JP3132764B2 - Adhesive polyolefin resin composition - Google Patents

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 an adhesive property to polyolefin, particularly to polypropylene. Specifically, the present invention 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 product of polypropylene. Is applied to impart adhesiveness.

[0003]

Conventionally, a composition containing a chlorinated polyolefin has been used as the adhesive resin. Those containing chlorine have various problems and development of an adhesive composition not using chlorine is desired.

[0004]

Means for Solving the Problems The present inventors diligently searched for a resin composition which does not contain chlorine and has excellent adhesiveness. It has been found that a solution of a specific copolymer has excellent adhesiveness. And completed the present invention.

That is, the present invention relates to an olefin obtained by graft-polymerizing 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 with a styrene derivative or an acrylic acid derivative. An adhesive polyolefin resin composition obtained by dissolving a copolymer in a solvent.

In the present invention, 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 can be obtained by using various Ziegler catalysts. When polymerization is performed, a copolymer obtained by polymerizing propylene and an α-olefin having 4 or more carbon atoms using a catalyst system that gives a polymer having a highly isotactic structure or a syndiotactic structure is obtained. 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. The catalyst used for the polymerization may be a trivalent or tetravalent titanium halide, a transition metal catalyst having the same supported on various carriers, or two linked cyclopentadienyl groups or derivatives thereof as ligands. A catalyst system comprising a metallocene compound such as zirconium, hafnium or titanium and an organometallic compound is preferably used.

[0008] The polymerization conditions are also not limited and are at room temperature to
It is carried out at a temperature of 200 ° C. and normal pressure to 50 kg / cm ² . As the molecular weight of polypropylene, one having an intrinsic viscosity of about 0.1 to 10 dl / g measured with a tetralin solution at 135 ° C. is preferably used.

In the present invention, a copolymer obtained by graft-polymerizing a styrene derivative or an acrylic acid derivative to the above copolymer is used. The method of the graft polymerization is not particularly limited, and is carried out by heating a mixture of a normal polymer, a monomer and a radical polymerization initiator, and even if the graft polymerization is performed in a molten state, the graft polymerization is performed in a solution state. Available even if there is. A peroxide is used as a radical polymerization initiator, and the content of the monomer graft-polymerized by heating and mixing at 50 to 300 ° C is 0.1 to 50% by weight.
A degree is preferably used.

What is important here is that the content of the α-olefin of the copolymer and the content of the graft-polymerized monomer are adjusted within an appropriate range so that the polymer is soluble at normal temperature in the hydrocarbon compound or the halogenated hydrocarbon compound. Must be
Moreover, the copolymer of propylene and α-olefin is stereoregular.

The term "stereoregularity" as used herein means that the peak attributed to each carbon in the spectrum as measured by ¹³ C-NMR mainly comprises one large peak,
Usually, a peak belonging to the mmmm pentad or the rrrr pentad appears as a main peak.

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

In the present invention, the above graft copolymer can be dissolved in a solvent to form an adhesive composition. Preferred examples of the solvent used herein include a hydrocarbon compound having 6 to 20 carbon atoms or a halogenated hydrocarbon compound.

The composition of the present invention may further contain various additives usually added to polypropylene, such as a stabilizer, an ultraviolet absorber, a lubricant, and a surfactant.

[0015]

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

Example 1 Diphenylmethylene (cyclopentadienyl-1) obtained by lithiating diphenylcyclopentadienyl-1-fluorenylmethane synthesized according to a conventional method, reacting with zirconium tetrachloride and recrystallizing. -Fluorenyl) Using 0.01 g of zirconium dichloride and 0.6 g of methylaluminoxane (degree of polymerization 16.1) manufactured by Tosoh Akzo Co., Ltd., 300 g of propylene and 1-
After charging 338 g of butene and polymerizing at 20 ° C. for 2 hours, the mixture was decalcified with methanol and methyl acetoacetate, washed with an aqueous hydrochloric acid solution, and then filtered to obtain 205 g of a copolymer of propylene having a syndiotactic structure and 1-butene. A polymer was obtained.

According to ¹³ C-NMR of the polymer, a large peak attributed to a 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 dl / g , and the molecular weight distribution (MW / MN) measured with 1,2,4-trichlorobenzene was 2.2.

Using this copolymer, styrene was graft-polymerized. 500 ml of toluene and 42 g of the above copolymer were placed in a 1-liter glass reactor equipped with swept wings, and the inside of the reactor was purged with nitrogen. The temperature was raised to 90 ° C., and 100 ml of toluene was stirred while stirring at 200 rpm. A solution of 5 g of dicumyl peroxide and a solution of 9.9 g of styrene in 100 ml of toluene were introduced from a 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. The polymer was extracted with boiling methyl ethyl ketone and the extraction residue was analyzed.
% By weight. Η was 1.30 dl / g .

The toluene solution of the polymer thus obtained is applied as it is to a polypropylene sheet (made by Mitsui Toatsu Chemicals, Inc., trade name: Mitsui Noblen BJHH-M), and a cloth (trade name: Toletetron, trade name) Put TS-303B (made by Toray Industries, Inc.), hold it with a glass rod, heat it in an air oven at 80 ° C. for 30 minutes, then leave it for 24 hours, and use a tensile tester to pull it at a speed of 50 mm / min. When a 180 ° peel test was carried out, a peel strength of 450 g / 25 mm was shown. A cross-cut peel test according to JIS-5400 showed an adhesion of 100/100.

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

Comparative Example 1 Commercially available chlorinated polypropylene (Sanyo Kokusaku Pulp Co., Ltd.)
The same test was carried out using a product manufactured by Supercron 803 MW (trade name), 405 g / 25 mm, 100/10
A peel strength of 0 was shown. Comparative Example 2 In the copolymerization, ethylene was used instead of 1-butene,
Propylene-ethylene copolymer with 5% by weight of
Obtained. Except that this copolymer was used, the procedure was the same as in Example 1.
Styrene content 7.5% by weight, η 1.50 dl / g
A graft copolymer was obtained. Using this copolymer,
When the strike was carried out, 110 g / 25 mm, 30/1
The degree of adhesion was only 00. Comparative Example 3 Instead of copolymerization of propylene and 1-butene,
The styrene content was the same as in Example 1 except that
6.0% by weight, η1.25 dl / g graft copolymer
I got A similar test was conducted using this copolymer.
Roller, 40g / 25mm, adhesion degree of 10/100
And did not substantially adhere.

[0022]

Industrial Applicability The composition of the present invention has the same adhesive strength as that of the conventionally known composition, but the polymer does not contain any halogen, which is advantageous in its use and regeneration and is extremely industrially useful. worth it.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 255/02 C09D 151/06

Claims (1)

(57) [Claims] An olefin copolymer obtained by graft-polymerizing 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 with a styrene derivative or an acrylic acid derivative. Is dissolved in a solvent.