JP2708494B2 - Polyolefin resin composition for bonding ceramics - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyolefin resin composition for bonding ceramics. More specifically, the present invention relates to a polyolefin resin composition excellent in adhesion between polyolefin and ceramics or between ceramics.

[Conventional technology]

There is no known technology for easily bonding polyolefins to ceramics such as glass, and it is only known that some ceramics and polyolefins can be bonded by using a special adhesive. There is no known method for heating and fusing.

[Problems to be solved by the invention]

The method of using a special adhesive is complicated in operation and does not exhibit sufficient functions depending on the type of polyolefin, and has a problem that it is extremely difficult to produce a multilayer structure such as ceramics-polyolefin-ceramics. It has been desired to develop an adhesive that can easily fuse ceramics.

[Means for solving the problem]

The present inventors diligently studied an adhesive that solved the above-mentioned problems, found a polyolefin resin composition having excellent adhesiveness, and completed the present invention.

That is, the present invention includes a copolymer of an alkenylsilane having at least one Si-H bond and an olefin, or a copolymer obtained by graft-polymerizing an alkenylsilane having at least one Si-H bond to a polyolefin. It is a polyolefin resin composition for bonding ceramics.

The alkenyl silane and olefin copolymer having at least one Si-H bond used in the present invention is a random copolymer of an alkenyl silane and olefin having at least one Si-H bond, and at least one Si-H A so-called block copolymer of alkenylsilane and polyolefin obtained by polymerizing an olefin using a catalyst composed of a transition metal compound and an organometallic compound treated with an alkenylsilane having an H bond,
A copolymer obtained by graft-polymerizing an alkenylsilane having at least one Si-H bond to a polyolefin is a graft copolymer obtained by grafting an alkenylsilane having at least one Si-H bond to a polyolefin in the presence of a radical generator. Means a polymer.

Here, the alkenyl silane having at least one Si-H bond includes, for example, vinyl silane, allyl silane,
Examples thereof include butenyl silane, pentenyl silane, and compounds in which one or two Si-H bonds of these monomers are substituted with an alkyl group or halogen.

As a catalyst preferably used for producing a random or random copolymer of alkenylsilane and olefin, a known stereoregular catalyst comprising a transition metal catalyst and an organometallic compound, particularly an organoaluminum compound can be used, and there is no particular limitation.

Titanium halide is preferably used as the transition metal catalyst. For example, titanium trichloride obtained by reducing titanium tetrachloride with metallic aluminum, hydrogen or organic aluminum or those obtained by modifying them with an electron donating compound and an organic aluminum compound And a catalyst system comprising a stereoregularity improver such as an oxygen-containing organic compound, or a carrier such as magnesium halide, or those obtained by treating them with an electron-donating compound, as necessary, and then obtaining a titanium halide. A catalyst system comprising a transition metal catalyst and a stereoregularity improver such as an organic aluminum compound and, if necessary, an oxygen-containing organic compound is exemplified. For example, various examples are described in the following documents.

Ziegler-Natta Catalysts and Polymerization by J
ohn Boor Jr. (Academic Press), Journal of Macromor
ecular Sience-Reviews in Macromolecular Chemistry
and Physics, C24 (3) 355-385 (1984), C25
(1) 578-597 (1985)).

Here, as the stereoregularity improver or the electron-donating compound, oxygen-containing compounds such as ethers, esters, orthoesters, and alkoxysilicon compounds can be preferably exemplified. Examples of the electron-donating compound further include alcohols, aldehydes, and water. Can be used.

Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide.Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Examples of the halide include chlorine, bromine and iodine.

The polymerization method is not particularly limited, and a bulk polymerization method or a gas phase polymerization method can be employed in addition to a solvent method using an inert solvent.In the production of an alkenylsilane-olefin block copolymer, alkenylsilane treatment is performed. Depending on the activity of the catalyst, the polymerization amount of alkenyl silane relative to the polymerization amount of olefin after polymerization of olefin is 100 wtp.
It is preferable to set it to pm or more from the viewpoint of adhesive strength to ceramics. The treatment conditions are not particularly limited, but the above catalyst is dispersed in a usual inert solvent, and at a temperature not higher than the room temperature to the polymerization temperature of the olefin, a monomer concentration and a time sufficient for the alkenylsilane in the above-mentioned quantitative ratio to be polymerized. Done. Subsequently, the olefin is polymerized in the presence of the treated catalyst, and ethylene, propylene, butene, pentene, hexene, and 2-methylpentene are used as the olefin. Copolymerization or block copolymerization is performed.
The molecular weight of the polymer is not particularly limited and may be determined according to the purpose of using the composition. For example, if it is used as it is for bonding to ceramics, 135
In general, the intrinsic viscosity is about 0.5 to 5 as measured with a tetralin solution, and about 0.1 to 3 when blended with another polyolefin.

The production of a random copolymer of alkenylsilane and olefin is carried out by copolymerizing olefin and alkenylsilane without previously treating with alkenylsilane. Already on how to do that USP3,2
No. 23,686, and the method is used as such, or various improved catalysts are known as described above and can be used. The preferred ratio of the alkenylsilane to the olefin is 30 wt% or less because the content of the alkenylsilane in the copolymer is 100 wtppm or more, and the activity of the copolymer is usually or the blending with other polyolefin is easy.

There are no particular restrictions on the polymerization method or polymerization conditions, and the conditions employed in ordinary olefin polymerization can be applied as they are. Normal 0 ~ 200 ℃, normal pressure ~ 150kg / c
It is carried out in m ^2. The molecular weight is the same as that of the above-mentioned block copolymer.

Various methods are already known for graft copolymerization of alkenylsilane and polyolefin, and there is no limitation on the production method.

Basically, this can be achieved by treating alkenyl silane and polyolefin under the condition that a radical generator such as peroxide is thermally decomposed, and in the presence of a solvent, in a dissolved state of a polymer, or a Henschel mixer or extruder The method is generally performed under melt mixing, and various methods have already been proposed (JP-B-48-1711;
−40701, 54-117549 etc.). It can also be obtained on the market as a polyolefin for crosslinking.

As ceramics used for bonding in the present invention, metal oxide ceramics can be particularly preferably exemplified,
Examples include various ceramics and glasses obtained by mixing various inorganic compounds based on silica, alumina, or the like depending on the application.

In the present invention, a copolymer of an alkenylsilane having at least one Si-H bond and an olefin, or a copolymer obtained by graft-polymerizing an alkenylsilane having at least one Si-H bond to a polyolefin, as it is, or It is mixed with other polyolefin and used for bonding, but there is no particular limitation on the mixing method, and it is a general method such as pre-mixing with a Henschel mixer, then melt-mixing with an extruder and granulating. It is enough. Heating can also be performed when mixing with Henschel, and mixing can also be performed using a roll. At this time, it is of course possible to mix various known additives such as stabilizers.

As the polyolefin used by mixing, its composition,
The molecular weight is not particularly limited as long as it is well mixed with the above-mentioned polyolefin, and examples thereof include polymers of ethylene, propylene, butene, hexene, and 4-methylpentene-1, and polymers of various molecular weights as needed, or Mutual random or block copolymers can be used,
Usually, an olefin containing alkenyl silane and a polymer or copolymer having a similar composition and molecular weight except for not containing alkenyl silane are generally used.

These polyolefins used for mixing can be produced by various known production methods, and various products can be obtained on the market. However, they can also be produced by utilizing the above-mentioned catalyst and polymerization method upon polymerization.

In the present invention, a copolymer of an alkenyl silane having at least one Si-H bond and an olefin, or a copolymer obtained by graft-polymerizing an alkenyl silane having at least one Si-H bond to a polyolefin and another polyolefin The mixing ratio is generally such that the alkenylsilane unit is present in an amount of about 1% by weight to 100% by weight in the total composition after mixing.

The composition of the present invention can be used by a method in which the composition of the present invention is usually sandwiched between a polyolefin layer and a ceramics layer and bonded to each other, or the composition of the present invention is sandwiched between two ceramics. The composition of the present invention can be mixed with a polyolefin and used as a polyolefin layer. The adhesion may be at least one copolymer of alkenylsilane and olefin having at least one Si-H bond, or at least one
The alkenyl silane having two Si-H bonds is fused to the polyolefin by heating it to a temperature equal to or higher than the melting point of the copolymer obtained by graft-polymerizing the polyolefin, whereby sufficient adhesive strength can be obtained.

〔Example〕

 Hereinafter, the present invention will be described with reference to Examples.

Example 1 A vibration mill equipped with four crushing pots having an internal volume of 4 and containing 9 kg of steel balls having a diameter of 12 mm was prepared. Under a nitrogen atmosphere, 300 g of magnesium chloride, 60 ml of tetraethoxysilane, and 45 ml of α, α, α-trichlorotoluene were added to each pot, followed by addition of 40 ml.
Crushed for hours. 300 g of the co-ground product thus obtained was placed in a flask (5), and titanium tetrachloride (1.5) and toluene (1.5) were added.
Stir at 0 ° C for 30 minutes, then remove the supernatant, add 1.5 parts of titanium tetrachloride and 1.5 parts of toluene, stir at 100 ° C for 30 minutes, remove the supernatant, and repeat the solid content with n-hexane. After washing, a transition metal catalyst slurry was obtained. 1.9 wt% when a part was sampled and analyzed for titanium content
Met.

In a pressure-resistant glass autoclave having an internal volume of 200 ml, under a nitrogen atmosphere, 40 ml of toluene, 20 mg of the above transition metal catalyst, 0.128 ml of diethylaluminum chloride, and methyl p-toluate
0.06 ml and 0.03 ml of triethylaluminum were added, and then 0.5 g of vinylsilane was injected thereinto, and the mixture was stirred at 20 ° C. for 60 minutes. After that, 0.05 ml of triethylaluminum was added.
8 kg and 3.3 Nl of hydrogen were added, and a polymerization reaction was performed at 75 ° C. for 2 hours. After the polymerization reaction, the unreacted propylene was purged and the polymer taken out was dried at 80 ° C. and 60 mmHg for 12 hours. 380g
Was obtained and the intrinsic viscosity (hereinafter abbreviated as η) measured with a tetralin solution at 135 ° C. and the extraction residue ratio (hereinafter abbreviated as II, abbreviated as II) after extraction with boiling n-heptane for 6 hours with a Soxhlet extractor (Weight of powder / weight of powder before extraction is expressed as a percentage). In addition, a phenol-based stabilizer (10/10000 weight ratio) and calcium stearate (15 / 10,000 weight ratio) were added to some of the powders, followed by granulation to obtain a resin composition for bonding. The melt flow index was measured using a part (Melt Flow Index (MI) AS
TM D1238 (230 ° C)) was 6.5 g / 10 min.

The pellet thus obtained was compression molded at 220 ° C. and 100 kg / cm ² to obtain a 200 μm sheet.

To measure the adhesive strength, a glass plate (E plate glass) having a thickness of 2 mm (10 cm × 2.5 cm) degreased with acetone was superimposed on the sheet in the order of glass plate-sheet-glass plate at 240 ° C.
After pressurizing at 0 kg / cm ² for 3 minutes, the resultant was cooled with water to obtain a laminate. The shear peel strength of this laminate was 10.2 kg / cm ² or more (glass cut). The polymerization amount of vinylsilane in the polypropylene was 140 wtppm.

Comparative Example 1 475 g of polypropylene was obtained in the same manner as in Example 1 except that propylene was polymerized without pretreatment with vinylsilane.
I got Using this, evaluation was performed in the same manner as in Example 1 but spontaneous peeling was performed.

Example 2 A sintered alumina plate (2 cm × 5 cm ×
Evaluation was made in the same manner as in Example 1 except that 0.2 mm) was used. As a result, the shear peel strength was 31 kg / cm ² .

Comparative Example 2 The same procedure as in Example 2 was carried out except that vinyl silane was not used.

Example 3 Using a catalyst pretreated with vinylsilane as in Example 1, ethylene and butene-1 were copolymerized in a hexane solvent. At a polymerization temperature of 70 ° C, the total pressure is 10 kg / cm ² , and the initial hydrogen partial pressure is 3 kg / cm
Feed rate of ethylene in ² to obtain a copolymer of polymerized butene-1 content 8 wt% of ethylene until 400 g. When this copolymer was evaluated in the same manner as in Example 1, the shear peel strength was as good as 10.2 kg / cm ² or more. This copolymer contained 135 ppm of vinylsilane, and the melt flow rate at 190 ° C. was 15 g / 10 min.

Example 4 The procedure of Example 1 was repeated except that allylsilane was used instead of vinylsilane. The shear peel strength was as good as 10.2 kg / cm ² or more.

Example 5 In a pressure-resistant glass autoclave having an inner volume of 200 ml, under a nitrogen atmosphere, 40 ml of toluene, 20 mg of the transition metal catalyst obtained in Example 1,
0.128 ml of diethylaluminum chloride, 0.06 ml of methyl p-toluate and 0.20 ml of triethylaluminum
Was added, and then 2.0 g of vinylsilane was injected thereinto. Then, propylene was charged until the pressure reached 5 kg / cm ^2, and polymerization was carried out at 70 ° C. under a constant pressure for 2 hours. Thereafter, the slurry was taken out and filtered and dried to obtain 43 g of a powder. Η of the obtained powder is 1.45
The melting point was 156 ° C and the crystallization temperature was 118 ° C. According to elemental analysis, the product contained 1.6% by weight of vinylsilane units.

Separately, propylene and a small amount of ethylene were prepared in the same manner as in the above polymerization, with an ethylene content of 2.5 wt%, η of 1.60,
%, And a polypropylene copolymer having a melting point of 154 ° C. was obtained.

10 g of the copolymer obtained above in 200 g of the polypropylene copolymer powder obtained here, a phenol-based stabilizer 10/1000
0 weight ratio and 15 / 10,000 weight ratio of calcium stearate were added and granulated to obtain a resin composition for bonding. The adhesive strength to glass was measured in the same manner as in Example 1 except for using this adhesive polymer, and the shear peel strength was as good as 10.2 kg / cm ² or more.

〔The invention's effect〕

The polyolefin resin composition for adhesion of the present invention has excellent adhesiveness to ceramics and is extremely industrially significant.

Claims (1)

(57) [Claims] 1. A ceramic containing a copolymer of an alkenylsilane having at least one Si-H bond and an olefin, or a copolymer obtained by graft-polymerizing an alkenylsilane having at least one Si-H bond to a polyolefin. Polyolefin resin composition for bonding.