JPH0532737A - Adhesive polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having adhesivity especially to polypropylene by graft-polymerizing a styrene derivative, etc., to a copolymer of propylene and an alpha-olefin and dissolving the obtained copolymer in a solvent. CONSTITUTION:The objective composition is produced by graft-polymerizing (A) a styrene derivative (e.g. styrene) or an acrylic acid derivative (e.g. methacrylic acid) to (B) a copolymer composed of (i) 95-50wt.% of propylene and (ii) 5-50wt.% of a >=4C alpha-olefin (e.g. 1-butene) in the presence of a radical polymerization initiator at 50-300 deg.C and dissolving the obtained olefin polymer in a solvent selected from a 6-20C hydrocarbon and a halogenated hydrocarbon compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having adhesiveness to polyolefin, especially polypropylene. Specifically, it relates to an adhesive polyolefin resin composition in which a specific copolymer is dissolved.

[0002]

2. Description of the Related Art Polypropylene is an inexpensive resin having excellent heat resistance and rigidity, but it is extremely difficult to bond other polymers to the surface of a molded polypropylene product. Is applied to give adhesiveness.

[0003]

A composition containing a chlorinated polyolefin has hitherto been used as an adhesive resin. However, when recovering and reusing a molded article or incinerating it to recover heat. Since those containing chlorine have various problems, it is desired to develop an adhesive composition containing no chlorine.

[0004]

[Means for Solving the Problems] The inventors of the present invention have made an earnest search for a resin composition containing no chlorine and having excellent adhesiveness, and found that a solution of a specific copolymer has excellent adhesiveness. Then, the present invention was completed.

That is, the present invention relates to an olefin obtained by graft-polymerizing a styrene derivative or an acrylic acid derivative onto a copolymer of 95 to 50% by weight of propylene and 5 to 50% by weight of an α-olefin having 4 or more carbon atoms. An adhesive polyolefin resin composition obtained by dissolving a copolymer in a solvent.

In the present invention, the copolymer of 95 to 50% by weight of propylene and 5 to 50% by weight of α-olefin having 4 or more carbon atoms can be obtained by using various Ziegler type catalysts. A copolymer obtained by polymerizing propylene and an α-olefin having 4 or more carbon atoms with a catalyst system that gives a polymer having a highly isotactic structure or a syndiotactic structure when polymerized is preferable.

As the α-olefin having 4 or more carbon atoms, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene and the like are preferably used. Further, as a catalyst used for the polymerization, a trivalent or tetravalent titanium halide, a transition metal catalyst supporting the same on various carriers, or two linked cyclopentadienyl groups or their derivatives as ligands A catalyst system comprising a metallocene compound such as zirconium, hafnium and titanium and an organometallic compound is preferably used.

Also, there is no limitation on the polymerization conditions, and the temperature is from room temperature to
It is carried out at a temperature of 200 ° C. and atmospheric pressure to 50 kg / cm ² . The polypropylene preferably has a molecular weight of about 0.1 to 10 as an intrinsic viscosity measured with a tetralin solution at 135 ° C.

In the present invention, the above copolymer is used by graft polymerization of a styrene derivative or an acrylic acid derivative. The method of graft polymerization is not particularly limited, and it is carried out by heating a mixture of an ordinary polymer, a monomer and a radical polymerization initiator. Even if it is graft polymerized in a molten state, it may be graft polymerized in a solution state. Available even if there is. Using peroxides as a radical polymerization initiator, the content of the monomer graft-polymerized by heating and mixing at 50 to 300 ° C is 0.1 to 50% by weight.
Those of a degree are preferably used.

What is important here is that the content of α-olefin in the copolymer and the content of the graft-polymerized monomer are within appropriate ranges so that the polymer becomes soluble in a hydrocarbon compound or a halogenated hydrocarbon compound at room temperature. Should be
Moreover, the copolymer of propylene and α-olefin is stereoregular.

The stereoregularity means that the peak assigned to each carbon of the spectrum as measured by ¹³ C-NMR consists mainly of one large peak.
Usually, the peak attributed to mmmm pentad or rrrr pentad appears as the main peak.

As the styrene derivative, one or more hydrogen atoms of styrene or its aromatic ring is an alkyl group,
Examples are those substituted with an alkoxy group, an amino group, a nitrile group, a nitro group, and the like. Examples of acrylic acid derivatives include acrylic acid or methacrylic acid or esters thereof, and examples of groups forming an ester include groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl and phenyl. To be done.

In the present invention, the above graft copolymer can be made into an adhesive composition by dissolving it in a solvent. As the solvent used here, a hydrocarbon compound having 6 to 20 carbon atoms or a halogenated hydrocarbon compound is preferably exemplified.

The composition of the present invention may further contain various additives which are usually added to polypropylene, such as stabilizers, ultraviolet absorbers, lubricants and surfactants.

[0015]

The present invention will be further described with reference to the following examples.

Example 1 Diphenylmethylene (cyclopentadienyl-1) obtained by lithiation of diphenylcyclopentadienyl-1-fluorenylmethane synthesized according to a conventional method, reaction with zirconium tetrachloride and recrystallization. -Fluorenyl) zirconium dichloride 0.01g and Tosoh Akzo Co., Ltd. methylaluminoxane (degree of polymerization 16.1) 0.6g, 300g of propylene and 1-
Introduce 338 g of butene, polymerize at 20 ° C. for 2 hours, then deash with methanol and methyl acetoacetate, wash with aqueous hydrochloric acid, and then filter and remove 205 g of syndiotactic propylene and 1-butene. A polymer was obtained.

According to ¹³ C-NMR of the polymer, a large peak attributed to the methyl group of propylene was observed at about 20.2 ppm, and the content of 1-butene was 32.0% by weight. 135 ° C
Intrinsic viscosity measured with tetralin solution (hereinafter abbreviated as η)
Was 1.98, and the molecular weight distribution (MW / MN) measured with 1,2,4-trichlorobenzene was 2.2.

Graft polymerization of styrene was carried out using this copolymer. 500 ml of toluene and 42 g of the above copolymer were placed in a glass reactor having an internal volume of 1 liter equipped with a retreating blade, the inside of the reactor was replaced with nitrogen, the temperature was raised to 90 ° C, and 100 ml of toluene was stirred at 200 rpm. A solution prepared by dissolving 5 g of dicumyl peroxide and a solution prepared by dissolving 9.9 g of styrene in 100 ml of toluene were introduced through the dropping funnel over 3 hours. After the introduction, the reaction was continued for another 2 hours. After cooling, a part of the solution was precipitated with a large amount of methanol and separated to take out a polymer. When this polymer was extracted with boiling methyl ethyl ketone and the extraction residue was analyzed, the graft ratio was 8.5.
% By weight. Further, η was 1.30.

The toluene solution of the polymer thus obtained was applied as it was to a polypropylene sheet (polypropylene manufactured by Mitsui Toatsu Chemicals, Inc., molded from Mitsui Noblen BJHH-M, trade name), and a cloth (trade name Toray Retron) was applied on the coating film. Put TS-303B (made by Toray Industries, Inc.) on the glass rod, press it with a glass rod, heat it in an air oven at 80 ° C for 30 minutes, and then leave it for 24 hours, then use a tensile tester to pull at a speed of 50 mm / min. A 180-degree peel test showed that the peel strength was 450 g / 25 mm. Further, when a cross-cut peeling test was performed according to JIS-5400, the adhesion was 100/100.

Example 2 1-Hexene was used instead of 1-butene in the copolymerization.
-A copolymer having a hexene content of 30% by weight was obtained, and acrylic acid was graft-polymerized to obtain a copolymer having an η 1.70 and an acrylic acid content of 6.2% by weight. When the same evaluation was performed using this copolymer solution, a peel strength of 430 g / 25 mm 2 and 100/100 was exhibited.

Comparative Example 1 Commercially available chlorinated polypropylene (Sanyo Kokusaku Pulp Co., Ltd.)
A similar test was carried out using a product name, Super Clone 803MW manufactured by K.K., and a peel strength of 405 g / 25 mm, 100/100 was shown.

[0022]

EFFECT OF THE INVENTION The composition of the present invention has the same adhesive strength as that of the conventionally known composition, but the polymer does not contain halogen at all, and it is advantageous in its use and regeneration and is industrially extremely useful. worth it.

Claims (1)

Claims: 1. Obtained by graft-polymerizing a styrene derivative or an acrylic acid derivative onto a copolymer of 95 to 50% by weight of propylene and 5 to 50% by weight of an α-olefin having 4 or more carbon atoms. An adhesive polyolefin resin composition obtained by dissolving an olefin copolymer in a solvent.