JPS61235438A - Polyolefin polymer molding having adhesive film - Google Patents

Abstract

PURPOSE:To obtain the title molding which can strengthen the adhesion of a paint, adhesive or the like applied to its surface, by providing a hydrocarbon polymer film and a specified reactive film on the surface of a polyolefin polymer molding. CONSTITUTION:A polymer molding consisting of a polyolefin polymer molding (a), a film (b) formed by coating on the surface of said molding and comprising a hydroxyl group-containing hydrocarbon polymer in which the main chain is saturated or partially saturated and a reactive film (c) formed by applying on the surface of said film and comprising either a compound containing a bond of the formula (wherein X is a halogen) in the molecule or an alkyl hypohalite.In this molding the hydroxyl group-containing hydrocarbon polymer film can be activated by the halogens in the reactive film, so that it is possible to obtain an adhesive film having excellent adhesion to polyolefin polymers and various paint and adhesives.

Description

Detailed Description of the Invention Object of the Invention (Field of Industrial Application) The present invention relates to a polyolefin polymer molded article having an adhesive coating that strengthens the adhesion of paints, adhesives, etc. applied to the surface. It is.

(Prior art) Polyolefin polymers, such as ethylene-propylene-diene terpolymer rubber (EPDM) and ethylene-
Polyolefin-based vulcanized rubber such as propylene copolymer rubber (EPM) or polyolefin-based synthetic resin such as polypropylene (PP) and polyethylene (PE) are similar to natural rubber (NR) and styrene-butadiene copolymer rubber (S).
BR), polybutadiene rubber (BR), isobutylene-
Synthetic rubbers such as isoprene copolymer rubber (IIR), polychloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), and polyisoprene rubber (IR), or ABS resin, polystyrene resin (PS),
Compared to synthetic resins such as acrylonitrile-styrene copolymer resin (AS) and ethylene-vinyl acetate copolymer resin (EVA), it has excellent characteristics such as superior performance in terms of weather resistance, aging resistance, and ozone resistance. Because it is a polymer with
Nowadays, it is used in many fields.

(Problem to be solved by the invention) However, the above EPDM-? ) Polyolefin-based vulcanized rubber such as EPM or polyolefin-based synthetic resins such as PP and PR do not contain polar groups in the main chain of their molecules, so even if paint or adhesive is applied to the surface, the coating will not occur. The disadvantage is that the film is easily peeled off. Therefore, it is currently extremely difficult to coat these polyolefin polymers, or to adhere them to each other or to metals.

Although many countermeasures have been attempted in the past to address these drawbacks, no satisfactory solution has yet been found.

As a result of repeated research on the adhesive properties of the above-mentioned polyolefin-based polymers, the present inventors have discovered an adhesive composition that has sufficient adhesion to the same polymer and various paints and adhesives, and have arrived at the present invention. It is something.

Structure of the Invention (Means for Solving Problems) That is, the present invention provides (1) a polyolefin polymer molded product, and (2) a polyolefin-based polymer molded product whose main chain containing a hydroxyl group is saturated or partially coated on the surface of the molded product. (3) a reactive coating made of either a compound in the molecule or an alkyl hypohalide, which is coated on the surface of the coating. The above-mentioned problems were solved by devising a polyolefin polymer molded article with an adhesive coating.

(Function) Since the polyolefin polymer does not contain a polar group in the main chain of its molecules, it is difficult for paints, adhesives, etc. to adhere to it as described above.

Therefore, a coating made of the hydroxyl group-containing hydrocarbon polymer is provided on the surface of a molded product made of the same polymer, and further, a coating containing a 10-N- bond (in the formula, X is a halogen) in the molecule is added to the coating. By providing a reactive coating made of a compound or an alkyl hypohalide, the hydroxyl group-containing hydrocarbon polymer coating is activated by the halogen in the reactive coating, making it excellent against polyolefin polymers and various paints and adhesives. It is possible to obtain an adhesive film with excellent adhesion.

(Example) Hereinafter, the structure of the polyolefin polymer molded article with an adhesive coating will be described in detail.

First, a hydrocarbon polymer with a saturated or partially saturated main chain containing a hydroxyl group is one that contains one or more, preferably 1.8 to 5.0, hydroxyl groups in the monomer molecule, and whose main chain is saturated or partially saturated. Polyhydroxypolybutadiene polymer with saturated or partially saturated chains and an average molecular weight of 500 to 50,000, preferably 100 to 20,000
695), or polyhydroxypolyolefins having an average molecular weight of 1,000 to 5,000 and having a hydroxyl group at the molecular end (Mitsubishi Chemical Industries type, "Polytail-H", "Polytail-HAJ"), etc.

In order to provide a coating made of these hydroxyl group-containing hydrocarbon polymers on the surface of the polyolefin polymer molded article, the hydrocarbon polymer may be diluted with a solvent to lower its viscosity and then applied. The solvents used at this time are saturated hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; chlorinated hydrocarbons such as ethyl chloride, chloroform, and carbon tetrachloride; acetic esters: The solvent is a solvent appropriately selected from ketones, etc., or a mixed solvent of two or more thereof.

When diluting with these solvents, the concentration of the hydroxyl group-containing hydrocarbon polymer is preferably 30% or less;
%, there is a risk that solid content will precipitate at room temperature.

Since the hydrocarbon polymer is a one-component type, it has a very long pot life, and if the viscosity increases due to evaporation of the solvent, the viscosity can be adjusted by adding the solvent again. In addition, no special equipment is required for the application method; dipping,
It can be easily applied using conventional painting methods such as spraying or brushing.

Next, alkyl hypohalides include normal, secondary or tertiary alkyl hypohalides, particularly stable tertiary alkyl chlorides and bromides.

Specifically, tertiary butyl hypochloride, tertiary butyl hypobromide, tertiary amyl hypochloride, tertiary amyl hypobromide, etc. are particularly preferred.
Further, halogen-substituted alkylhypochlorides such as dichloro, trichloro or fluoromethylhypochloride may be used.

Examples of compounds with a halogenated succinimide such as N-bromsuccinimide, incyanuric acid halides such as trichloroisocyanuric acid and dichloroisocyanuric acid, and further halogenated hydantoins such as dichlorodimethylhydantoin can be exemplified. .

To form an adhesive film on the surface of a polyolefin polymer molded product, the polyolefin polymer molded product coated with the hydroxyl group-containing hydrocarbon polymer is placed in the alkyl hypohalide or a solution containing a compound in the molecule at room temperature. You can simply dip it in water for 30 seconds to several minutes, or simply apply the same solution by spraying, brushing, etc.

This treatment halogenates the hydroxyl group-containing hydrocarbon polymer, forming an adhesive film with excellent adhesion to polyolefin polymers, various paints, and adhesives.

In addition, the concentration of alkyl hypohalide in the above solution is preferably 1 to 100 parts by weight per 100 parts by weight of the solvent,
More preferably, the amount is 25 to 100 parts by weight, and if it is less than 1 part by weight, there is almost no effect.

Further, the concentration of the compound having an X 11 -C-N- bond (in the formula, halogen) in the molecule is 0.5 to 5 parts by weight per 100 parts by weight of the solvent. If it is less than 0.5 parts by weight, there is no effect, and if it exceeds 5 parts by weight, there is a possibility that unreacted substances may be deposited on the treated surface.

In addition, examples of the solvent include various solvents used when diluting the hydroxyl group-containing hydrocarbon polymer, and in the case of a compound containing (X is halogen), water may be used as the solvent.

In addition to EPDM and EPM, the polyolefin vulcanized rubber may also contain NR, SBR, IIR, and CR in amounts within a range that does not lose these properties.

Rubber components such as NBR, or ABS, PS.

It also includes those containing resin components such as PE, PP, and EVA. Further, the content of these rubber components or resin components is usually 2 or less of that of EPDM, EPM, etc.

These polyolefin vulcanized rubbers contain compounds commonly used, namely: ■ sulfur, morpholine disulfide, and dicumyl peroxide as vulcanizing agents, and ■ 2-mercaptobenzothiazole and dimethyldithiocarbamic acid as vulcanization accelerators. Zinc, tetramethylthiuram disulfide, ■ Phenyl-α-naphthylamine as an anti-aging agent, antioxidant, and ozone deterioration inhibitor, monobutyl-p-cresol with 2,6-di, ■ Carbon black, magnesium carbonate, clay as a filler. , ■Dioctyl sebacate, mineral oil, etc. are added as plasticizers.

Example-1 A solution consisting of toluene/trichloroisocyanuric acid-99/1 (weight ratio) was prepared.

Example-2 N-bromsuccinimide was used in place of trichloroisocyanuric acid in the solution of Example-i (others were the same as in Example-I).

Example-3 The amount of trichloroisocyanuric acid in the solution of Example-1 was halved (others were the same as Example-1).

Example-4 The amount of trichloroisocyanuric acid in Example-1 was doubled (others were the same as Example-1).

Example-5 The amount of trichloroisocyanuric acid in Example-1 was increased 5 times (others were the same as Example-1).

Example-6 Xylene/tertiary butyl hypochloride = 99/1
A solution consisting of (weight ratio) was prepared.

Example-7 Xylene/tertiary butyl hypochloride ==1/1
A solution consisting of (weight ratio) was prepared.

Example-8 Xylene/tertiary butyl hypochloride-100/7
A solution consisting of 5 (weight ratio) was prepared.

Example-9 Xylene/tertiary butyl hypochloride-10015
A solution consisting of 0 (weight ratio) was prepared.

Example 10 A solution consisting of toluene/trichloroisocyanuric acid/tertiary butyl hypochloride-99/1/20 (weight ratio) was prepared.

Example 1) A solution consisting of toluene/trichloroisocyanuric acid/tertiary butyl hypochloride-99/1/30 (weight ratio) was prepared.

Next, a rubber compound having the composition shown in Table 1 was heated at 160°C for 3
An EPDM base material was manufactured by vulcanization treatment for 0 minutes.

Table-1 (Hereinafter, parts in the table are parts by weight.) Above EPD
Each base material made of M was dipped in a 5% toluene solution of the above "Polytail-H" for 1 minute and then heated at room temperature for 3 minutes.
After air-drying for 0 minutes, an adhesive film was formed on the surface by dipping it in the solutions of Examples-1 to 1) for 30 seconds and air-drying it at room temperature for 30 minutes.

Next, a urethane paint obtained by reacting a urethane compound having the composition shown in Table 2 at 80° C. for 3 hours in dry nitrogen gas was applied thereon and cured at room temperature for 24 hours.

Table 2 Next, as a result of examining the adhesion of the above urethane coating film by a goblin test, it was found that all base materials had sufficient adhesion (100/
100).

The compositions of Comparative Examples 1 to 3 below are conventionally used as primers for various rubber products.

Comparative Example 1 A composition was prepared by diluting Befucosol J-5344 (manufactured by Dainippon Ink and Chemicals, linseed oil-modified long oil alkyd resin) with a mineral base and further adding cobalt naphthenate as a desiccant.

Comparative Example 2 A composition was prepared by diluting OLESTAR M55-80AJ (manufactured by Mitsui Toatsu, a moisture-curing polyurethane resin) with toluene.

Comparative Example-3 "Ester Resin-20" (manufactured by Toyobo Co., Ltd., saturated polyester resin) was mixed with methyl ethyl ketone/toluene-1/9
A composition diluted with a mixed solvent of (weight ratio) was prepared.

Next, the compositions of Comparative Examples 1 to 3 above were applied to the EPDM base material, and a urethane paint having the composition shown in Table 2 was applied thereon, and after curing for 24 hours, the adhesion of the paint film was determined by a goblin test. I checked the force, but none of them were attached at all (
0/100).

Next, usage examples in which the structure of the present invention is applied to various molded articles for automobiles will be explained.

Usage Example 1: A polyolefin vulcanized rubber for glass run used in sliding parts with the windshield of glass land assash has the composition shown in Table 1, as an example.

After extrusion molding an EPDM blend of this composition,
A glass run for automobiles was produced by vulcanization for 0 minutes.

Next, this molded product was mixed with 5% toluene of "Polytail-H".
After dipping in the solution for 1 minute and air-drying at room temperature for 30 minutes, it was dipped in the solution of Example-1 for 30 seconds and air-drying at room temperature for 30 minutes to form an adhesive film.

Next, a urethane paint having the composition shown in Table 3 was applied. , and the resulting urethanes were mixed in a ratio of 100/40 (weight ratio).

Table 4 Table 5 Application example 2, Door weather strip A weather strip that seals the gap between the car body and the door is an example of a weather strip that seals the gap between the car body and the door after extrusion molding an EPDM compound with the composition shown in Table 6 at 200°C for 5 minutes. It is manufactured by vulcanization.

Table 6 Next, this weather strip was dipped in a 5% toluene solution of Polytail-HJ for 1 minute and
After air-drying for 0 minutes, it was dipped in the solution of Example-1 for 30 seconds and air-dried for 30 minutes at room temperature to form an adhesive film. Next, the formulation in Table 7 was heated at 80°C for 3 hours in dry nitrogen gas.
1.6-hexanediol 24.
8 parts of dimethylformamide and 170 parts of dimethylformamide were added and reacted for 20 minutes at 80° C. in dry nitrogen gas, and a urethane paint obtained was applied thereon and cured for 24 hours.

Thereafter, a 5% toluene solution of dimethyl silicone oil (100,000 C3t) was applied onto the urethane coating.

Table 7 Usage Example 3, Electrostatic Flocking Products Some of the glass runs in Usage Example 1 have electrostatic flocking processing using short fibers applied to the sliding parts of the glass.

, this glass run was mixed with 5% toluene of "Polytail-H".
After dipping in the solution for 1 minute and air-drying at room temperature for 30 minutes, it was dipped in the solution of Example-1 for 30 seconds and air-drying at room temperature for 30 minutes.

Furthermore, the formulations in Table 8 were heated at 80°C in dry nitrogen gas for 30 minutes.
After applying the urethane adhesive obtained by reacting for a period of time,
A pile made of nylon 66 short fibers was electrostatically flocked, and the same urethane adhesive was cured with hot air at 100° C. for 3 minutes to obtain an electrostatic flocked product.

Next, the abrasion resistance of the coating films applied to the surfaces of the adhesive coated molded products of Use Examples 1 and 3 was tested using the following method.

Testing machine: Kl type abrasion testing machine Test conditions: Friction element glass (thickness 5m) Load
3 kg Friction element cycle: 60 times/min Friction element stroke: 1450 The molded product was attached to the above testing machine, and its surface was rubbed under the conditions described above.

As a result, good results were obtained in which no peeling of the coating film was observed even after repeated friction 50,000 times.

In addition, the abrasion resistance of the coating film applied to the surface of the adhesive coated molded article of Use Example 3 was tested using the following method.

Testing machine: Reciprocating abrasion tester Test conditions: Friction element Glass (thickness 5m) Friction element cycle 60 times Friction element stroke 145 A crane molded product was attached to the above testing machine, and its surface was inspected under the conditions described above. There was friction.

As a result, a good result was obtained in which no peeling of the coating film was observed even after repeated friction 20,000 times.

In addition, for the followability of each molded product in Usage Examples 1 to 3, 18
A 0 degree bending test was conducted, and all showed extremely good followability, and the flexibility and flexibility, which are characteristics of polyolefin vulcanized rubber, were not impaired in any way.

Usage Example 4: Resin molding A molding attached to the side of an automobile body is attached to the body via a double-sided adhesive tape made of polyethylene foam or the like as a base material.

Therefore, we used 170% vinyl chloride resin with the formulation shown in Table 9.
A molding was produced by extrusion molding at ℃, and the following tests were conducted using this molding.

Table 9fa) As shown in Figure 1, a 5% solution of Polytail-HJ in toluene was sprayed on one side of the tape 3 made of 5x polyethylene foam, and after air-drying at room temperature for 30 minutes,
The tape 3 was dipped in the solution of Example 1 for 30 seconds and air-dried at room temperature for 30 minutes to form an adhesive film 4.

Next, G-17 (manufactured by Konishi, CR type adhesive) was applied as the adhesive 5a on the same film 4, and a commercially available acrylic adhesive 6 for double-sided tape was applied on the other side, and a double-sided adhesive tape was applied. 7a was adjusted, and the vinyl chloride resin molding 2 was attached to the acrylic-coated iron plate 1 via the double-sided adhesive tape 7a.

False) The solution of Example-5 was used as the solution in the above tal. (Others are the same as in (a).) (C) Above (the solution in Example-6 was used as the solution in Al. (Others are the same as in (a).) (dl Above (Implemented as a solution in Al) The solution of Example 1) was used. (Others are the same as in (a).) (a1 Next, as shown in Figure 2, "Polytail-HJ After spraying a 5% solution of toluene and air-drying at room temperature for 30 minutes, the same tape 3 was dipped in the solution of Example-1 for 30 seconds and air-dried at room temperature for 30 minutes to form an adhesive film 4. Then, on the same film 4, Dianal 882 (manufactured by Mitsubishi Rayon, acrylic adhesive) was applied as the adhesive 5b.
Also, on the other side, commercially available acrylic adhesive for double-sided tape 6
was applied to prepare a double-sided adhesive tape 7b, and the vinyl chloride resin molding 2 was attached to the acrylic-coated iron plate 1 via this double-sided adhesive tape 7b.

(f) The solution of Example-5 was used as the solution in +el above. (Others are the same as (81)) The solution of Example-6 was used as the solution in (phantom +6). (Others are the same as (a).) (Example-1 as the solution in +el above) (Others are the same as in (e).) (1) As a comparative example, as shown in FIG. Only G-17 was applied.

(Others are the same as in (a).) (J) As shown in FIG. 4, only Dial 882 was applied as the adhesive 5b to one side of the tape 3 made of 5x polyethylene foam. (Others are the same as in (e).) Next, a tensile shear test was performed on each molding 2 of (al to U) above at a tensile speed of 30 m/min, and Table 10
The results shown are obtained.

Table 10 (Unit: g/cd) From the above test results, the adhesion of the paint and adhesive applied to the surface of the automotive polyolefin polymer moldings with adhesive coating in each of the above usage examples is extremely strong. It turned out to be.

Effects of the Invention As detailed above, by forming an adhesive film on the surface of a molded product made of polyolefin vulcanized rubber or polyolefin synthetic resin, the adhesion of paints and adhesives applied thereon can be improved. It will be extremely strong. Therefore, this adhesive coated polyolefin polymer molded product is an excellent invention that can be used not only for various molded products for automobiles but also for a wide range of applications.

[Brief explanation of the drawing]

1 and 2 are cross-sectional views showing an attachment structure for a molding with an adhesive coating according to the present invention, and FIGS. 3 and 4 are cross-sectional views showing an example of a conventional molding attachment structure, respectively. 2...Mall, 4...Adhesive film. Patent applicant Toyoda Gosei Co., Ltd. agent
Patent Attorney Hironobu Onda Drawing Part 1 Part 2

Claims (1)

[Scope of Claims] Consisting of (1) a polyolefin polymer molded article, and (2) a hydrocarbon polymer whose main chain containing a hydroxyl group is saturated or partially saturated, which is coated on the surface of the molded article. (3) Either a compound containing a ▲ mathematical formula, chemical formula, table, etc. ▼ bond (in the formula, X is a halogen) in the molecule, or an alkyl hypohalide, which is coated on the surface of the coating. A polyolefin polymer molded article with an adhesive coating consisting of a reactive coating consisting of one side, and an adhesive coating consisting of a reactive coating consisting of one side;