JPS61103970A - Adherent polyolefin resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved adhesiviness to a base material, useful for covering the surface of the base material, obtained by subjecting a polyolefin resin to graft polymerization with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride to graft the polyolefin resin, and blending it with a specific amount of a vinyl chloride resin. CONSTITUTION:Polyolefin resin is subjected to graft polymerization with 0.01-1.0wt% unsaturated carboxylic acid or unsaturated carboxylic acid anhydride (preferably maleic anhydride) to give a modified polyolefin resin. 95-20pts. wt. of the modified polyolefin resin is blended with 5-80pts.wt. vinyl chloride resin (preferably having 650-1,300 polymerization degree), to give the aimed composition. EFFECT:The resin composition has no blocking properties when it is made into a film and it has improved workability. USE:An adhesive between layers of a base material and another base material (most preferably bonding steel pipe to vinyl chloride resin pipe, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an adhesive polyolefin resin composition.

[Conventional technology]

Vinyl chloride resin has many excellent properties such as toughness and transparency, and due to the use of plasticizers such as dioctyl phthalate, it can have a wide range of properties from highly rigid hard products to flexible soft products. Can be made into films, sheets,
It is used in a wide range of applications such as molded products.

However, as can be seen from the table, vinyl chloride resins having the above-mentioned excellent properties have the drawback of extremely poor adhesion to other base materials, such as synthetic resins, metals, or wood. Various attempts have been made to improve this adhesiveness.

For example, ■ A method of applying a known adhesive such as an acrylic adhesive or an epoxy adhesive; ■ A method of applying ethylene-vinyl acetate copolymer or tackification thereof with rosin, indene, coumaro/, modified rosin, aromatic petroleum resin, etc. (1) Method of using a modified ethylene-vinyl acetate copolymer by graft polymerization of unsaturated carboxylic acid or its anhydride as an adhesive layer (Japanese Patent Application Laid-Open No. 2002-120002) 47J Coro issue), ■ A method using a mixture of carboxylated ethylene-vinyl acetate copolymer with petroleum resin as an adhesive layer (see JP-A-Sho!3-/El,!3), ■ Ethylene-vinyl acetate A method in which a mixture of a copolymer and polyethylene is modified by graft polymerization of an unsaturated carboxylic acid or its anhydride as an adhesive layer (see JP-A-54-tO); Alternatively, a method in which a mixture of ethylene-vinyl acetate copolymer and aliphatic petroleum resin modified with anhydride is used as an adhesive layer (see JP-A-Sho!; 3-/27!; No. 4) , etc. have been proposed.

[Problem that the invention seeks to solve]

The above method (■) has insufficient adhesion and is difficult to apply.
It requires complicated steps such as drying and drying, which is complicated to operate, and there is also the problem of deterioration of the working environment due to the use of organic solvents. In addition, the above-mentioned methods (1) to (2) have the problem that not only are the adhesive properties somewhat insufficient, but also that when the adhesive is formed into a film, the films tend to block each other, resulting in poor workability.

Furthermore, in methods (1) and (2) above, when the adhesive layer is formed into a film, it has the advantage of no blocking property and good workability, but there is a problem that the adhesiveness is somewhat insufficient.

[Means for Solving the Problems] The present inventors improved the above-mentioned conventional technology and conducted intensive studies to develop a new adhesive that can sufficiently bond the vinyl chloride resin and the base material. As a result, when a polyolefin resin modified by graft polymerization with an unsaturated carboxylic acid or its anhydride is blended with a specific amount of vinyl chloride resin, it has excellent adhesive properties and is made into a film. The present invention was completed by discovering that an adhesive with no blocking properties and excellent workability can be obtained.
.

That is, the gist of the present invention is to add an unsaturated carboxylic acid or its anhydride to a polyolefin resin at a concentration of 0.0/-/, 0.
Weight% graft polymerized modified polyolefin resin 95
- An adhesive polyolefin resin composition comprising parts by weight of a vinyl chloride resin s-go mixed with parts by weight of a vinyl chloride resin.

The present invention will be explained in more detail below.

The modified polyolefin resin used in the present invention is one in which a monomer or polymer of an unsaturated carboxylic acid or its anhydride is chemically bonded to a polyolefin resin, and the amount of the bond is that of the unsaturated carboxylic acid or its anhydride. 0 for polyolefin resin in terms of monomer
．． 07-/, 0% by weight.

If the amount of bonding is less than 0.07% by weight, the adhesive strength will be low; if it is more than 0% by weight, the smelly gel-like substance will increase;
Undesirable. Within this range, preferably θ, 0/
'% - 0.3% by weight, most preferably 0.0.7-0
．． It is 3% by weight.

Polyolefin resins used as raw materials in the present invention include high-density polyethylene, low-density polyethylene, medium-density polyethylene, ethylene-propylene copolymer, ethylene-butene-7 copolymer, polypropylene, glopylene-butene-1 copolymer Coalescence, polybutene-l, poly-e
-Methylpentene-1 and the like. Preferred polyolefin resins vary somewhat depending on the mode in which the composition of the present invention is used; for example, when the composition of the present invention is used as an adhesive between polyvinyl chloride and metal, a polyolefin resin with a density of 0 is preferred.
．． Low-density polyethylene or nidistomeric ethylene-propylene copolymers of 9/0 to 0.9 j , t are suitable.

On the other hand, as the unsaturated carboxylic acid or anhydride thereof to be graft-polymerized, acrylic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, or anhydride thereof is used. In particular, it is preferable to use maleic anhydride.

Thus, the modified polyolefin resin of the present invention can be produced by adding an unsaturated carboxylic acid or its anhydride to a polyolefin resin and causing a graft polymerization reaction according to a known method.

The reaction method for causing the graft polymerization reaction may be a solution method or a slurry method, but the melt-kneading method is economically preferable. When using the melt mixing method, the polyolefin resin contains 0.
07-1.9% by weight of unsaturated carboxylic acid or its anhydride and Q, not more than 1% by weight, preferably 0.00/-0
, 05% by weight of organic peroxide, /20℃~30℃
Melt-kneading at 0° C. is advantageous because a modified polyolefin resin with high grafting efficiency, no viscosities or gels, good color, and no odor can be obtained.

To further explain the above melt mixing method, if the amount of unsaturated carboxylic acid or its anhydride blended into the polyolefin resin is less than 0.07% by weight, the adhesive strength will be low, and if it is more than 0% by weight, it will cause an odor. Unfavorable because of the increase in gel-like substances. 0.07 to 0.5% by weight within the above range
is preferably 0.0.7 to 117. ．． 7% by weight is most preferred. If the amount of organic peroxide used is greater than o or i weight %, it is not preferable because gel-like substances and viscosities in the film increase and the molecular weight decreases significantly. There is no particular lower limit on the lower limit, but if it is less than 0.00/wt%, the grafting efficiency will decrease, and problems such as a decrease in adhesive strength or the odor of unreacted monomers will likely occur.
/ii: Desirably 1 or more.

Examples of organic peroxides include benzoyl peroxide, acetyl peroxide, di-t-butyl peroxide,
. Pat-7'-tyl peroxylaurate, dicumyl peroxide, α, α'-bis(1-butylperoxy)-p-
Diisopropylbenzene, co,S-dimethyl-λ,!
-bis(i-butylperoxy)hexane, t-7'' tylperoxybenzoate, n-butyl router, terbis(1-butylperoxy)valerate, octanoylperoxide, co, s-dimethylco, j-bis(benzoylperoxy)hexane, Vinyltris (t-butyl 7.

peroxy)silane, methylvinyl(cumylperoxy)silane, and the like.

In the melt-kneading method, polyolefin resin powder or pellets are triblended with an unsaturated carboxylic acid or its anhydride and, if necessary, an organic peroxide at a predetermined mixing ratio using a Henschel mixer, or an unsaturated compound is mixed with an organic solvent. A solution of carboxylic acid or its anhydride and, if necessary, an organic peroxide is sprayed onto polyolefin resin powder or pellets, and further blended using a Henschel mixer or the like. In the present invention, the unsaturated carboxylic acid or its anhydride used as the graft monomer is used in a smaller amount than in the conventional method, so when kneading it with the polyolefin resin, an organic solvent is used as described above to mix it uniformly. It is preferable to measure Such organic solvents include acetone,
Examples include methyl ethyl ketone and cyclohexanone. The blended polyolefin resin powder or pellets is put into a kneading machine whose interior is purged with nitrogen gas, such as a Banbury mixer, a double screw mixer, an extruder, etc., at a temperature of 10°C to 30°C for a time of 0.5°C. /~JO
Melt and knead in minutes. If the kneading temperature is less than iao° C., the graft reaction described below is unlikely to occur, and if it exceeds 300° C., thermal deterioration of the polyolefin resin becomes noticeable, which is not preferable.

Therefore, when a polyolefin resin is subjected to a graft reaction with an unsaturated carboxylic acid or its anhydride by the above-mentioned melt mixing method, the organic peroxide used as an initiator for the above-mentioned graft reaction is completely removed in the resulting modified polyolefin resin. Most of the unsaturated carboxylic acids or their anhydrides are chemically bonded to the polyolefin resin.

As the vinyl chloride resin used in the present invention,
Generally, the polymerization degree of vinyl chloride monomer is goo~a
, o o o, preferably 430~/,,7 o o
A copolymer of vinyl chloride and vinyl acetate with a polymerization degree of 3O, O~3. Oo.

Copolymers of ethylene-vinyl acetate copolymers grafted with vinyl chloride, copolymers of vinyl chloride with small amounts of monomers that can be copolymerized with vinyl chloride, such as ethylene, propylene, acrylic esters, and vinylidene chloride. Semi-rigid and flexible vinyl chloride resins plasticized with polymeric stellate plasticizers are also included. In addition, these vinyl chloride resins may be supplemented with fillers, polymer modifiers, pigments, heat stabilizers, light stabilizers, and other compounding agents that are commonly added during the molding process of vinyl chloride resins. Can be blended.

The blending ratio of each component above is modified polyolefin resin 9j-
20 parts by weight, preferably 90 parts by weight, and 5 parts by weight of vinyl chloride resin, preferably 20 to 6 parts by weight.
It is in the range of 0 parts by weight. If the amount of the vinyl chloride resin is less than the above 5 parts by weight, the adhesiveness will not be improved, while if it is more than the above 20 parts by weight, the adhesive strength will be significantly reduced, which is not preferable.

In addition, as for the method of blending each of the above components, the modified polyolefin resin and the vinyl chloride resin are mixed using a Henschel mixer.
A method of mixing in a V-shaped blender etc. and pelletizing by using an extruder, double screw mixer etc., or a method of blending the modified polyolefin resin and vinyl chloride resin in a Banbury mixer-1 twin-roll mixer and forming a sheet. Examples include a method of making pellets by using a cutter.

As described above, the composition of the present invention can be used as a surface coating for substrates or as an interlayer adhesive between substrates. For example, the composition of the present invention can be melt-extruded into a film or sheet using an extruder and laminated onto a base material, or it can be used by sandwiching the composition between two base materials and then heat-compression bonding. . The above base material includes vinyl chloride resin,
Examples include synthetic resins such as polyethylene, polystyrene, and polyamide resins, metals such as iron and aluminum, and cellulose-based natural materials such as wood, cotton, and hemp.

The composition of the present invention is particularly suitable for steel pipes and vinyl chloride wood.

It can be used for adhesion with fat pipes, adhesion between steel plates and vinyl chloride resin plates, adhesion between aluminum plates and vinyl chloride resin plates, adhesion between steel plates and steel plates, and as a laminating agent for co-axial stretching.

〔Example〕

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

In addition, the melt index (hereinafter abbreviated as MI) in the examples was measured in accordance with ASTM D-/CO, YR-R-TK1), and the shear adhesive strength was measured in accordance with JIS K.
bK! This was measured in accordance with 0. In addition, regarding the film blocking test, when a film wound on a roll is peeled off by hand, a film that can be easily peeled off is marked as O, a film that has a little resistance is marked as △, a film that has considerable resistance and a film that tears when peeled off is marked as ×. expressed.

Example/-j and Comparative Example 1 fil Production of resin composition High-pressure low-density polyethylene [density: 0.930f/
ad, M I: J, 2 f//0 min] lO
Parts by weight of O, 0.0 = 5 parts by weight of α,α'-bis(t-butylperoxy)-p-diisopropynetic benzene dissolved in a small amount of a7tone, and 0.30 parts by weight of maleic anhydride were mixed into a blender. Blend inside. This mixed pellet was extruded into pellets using an extruder with an inner diameter of 0% φ and L/D = 2 g at 3 oc. When maleic anhydride was quantified using an infrared absorption spectrum for a part of this pellet, it was found that 0.6 % by weight of maleic anhydride had been graft-polymerized.The maleic anhydride-modified low-density polyethylene pellets (MI: ha!r) thus obtained were
fP/ / 0 minutes), vinyl chloride resin [Nica Vinyl 5G-700 (trademark; manufactured by Hishiusu Co., Ltd.; vinyl chloride homopolymer, degree of polymerization qQo) too many parts by weight, 2.0 parts by weight of tin stabilizer, Lubricants, heavy ropes and plasticizers λ, Ot'J
ii: parts] were blended in a blender in the proportions shown in Table 1.

(2) Production of laminate The above blend is placed in a molding machine equipped with a small Koda extruder with a downward T-die attached to a small extruder with a diameter of 0.
A T-die film with a thickness of 0-/% was made using YuOO~KoniOC. Using this film as an adhesive, a galvanized steel plate (width: S, thickness: IIm) and a hard vinyl chloride resin plate [
365 parts by weight of lead stabilizer, parts by weight of metal soaps O and S, and 011 parts by weight of lubricant were kneaded with too parts by weight of Nika Vinyl 5a-too (trademark; manufactured by Ryoichi Co., Ltd.; vinyl chloride homopolymer pot polymerization degree goo). Made: 5mm width, thickness J
, a parrot], and after preheating at -00C for 3 minutes, thermocompression bonding was performed by holding at -00C and a pressure of 2oky/a/la for 5 minutes. The shear adhesive strength of the obtained laminate was measured using the method described above.

The results are shown in Table 1.

Comparative Examples C and 3 In Example 1, ethylene-vinyl acetate copolymer (vinyl acetate containing fk=
- weight t%, Ml-/sf//θ min) or modified ethylene-vinyl acetate copolymer grafted with maleic anhydride (maleic anhydride graft ik: 0./J
% by weight), and the same operation was performed except that no vinyl chloride resin was blended. The results are shown in Table 1.

Table l *l: Vinyl chloride vinyl resin board 2: Ethylene-vinyl acetate copolymer
Concern 3: Modified ethylene-vinyl acetate copolymer [Effects of the invention] According to the present invention, a specific amount of vinyl chloride-based w fat is added to a polyolefin resin modified by graft polymerization with an unsaturated carboxylic acid or its anhydride. The resin composition obtained by blending has particularly excellent adhesion to substrates compared to conventional ones, and when the resin composition is made into a film, it has no blocking property and has excellent workability.

Therefore, the resin composition of the present invention can be used as a surface coating for a substrate.
It can also be widely used as an interlayer adhesive between base materials.

Patent applicant: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - 1 other person

Claims (1)

[Claims] (1) 5 to 80 parts by weight of a vinyl chloride resin is mixed with 95 to 20 parts by weight of a modified polyolefin resin obtained by graft polymerizing 0.01 to 1.0% by weight of an unsaturated carboxylic acid or its anhydride to a polyolefin resin. An adhesive polyolefin resin composition.