parts by weight of (C) an organic titanate ester. Achieved by the composition.

Explaining this, the polyphenylene oxide resin as the component (A) used in the present invention is a polymer compound composed of phenylene oxide units, and may be the polyphenylene oxide resin alone, or other resin, For example, a mixture with polystyrene or the like (generally called modified polyphenylene oxide) may be used.

The (B) component alkoxysilane or a partial hydrolyzate thereof used in the present invention is a component for imparting adhesiveness to the polyphenylene oxide resin composition of the present invention when used in combination with the (C) component, In the above formula, R ¹ is an alkyl group such as a methyl group, an ethyl group or an octyl group; an aryl group such as a phenyl group, or a hydrogen atom of these groups substituted with a halogen atom, a cyano group or the like; There are monovalent organic groups having condensation-reactive functional groups. Examples of such monovalent organic groups include vinyl groups and allyl groups, and further epoxy groups, methacryloxy groups,
Any of mercapto group, amino group, N-alkylamino group is methylene group, ethylene group, propylene group, phenylene group, fluoroethylene group, or -CH ₂ OCH ₂ CH ₂ CH
₂₋ , −CH ₂ CH ₂ OCH ₂ CH ₂ −, −CH ₂ OCH ₂ C ₂ OCH ₂ CH ₂ −, −
An example is a monovalent organic group bonded to a silicon atom via a divalent organic group such as (CH ₂ ) ₃ (NHCH ₂ CH ₂ ) ₁ to ₅ .
R ² is a monovalent organic group exemplified by an alkyl group such as a methyl group, an ethyl group and a propyl group; an aryl group such as a phenyl group; an alkoxy group such as a 2-methoxyethyl group and a 2-ethoxyethyl group. a is 0 or 1. (B)
Specific examples of the component include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, methyltris (β-methoxyethoxy) silane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl. Triethoxysilane, allyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane , Ethyl orthosilicate, methyl cellosolve orthosilicate and one or more partially hydrolyzed condensates thereof.
The mixing ratio of the component (B) is 1 to 1000 parts by weight, preferably 5 to 200 parts by weight, based on 100 parts by weight of the component (A).

The organic titanate ester as the component (C) used in the present invention is an important component that remarkably improves the adhesiveness of the composition of the present invention when used in combination with the component (B).
Specific examples of the component (C) include, for example, tetraisopropyl titanate, tetra-n-propyl titanate, tetraamyl titanate, tetra (2-ethylhexyl) titanate, tetrabutyl titanate, dibutyl diisopropyl titanate, ethylene glycol titanate, bis (acetylacetate). Nato) diisopropoxy titanium,
Examples thereof include tetrakis (trimethylsilyl) titanate, isopropyldimethacrylisostearoyl titanate, isopropyldiacrylisostearoyl titanate, dibutyldiacrylic titanate, dibutylisostearoyl methacryl titanate and their partial hydrolysis-condensation products. The mixing ratio of the component (C) is 0.01 to 2000 parts by weight with respect to 100 parts by weight of the component (A), and (B)
1 to 200 parts by weight, preferably 10 to 100 parts by weight of the component
It is 1000 parts by weight.

When the composition of the present invention is used as an adhesive or a coating agent, it is preferable to use an organic solvent as the component (D) in addition to the above components (A) to (C) because the adhesiveness is excellent. The organic solvent is not particularly limited as long as it can uniformly dissolve the composition of the present invention, and is appropriately selected and used in consideration of the solubility of the polyphenylene oxide resin and the evaporating property in the coating operation. ,Normal,
Toluene, xylene, trichloroethylene, acetone,
Methyl ethyl ketone and ethyl acetate are preferably used.
The blending ratio of the component (D) is not particularly limited because it is used by adjusting the coating workability of the composition of the present invention and the target coating film according to the thickness.

The composition of the present invention can be easily obtained by uniformly mixing the above-mentioned components (A) to (C). Further, addition of various additives such as glass fiber and carbon black to the composition of the present invention may be added as long as the intended properties of the present invention are not impaired.

The polyphenylene oxide resin composition of the present invention can be adhered to plastics such as metals, nylon resins, ABS resins, silane-grafted polyethylene resins, and silane-grafted polypropylene resins, and is useful as a primer, but other than that. It can be coated as a coating agent, can be used as an adhesiveness improver by adding it to various resins, paints, or the like, or can be used as an adhesive cured product itself.

EXAMPLES Next, the present invention will be described with reference to examples. However, all parts in the examples are parts by weight.

Example 1 100 parts of polyphenylene oxide resin [NORYL 731J-802 manufactured by Engineering Plastics Co., Ltd.], vinyltrimethoxysilane [SZ manufactured by Torre Silicone Co., Ltd.
6300] 100 parts, tetrabutyl titanate 100 parts and toluene 100 parts were uniformly mixed to obtain a polyphenylene oxide resin composition. Next, 100 parts of polyethylene resin [HIZEX 1300J manufactured by Mitsui Petrochemical Industry Co., Ltd.] and vinyltrimethoxysilane [SZ630 manufactured by Torre Silicone Co., Ltd.
0] 100 parts and dicumyl peroxide 0.12 parts were heated and mixed to obtain a vinyltrimethosisilane-grafted polyethylene resin, which was then molded into a sheet having a thickness of 2 mm.
Then, the polyphenylene oxide resin composition obtained above was applied to the surface of this sheet and left to stand at room temperature for 60 minutes and dried to obtain a molded body in which the polyphenylene oxide resin composition and the grafted polyethylene resin were integrated. Was given. The end of this polyphenylene oxide resin and the end of the grafted polyethylene resin were sandwiched between jigs for measuring tensile strength, and both sides were tried to be pulled and pulled in opposite directions, but the polyphenylene oxide resin portion broke and peeled. I couldn't.

For comparison, with respect to the polyphenylene oxide resin composition obtained in the same manner as above except that vinyltrimethoxysilane and tetrabutyl titanate are not used in the above, adhesion with the vinyltrimethoxysilane-grafted polyethylene resin in the same manner as above. As a result of a property test, a molded product in which the polyphenylene oxide resin and the grafted polyethylene resin were integrated was not obtained, and both were easily separated.

Example 2 Polyphenylene oxide resin composition obtained by uniformly mixing 100 parts of polyphenylene oxide resin [NORYL 731J-802 manufactured by Engineering Plastics Co., Ltd.], 100 parts of methyl cellosolve orthosilicate, 100 parts of tetrabutyl titanate and 100 parts of toluene. Got Next, polypropylene resin [Sumitomo Chemical Co., Ltd. Nobren Y10
1] 100 parts, 3 parts of vinyltrimethoxysilane and 0.12 part of dicumyl peroxide were heated and mixed to obtain a vinyltrimethoxysilane grafted polypropylene resin, which was then formed into a sheet having a thickness of 2 mm. Then, the polyphenylene oxide resin composition obtained above was applied onto the surface of the sheet, and left standing at room temperature for 60 minutes and dried, whereby a molded product in which the polyphenylene oxide resin composition and the grafted polypropylene resin were firmly integrated was gotten.

For comparison, with respect to the polyphenylene oxide resin composition obtained in the same manner as above except that only vinyltrimethoxysilane is not used, the adhesiveness with the vinyltrimethoxysilane-grafted polypropylene resin obtained in the same manner as above As a result of a test, a molded product in which the polyphenylene oxide resin and the grafted polypropylene resin were integrated was not obtained, and both were easily peeled off.

Example 3 100 parts of polyphenylene oxide resin [NORYL 731J-802 manufactured by Engineering Plastics Co., Ltd.], 100 parts of methyl cellosolve orthosilicate, 100 parts of vinyltrimethoxysilane, 100 parts of tetrabutyl titanate and 100 parts of toluene are uniformly mixed. Then, a polyphenylene oxide resin composition was obtained. Then, this composition was applied to the surface of a stainless steel plate (SUS304) and left at room temperature for 60 minutes to obtain a stainless steel plate coated with the polyphenylene oxide resin composition.

Next, a silicone rubber compound [SH52U manufactured by Toray Silicone Co., Ltd.] with 0.5% 2,5 dimethyl 2,5 di (t-butylperoxy) hexane added as a cross-linking agent was used for unvulcanization molding with a thickness of 4 mm. The product was adhered onto a stainless steel plate coated with the above polyphenylene oxide resin composition, and pressure was 10 kg under conditions of 25 kg / cm ² and 170 ° C.
When the silicone rubber compound was cured by heating under pressure for a minute, a molded body in which the silicone rubber and the stainless steel plate were firmly integrated was obtained.

For comparison, a polyphenylene oxide resin composition obtained in the same manner as above except that methylcellosolve orthosilicate and tetrabutyl titanate were not used in the above, was subjected to an adhesion test in the same manner as above, and a silicone rubber was obtained. A molded body integrated with the stainless steel plate could not be obtained, and both were easily separated.

Example 4 100 parts of polyphenylene oxide resin [NORYL 731J-802 manufactured by Engineering Plastics Co., Ltd.], 100 parts of a partially hydrolyzed condensate of ethyl orthosilicate, 100 parts of isopropyl dimethacryl isostearoyl titanate.
The parts were uniformly heated and mixed to obtain a polyphenylene oxide resin composition. Next, this was placed on a nylon 6 resin sheet and heated under pressure at a pressure of 25 kg / cm ² and a temperature of 230 ° C. to obtain a molded body in which the polyphenylene oxide resin composition and the nylon 6 resin were integrated. Was given.

For comparison, a polyphenylene oxide resin composition obtained in the same manner as above except that isopropyldimethacrylisostearoyl titanate was not used in the above was subjected to an adhesion test in the same manner as above, showing that silicone rubber and stainless steel were used. A molded body integrated with the plate was not obtained, and both were easily separated.

EFFECTS OF THE INVENTION The present invention relates to (A) polyphenylene oxide resin, (B)
Since it is a polyphenylene oxide resin composition comprising organosilane or a partial hydrolyzate thereof, and (C) organic group titanic acid esters, it is characterized by having excellent adhesiveness to various substrates.

Claims (1)

[Claims] 1. (A) 100 parts by weight of polyphenylene oxide resin, (B) General formula R ¹ aSi (OR ² ) _4- a (wherein R ¹ and R ² are monovalent organic groups, and a is 0 or 1) 1 to 1000 parts by weight of organosilane or a partial hydrolyzate thereof, and (C) 0.01 to 2000 parts by weight of organic titanic acid ester, a polyphenylene oxide resin composition.