KR910008617B1 - Poly olefine composition for adhesion and painting - Google Patents

Abstract

No content.

Description

Polyolefin resin composition for adhesion and painting

The present invention relates to the use of copolymers of α-olefins, in particular of random copolymers of alkenyl silanes and α-olefins.

That is, the present invention relates to a polyolefin resin composition containing a random copolymer of an alpha -olefin and an alkenyl thread used for bonding a polar group-containing polymer, a metal, and the like to a polyolefin or for coating various paints.

Polymers containing polar groups, such as ethylene-vinyl acetate copolymer saponification (EVA), nylon and polyester, for the purpose of utilizing the properties of polyolefins and imparting characteristics not originally possessed by polyolefins such as gas barrier properties. And a multilayer structure or a multilayer structure with a metal such as aluminum or iron is widely used. Since the polyolefin and the polar group-containing polymer are incompatible with each other, and the polyolefin and the metal have poor relativity, they are not bonded by only pulling, and the resin for adhesion is sandwiched therebetween. For this purpose, a resin composition containing a polymer obtained by grafting maleic anhydride to a polyolefin is used. Moreover, polyolefin utilizes the characteristic and is used for the various uses in the exterior, attaching suitable paint on the surface. Polyolefins are inherently poor in paintability with respect to various paints, and have problems such as peeling of the coating film as they are. Therefore, the substance which has a coating film and the polyolefin adhesiveness on the surface of the molded object of polyolefin is first apply | coated, or the surface of the molded object is plasma-processed etc., and is performed.

Polymers grafted with maleic anhydride to polyolefins have a certain effect on improving the adhesion between olefinic and polar group-containing polymers, but are still insufficient for adhesion between Evar and polyolefins or adhesion to gold, In addition, when used for large metals, there is a problem of corrosiveness, and development of a resin composition for adhesion with improved adhesion is desired. On the other hand, for coating, the above method needs to apply another substance before application, and there is a problem that the operation becomes complicated, and therefore, there is a problem that a special facility is required for the treatment by plasma. .

Therefore, there is a demand for a composition capable of improving paintability by merely mixing the polyolefin without impairing the physical properties of the polyolefin.

The inventors of the present invention have focused on this problem, and as a result of their studies, block copolymers of α-olefins obtained by first polymerizing alkenyl silanes and then polymerizing α-olefins using a stereoregular catalyst are these problems. It was found that the solution can be solved and provided a novel block copolymer and its use. As a result of further studies, the present inventors reached the present invention.

Moreover, about the random copolymer obtained by superposing | polymerizing the alkenyl silane and ethylene used in this invention demonstrated later in presence of a transition metal compound and an organometallic compound, it describes in US Patent 3,223,686, The use of copolymers as crosslinked polymers is shown in US Pat. No. 3,644,306, but it is not known that they are useful as polymers for adhesive resin compositions.

It is an object of the present invention to provide novel uses of random copolymers of alkenyl silanes and α-olefins.

That is, the first invention of the present invention is an adhesive polyolefin resin composition containing a copolymer obtained by random copolymerization of α-olefin and alkenyl silane using a catalyst composed of a transition metal compound and an organometallic compound. The invention is also a polyolefin resin composition for coating containing a copolymer obtained by random copolymerization of α-olefin and alkenyl silane using a catalyst composed of a transition metal compound and an organometallic compound.

As the alkenyl silanine used for copolymerization in the present invention, the general formula CH₂ = CH- (CH₂) n SiHm R ₃ -m (where n represents 0-12, m represents 1-3, R represents a methyl group and a phenyl group) Or general formula CH₂ = CH- (CH₂) n SiHpCl ₃ -p (where n represents 0-12 and p represents 0-3), for example, vinylsilane, allylsilane, Examples of butenylsilane, pentenylsilane, and hydrogen of 1-2 Si-H groups in their alkenylsilane molecules are substituted by chlor atoms of hydrogen of methyl group, phenyl group or 1-3 Si-H group .

As the α-olefin used in the present invention, one kind or a mixture of two or more kinds of α-olefins having 2 to 12 carbon atoms is used. For example, ethylene, propylene, butene-1, pentene-1, hexene-1, 2- Methylpentene-1, octene-1, etc. are illustrated.

As a catalyst composed of a transition metal compound and an organometallic compound which can be used in the present invention, not only the catalysts described in the above-mentioned US patent but also the polymers for the polymerization of? -Olefins improved in many of the performances described thereafter can be used without any problems.

In the catalyst composed of a transition metal compound and an organic metal compound, titanium halide or vanadium halide is preferably an organic aluminum compound as the organic metal compound. For example, titanium trichloride obtained by reduction of titanium tetrachloride, metal aluminum, hydrogen or organoaluminum, or electron donating compounds such as an organic donor compound such as an organic aluminum compound or an oxygen-containing organic compound if necessary. Catalyst system, vanadium halide, or vanadium oxyhalide and organoaluminum catalyst system, or a carrier such as magnesium halide, or a transition metal compound obtained by supporting titanium halide, vanadium halide or vanadium halide with an electron donating compound A catalyst system consisting of an electron donating compound such as a catalyst and an organoaluminum compound, an oxygen-containing organic compound or, if necessary, or a reactant of magnesium chloride and an alcohol is dissolved in a hydrocarbon solvent, and then treated with a precipitant such as titanium tetrachloride to insolubilize the hydrocarbon solvent. and, If necessary, an electron-donating compound such as a transition metal compound catalyst, an organic aluminum compound, and an oxygen-containing organic compound may be obtained by treating with an electron donating compound such as ester or ether and then treating with titanium halide. The catalyst system etc. which were made are illustrated (for example, various examples are described in the following document).

Ziegler-Natta Catalysts and Ploymerization by John Boor Jr (Academic Press), Journal of Macromorecular Sience Reviews in Macromolecular Chemistry and Physics, C24 (3) 355-385 (1984), E C25 (1) 578-597 (1985), where As the electron donating compound, oxygen compounds such as ethers, esters, orthoesters, and alkoxysilicon compounds are usually exemplified, and alcohols, aldehydes, water and the like can also be used.

Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halides, alkylaluminum sesquihalides, and alkylaluminum dihalides. Examples of the alkyl group include methyl, ethyl, propyl, butyl, and hexyl groups. Bromine, iodine are illustrated.

Although it is common to use the solvent method which uses an inert solvent also as a polymerization method, a mass polymerization method and a gas phase polymerization method are also employ | adopted.

As for the polymerization method and polymerization conditions, well-known methods and conditions for the polymerization of α-olefins are applied. Usually, the temperature and pressure are 0-200 ° C., atmospheric pressure-150 kg / cm 2, preferably room temperature-150 ° C., atmospheric pressure. -100kg / ㎠

As the polymerization ratio of the alkenylsilane and the α-olefin, the activity of the catalyst decreases when the ratio of the copolymerization of the alkenylsilane increases, so in general, the upper limit of the content rate of the alkenylsilane is preferably 30% by weight or less, and the lower limit. It is about 1 ppm by weight for adhesion and about 10 ppm for coating.

There is no patent limitation as the molecular weight of the copolymer, but it is preferable from the viewpoint that it is easy to mix with other olefins so that it is not more than 10 as the intrinsic viscosity measured by a very high molecular weight, for example, 135 ° C tetralin solution, and is usually intrinsic viscosity It is about 0.1-5 dl / g.

In the present invention, a random copolymer of alkenyl silane and olefin may be used as it is for adhesion and coating, but industrially, a relatively high concentration random copolymer of alkenyl silane is produced and does not contain alkynylsilane. It is economical and preferable to mix the polyolefin which does not mix, and to adjust it to the composition of 1 ppm or more as a content of alkenylsilane for adhesion | attachment, and 10 ppm or more for coating.

There is no restriction | limiting in particular as polyolefin which does not contain the alkenylsilane mixed here, The polymer of various molecular weights, or the random or block copolymer between olefins can be used as needed, The composition and molecular weight similar to the polyolefin to adhere | attached Using one is one way. As the α-olefin forming the polyolefin, those exemplified as the α-olefins used for the copolymerization with the alkenylsilane described above are used, and each of the homopolymers or the random or block copolymers between the monomers has a smaller amount of carbon more. Copolymers with α-olefins are also exemplified. These polymers can be polymerized under the same catalyst system as those used for copolymerization of the alkenylsilane described above and under the same conditions, and polyolefins can be used for various kinds of products available on the market.

In the present invention, the composition may add various additives added to conventional polyolefins, such as antioxidants and ultraviolet absorbers, as necessary. If necessary, coating properties and adhesive properties can be obtained by using a compound selected from an organic acid or a salt thereof, an organic base or an alkoxy compound of an alkali metal or an alkaline earth metal, or a noble metal such as hydroxide, oxide or palladium platinum. Further improvements may be made, but sufficient adhesion and paintability for normal purposes, in particular, without the presence of such a catalyst activating Si-H.

In the present invention, the mixing ratio of the copolymer containing alkenyl silane and the polyolefin containing no silane compound is different depending on the amount of alkenylsilane present in the copolymer containing alkenylsilane. It is common for the kenylsilane units to be present in the total composition in the range of about 1wt% -1wtppm for adhesion and about 1wt% -10wtppm for coating. Moreover, an additive, such as a stabilizer, can also be made into a composition in the copolymer containing alkenylsilane. There is no restriction | limiting in particular as a mixing method at the time of manufacturing a composition, It is common to mix uniformly with a Henschel mixer etc., and to melt-mix by an extruder etc., and to granulate. It is of course also possible to mold the film, sheet or the like according to a method using a blower or the like which simultaneously mixes and melts or a form used as it is after melting.

Example 1

A vibration mill equipped with four grinding pots with a volume of 4 liters containing 9 kg of steel balls having a diameter of 12 mm is prepared. 300 g of magnesium chloride, 60 ml of tetraethoxysilane, 45 ml of α, α, α-trichlorotoluene were added to each pot under nitrogen atmosphere, and the mixture was pulverized for 40 hours. 300 g of the co-pulverized product thus obtained was put into a 5 L flask, 1.5 L of titanium tetrachloride and 1.5 L of toluene were added, followed by stirring at 100 DEG C for 30 minutes, followed by removal of the clearest liquid. 1 liter of toluene was added, and it stirred for 30 minutes at 100 degreeC, the clearest liquid was removed again, and the obtained solid content was wash | cleaned repeatedly with n-hexane, and the transition metal catalyst slurry was obtained. One part was sampled and the titanium of solid content was analyzed and it was 1.9 wt%.

40 ml of toluene under nitrogen atmosphere, 20 mg of the transition metal catalyst, 0.128 ml of diethyl aluminum chloride, 0.06 ml of methyl p-toluate and 0.20 ml of triethyl aluminum were added to a 200 ml inner pressure glass autoclave, followed by vinylsilane 2.0. g was charged, and then propylene was charged until it became 5 kg / cm < 2 > and polymerized at 70 DEG C under constant pressure for 2 hours. The slurry was then taken out, filtered and dried to give 43 g of powder. The obtained powder had an intrinsic viscosity (hereinafter abbreviated as n) of 1.45 dl / g as measured by a tetralin solution at 135 ° C. and a melting point by raising or lowering to 10 ° C./min using a differential thermal analyzer. And the crystallization temperature was measured as the maximum peak temperature. The melting point was 156 ° C and the crystallization temperature was 118 ° C. Moreover, according to this elemental analysis, it contained 1.6 wt% of vinylsilane units.

In addition, propylene and a small amount of ethylene were polymerized in the same manner as in the above polymerization, and the extraction residual ratio when the ethylene content was 2.5 wt%, n was 1.60 dl / g and extracted with a soxhlet extractor (hereinafter abbreviated as II, powder after extraction A random copolymer of propylene and ethylene having 91.5% and melting point of 154 ° C. was obtained by expressing the weight / weight of the powder before extraction in 100 fractions).

To the copolymer powder of propylene and ethylene obtained here, 10 g of the random copolymer of propylene and vinylsilane obtained above, 0.2 g of a phenolic stabilizer and 0.3 g of calcium stearate were added and granulated to obtain a resin composition for adhesion. In order to measure the adhesive strength, a sheet 0.2 mm thick of Ebar (Craye Co., Ltd.) and a copolymer of propylene and ethylene 0.2 mm thick (manufactured by copolymerization of propylene and ethylene) The sheet (thickness 0.1mm) of the said resin composition for adhesion | attachment was sandwiched in between, and it crimped at 220 degreeC, 4g / cm <2>, 3min. The peeling strength of the multilayer sheet (using an Instron tensile tester and measuring a T-type peeling strength at a tensile rate of 100 mm / min at 23 ° C. for a 2.5 cm wide test piece) was 2 kg / cm or more.

As a contrast, the experiment was repeated with the addition of the propylene-vinylsilane copolymer in the same manner as the above method, but spontaneously peeled, the adhesive strength could not be measured.

Example 2

In the same manner as in the polymerization method of Example 1, vinylsilane was not added, and propylene was polymerized instead of ethylene to obtain polyethylene having n of 1.75 dl / g. A sheet having a thickness of 0.2 mm and Evar obtained in the same manner by using a sheet (thickness of 0.1 mm) obtained by mixing the polyethylene and the propylene and vinyl silane obtained in Example 1 in the same manner as in Example 1 as an adhesive layer Adhesion test with the sheet was conducted and the peel strength was 2 kg / cm or more.

As a contrast, the experiment was repeated with the addition of the copolymer of propylene and vinylsilane in the same manner as in the above method, but due to natural peeling, the adhesive strength could not be measured.

Example 3

In the same manner as in Example 1, in the copolymerization, allylsilane was used instead of vinylsilane to obtain a random copolymer of propylene and allylsilane having an allylsilane content of 2.1 wt%, a melting point of 152 ° C., n 1.28 dl / g, and Example 1. As evaluated in the same manner, the peel strength was 2 kg / cm or more.

Example 4

Ethylene was used instead of propylene in Example 1 to perform random copolymerization of ethylene and vinylsilane.

40 ml of toluene under nitrogen atmosphere, 50 mg of the transition metal catalyst obtained in Example, 0.128 ml of diethyl aluminum chloride, 0.06 ml of methyl p-toluate, and 0.20 ml of triethyl aluminum were added to a 200 ml inner pressure glass autoclave. Next, 4.0 g of vinylsilane was press-fitted, charged with hydrogen until 0.2 kg / cm 2 and ethylene became 1 kg / cm 2, and polymerized at 70 ° C. under constant pressure for 2 hours. The slurry was then taken out, filtered and dried to obtain 6.3 g of powder. The melting point and crystallization temperature were measured, and the powder obtained was a copolymer of ethylene-vinylsilane having n of 1.81 dl / g and a melting point of 126 ° C and a crystallization temperature of 104 ° C.

In addition, elemental analysis revealed that the vinylsilane unit contained 1.3 wt%. Ethylene was further polymerized separately to obtain polyethylene with n of 1.88 dl / g.

To 200 g of the obtained polyethylene powder, 10 g of the random copolymer of ethylene and vinylsilane, 0.2 g of a phenolic stabilizer, and 0.3 g of calcium stearate were added and granulated to obtain a resin composition for bonding. The peeling strength was 2 kg / cm or more as evaluated in Example 1 using this composition.

As a contrast, the experiment was repeated with the addition of the copolymer of ethylene and allylsilane in the same manner as in the above method, but spontaneous peeling did not determine the adhesive strength.

Example 5

10 g of the ethylene and vinyl silane random copolymer obtained in Example 4 and 200 g of the propylene and ethylene polymerized in Example 1 were added with additives in the same proportion as in Example 4 to obtain a resin composition for bonding.

This composition was made into an adhesive layer, and the peeling strength was 2 kg / cm or more as the adhesion test of the sheet layer of the copolymer of propylene and ethylene obtained in Example 1, and the sheet layer of Evar similarly to Example 1.

Example 6

In the method of Example 4, copolymerization was carried out using allylsilane instead of vinylsilane to obtain a random copolymer of ethylene and allylsilane having an allylsilane content of 1.81 wt% and a melting point of 123 ° C and n 1.31 dl / g. The random copolymer of ethylene and arylsilane and polyethylene were assembled and evaluated in the same manner as in Example 4, and the peel strength was 2 kg / cm or more.

Example 7

2 parts by weight of the random copolymer of propylene and vinylsilane obtained in Example 1, 97 parts by weight of polypropylene having n of 1.65 dl / g and II of 97.1%, 0.1 part by weight of a phenolic stabilizer and 0.15 part by weight of calcium stearate The mixture was mixed for 5 minutes with a Hansell mixer, and then assembled at 220 ° C. with an extruder of 20 mmΦ. The pellet thus obtained was compression molded at 220 ° C. and 100 kg / cm 2 to obtain a sheet having a thickness of 200 μm. In order to measure the adhesive strength, this sheet was laminated with an aluminum plate having a thickness of 100 µm degreased with acetone in the order of an aluminum plate-sheet-aluminum plate, pressurized at 10 kg / cm 2 at 220 ° C. for 10 minutes, and cooled to obtain a laminate. The peeling strength of this laminated sheet was 1.8 kg / cm.

As a contrast, the experiment was repeated with the addition of the random copolymer of propylene and vinylsilane in the same manner as in the above method, but the adhesive strength could not be measured due to natural peeling.

Example 8

In the method of Example 7, except that the random polymer of propylene and allyl silane obtained in Example 3 was used instead of the random copolymer of propylene and vinylsilane, it mixed and granulated with polypropylene similarly to Example 7. The obtained pellets were evaluated in the same manner as in Example 7, and the peel strength was 1.6 kg / cm.

Example 9

The peeling strength which measured the adhesive strength with the galvanized plate (JIS-J-3302) by operation similar to Example 7 using the sheet | seat (0.1 mm in thickness) obtained in Example 7 as the adhesive layer was 1.1 kg / cm.

As a contrast, the experiment was repeated with the addition of the random copolymer of propylene and vinylsilane in the same manner as in the above method, but spontaneous peeling did not determine the adhesive strength.

Example 10

Using the sheet obtained in Example 8 as the adhesive layer, the adhesive strength with the soft iron plate was measured in the same manner as in Example 7, and the peel strength was 1.7 kg / cm.

As a contrast, the experiment was repeated with the addition of the random copolymer of propylene and vinylsilane in the same manner as in the above method, but spontaneous peeling did not determine the adhesive strength.

Example 11

10 g of a propylene and vinylsilane random copolymer obtained in Example 1 and 200 g of a polyethylene powder obtained by separately polymerizing ethylene with the catalyst of Example 1 obtained with n of 1.88 dl / g, 0.2 g of a phenolic stabilizer and stearic acid 0.3 g of calcium was added and granulated to obtain a resin composition for coating. In order to measure the coating strength, the composition was again compression molded at 220 ° C. and 40 kg / cm 2 to obtain a sheet having a thickness of 1 mm. Two kinds of paint (A urethane-based paint Orester-Q 182 (manufactured by Japan Mitsui Oatsugagaku Co., Ltd., brand name), acrylic paint uni-rock (Rock Paint Co., Ltd. brand name) to this sheet Apply with a brush, and then bake it in an air oven for 30 minutes at 60 ° C. Dry the coated film using the method of JIS K-5400 (Cross Cellophane Tape Test Method, CROSS HATCH TEST). As a result of measurement, the remaining number of the checkerboard coating film was 100 (all 100 checkerboard, the same applies below).

As a contrast, the experiment was repeated in the same manner as in the above method, omitting the addition of a random copolymer of propylene and vinylsilane. In this case, the remaining number of checkerboard coatings were 5 and 10.

Example 12

At the time of copolymerization, the allylsilane content obtained in the same manner as in Example 4 was 1.7 wt%, the melting point was 126 ° C, and n was 0.48 dl / g, except that the content of hydrogen was 0.1 kg / cm 2 using allylsilane instead of vinyl silane. A random copolymer of phosphorus ethylene and allylsilane was used and evaluated in the same manner as in Example 11 except that a copolymer of ethylene and butene-1 (butene-1 content 6.5 wt%) was used as the polyolefin. 100 was good in all cases.

In contrast, the experiment was repeated in the same manner as in the above method, omitting the addition of ethylene and allylsilane copolymer. In this case, the remaining number of checkerboard coatings was five or ten.

Example 13

40 ml of toluene under nitrogen atmosphere, 50 mg of the transition metal catalyst obtained in Example 1, 0.028 ml of diethylaluminum chloride 0.128 ml p-toluate and 0.20 ml of triethyl aluminum were added to a 200 ml inner pressure glass autoclave. 4.0 g of silane was press-fitted, charged with hydrogen until 0.2 kg / cm 2 and ethylene became 1 kg / cm 2, and polymerized at a constant pressure at 70 ° C. for 2 hours. Thereafter, the slurry was taken out, filtered and dried to obtain 63 g of a powder. n was a random copolymer of crystalline ethylene and vinylsilane of 1.81 dl / g, melting point of 126 ° C, and crystallization temperature of 104 ° C. In addition, elemental analysis revealed that the vinylsilane unit contained 1.3 wt%. Ethylene was further polymerized to obtain polyethylene having n of 1.88 dl / g.

Except for using 10 g of the random copolymer of ethylene and vinyl silane in 200 g of the obtained polyethylene powder, the resin composition for the coating film was evaluated in the same manner as in Example 11, and the remaining number of the checker coating film was 100.

As a contrast, the experiment was repeated in the same manner as in the above method, omitting the addition of a random copolymer of ethylene and vinylsilane. In this case, the remaining number of checkerboard coatings was five or ten.

Example 14

Polypropylene (Japanese Mitsui Tooatsu Chemical Co., Ltd.) was used as a polyolefin using a random copolymer of ethylene and allylsilane having an allylsilane content of 1.7 wt% obtained in Example 12, a melting point of 126 ° C, and n of 1.48 dl / g. Was evaluated in the same manner as in Example 11 using Mitsui-no-Brene JHH-G), and the remaining number of the checkerboard coating film was 100.

In contrast, the experiment was repeated in the same manner as in the above method, omitting the addition of a random copolymer of ethylene and allylsilane. In this case, the remaining number of the checkerboard coating was five or five.

Example 15

In the method of Example 14, the experiment was repeated in the same manner except that the amount of the random copolymer of ethylene and allylsilane was 5 g. The remaining number of the checker coating films was 85 and 90, respectively.

Example 16

When 0.1 g of lithium ethoxide was further added, the experiment was repeated and evaluated in the same manner as in Example 15, and the remaining number of the checker coating film was 100.

As a contrast, the experiment was repeated in the same manner as in the above method, omitting the participation of the random copolymer of ethylene and arylsilane. In this case, the remaining number of the checkerboard film was five.

Example 17

In the method of Example 1, it polymerized using only propylene without adding a vinylsilane, and obtained polypropylene whose n is 1.65 dl / g and II is 97.1%.

To 200 g of the obtained polypropylene powder, 10 g of a random copolymer of propylene and vinyl silane of Example 1, 0.2 g of a phenol stabilizer and 0.3 g of calcium stearate were added and granulated to obtain a resin composition for a coating film. As in Example 11, the remaining number of checkers was 100.

As a contrast, the experiment was repeated in the same manner as in the above method, omitting the addition of a random copolymer of propylene and vinylsilane. The remaining number of checkerboard films in this case was 5 and 10, respectively.

Example 18

In the method of Example 17, the experiment was repeated in the same manner except that the amount of the random copolymer of propylene and allylsilane was 5 g, and the remaining number of the checker coating films was 90 and 95, respectively.

Example 19

After the adhesive resin composition obtained in Example 18 was formed into a sheet shape, the resultant was treated for 1 hour at 40 ° C. in ethanol, and then evaluated in the same manner as in Example 11, and the remaining number of checkerboard eyes was 100 pieces.

Example 20

To a 200 ml internal pressure glass autoclave, 40 ml of toluene under nitrogen atmosphere, 50 mg of the transition metal catalyst obtained in Example 1, 0.128 ml of diethyl aluminum chloride, 0.06 ml of methyl p-toluate and 0.20 ml of triethyl aluminum were added. 4.0 g of vinyl trichlorsilane was press-fitted, propylene was charged until it became 5 kg / cm <2>, and it superposed | polymerized at 70 degreeC by the constant pressure for 2 hours. The slurry was then taken out, filtered and dried to obtain 28 g of powder. The obtained powder was a crystalline propylene copolymer having n of 1.4 dl / g and a melting point of 148 ° C and a crystallization temperature of 102 ° C. In addition, the elemental analysis contained 1.8 wt% of vinyl trichlorsilane units. In addition, propylene was polymerized separately to obtain polypropylene having n of 1.65 dl / g II of 97.1%.

To the obtained polypropylene powder, 20 g of the random copolymer of propylene and vinyl trichlorsilane, 0.9 g of phenolic stabilizer and 1.35 g of calcium stearate were added and granulated to obtain a resin composition for coating, similarly to Example 11 As evaluated, the remaining number of checkerboard coatings was 100.

As a contrast, the experiment was repeated in the same manner as in the above method, omitting the addition of a random copolymer of propylene and vinyltrichlorsilane. The remaining number of checkerboard films in this case was five and five, respectively.

Example 21

The experiment was repeated in the same manner as in Example 20 except that 10 g of the random copolymer of propylene and vinyl trichlorsilane was used, and the remaining number of checkerboard coating films was 70 and 80, respectively.

Example 22

The resin composition for adhesion obtained in Example 21 was formed into a sheet shape, and then treated at 40 ° C. for 1 hour in ethanol, and then evaluated in the same manner as in Example 11, and the remaining number of the checkerboard coating film was 100.

As a contrast, the experiment was repeated in the same manner as in the above method, omitting the addition of a random copolymer of propylene and vinyltrichlorsilane. In this case, the remaining number of the checkerboard film was 5 pieces each.

Example 23

Example 20 A random copolymer of propylene and allyl trichlorsilane obtained by using allyl trichlorsilane instead of vinyl trichlorsilane, having an allyl trichlor silane content of 2.3 wt% and a melting point of 135 ° C., 1.34 dl / g, was used. Thus, the experiment was repeated and evaluated in the same manner as in Example 20, and the remaining number of the checkerboard coating film was 100.

Claims (12)

A polyolefin resin composition for adhesion and painting containing a random copolymer obtained by copolymerizing α-olefin and alkenylsilane in the presence of a catalyst composed of a transition metal compound and an organic metal compound. The polyolefin resin composition according to claim 1, wherein the content of alkenylsilane in the copolymer is in the range of 1 wtppm to 30 wt%. The polyolefin resin composition according to claim 1, wherein the molecular weight of the random copolymer is in the range of 0.1-10 as the intrinsic viscosity measured with a 135 ° C tetralin solution. The polyolefin resin composition according to claim 1, which is blended with a homopolymer or copolymer of alpha -olefin containing no alkenylsilane. The adhesive polyolefin resin composition according to claim 1, wherein the amount of alkenylsilane in the composition is in the range of 1 wt% to 1 wt%. The coating polyolefin resin composition according to claim 1, wherein the amount of alkenylsilane in the composition is in the range of 1 wt% to 1 wt%. The alkenylsilane of claim 1, wherein the alkenylsilane is represented by the general formula CH 2 = CH— (CH 2) n SiHmR _3-m (wherein n represents 0-12, m represents 1-3 and R represents a methyl group or a phenyl group) or general A polyolefin resin composition represented by the formula CH 2 = CH— (CH 2) n SiHp Cl 3 -p where n represents 0-12 and p represents 0-3. The polyolefin resin composition according to claim 1, wherein the alkenylsilane is selected from vinylsilane, allylsilane, butenylsilane, and pentenyl silane. The polyolefin resin composition according to claim 1, wherein the α-olefin is selected from ethylene, propylene, butene-1, pentene-1, hexene 1, 2-methylpentene-1 and octene-1. The polyolefin resin composition according to claim 1, wherein the transition metal compound is titanium halide or vanadium halide, and the organic metal compound is an organoaluminum compound. A polyolefin resin composition containing a random copolymer obtained by copolymerizing α-olefin and alkenyl silane in the presence of a catalyst composed of a transition metal compound and an organometallic compound. Bonding method. A method for coating a polyolefin molding comprising using a polyolefin resin composition containing a random copolymer obtained by copolymerizing α-olefin and alkenyl silane in the presence of a catalyst composed of a transition metal compound and an organic metal compound.