JPS5951427B2 - Electrostatic flocking products for automobiles - Google Patents

Description

[Detailed description of the invention] This invention relates to electrostatic flocking products for automobiles.

In addition to the functions of the flocked product itself, flocked products for automobiles are required to have performances such as soundproofing, weather resistance, and abrasion resistance. Conventionally, chloroprene rubber, styrene-butadiene copolymer rubber, and the like have been used as rubber base materials for electrostatic flocking products.

These synthetic rubbers have poor weather resistance, aging resistance, and ozone resistance, and in recent years, EPDM rubber (ethylene-propylene-diene terpolymer rubber) and EPR (ethylene-propylene rubber), which cover these physical properties, have been used for automobiles. It has come to be used as a base material for electrostatic flocking products. However, in these conventional flocked products, satisfactory abrasion resistance could not be obtained due to poor adhesion between the EPDM rubber or EPR rubber and the flocking adhesive. In order to improve such defects in adhesion, many treatment methods have been attempted in the past.

For example, 1. Polish the surface with a wire brush, sandpaper, etc. 2. Irradiate with ultraviolet rays. 3. Immerse in concentrated sulfuric acid. 4. Treat with a mixed solution of organic monocarboxylic acid and phosphoric acid. 5. Treat with aldehydes. 6. Chlorinated polypropylene. The following methods are known: 7. Treating with iodinated isocyanate; 8. Oxidizing the surface by exposing it to ozone; 9. Treating with alkyl hypohalite.@Painting epoxy tree paper. However, in case 1, these conventional processing methods tend to cause uneven polishing and cause hygiene problems due to the generation of dust, and in case 2, the vulcanized part deteriorates, and in case 3, the processing agent It is dangerous to handle, and in the case of □, 5, 7, and 9, the processing agent is special and the processing process is complicated, and 6, 8, [phase]
In this case, there were disadvantages such as high equipment costs. Furthermore, even if these treatments are applied, the adhesive and EPDM
Adhesion to rubber or EPR rubber was insufficient. As a result of research to improve the abrasion resistance of electrostatic flocking products for automobiles, the present inventors found that electrostatic flocking products for automobiles with excellent adhesion between the EPDM rubber or EPR rubber base material and the adhesive layer. Successfully developed the product.

That is, the present invention is a product obtained by applying an adhesive to a base material, electrostatically flocking short fibers thereon, and then curing the adhesive layer. Vulcanized rubber or ethylene-propylene
Using polymer vulcanized rubber, a functional hydrocarbon polymer containing a saturated aliphatic ring is used as a primer for the base material, and a urethane having an isocyanate group at the terminal consisting of polyol and polyisocyanate is used as an adhesive. The present invention provides an electrostatic flocking product for automobiles that is characterized by using a prepolymer and has excellent wear resistance.

The invention will be explained in detail below.

In the electrostatic flocking product for automobiles of the present invention, ethylene-propylene-polymer mono-vulcanized rubber or ethylene-propylene-polymer vulcanized rubber is used as the base material. Used as a functional hydrocarbon polymer primer containing group rings.

This polymer can be used as it is or by dissolving it in an organic solvent. Examples of the organic solvent in this case include n-hexane, cyclohexane, benzene, toluene, xylene, chloroform, carbon tetrachloride, trichloroethylene, tetrahydrofuran, carbon disulfide, and the like. These solvents can be used alone or as a mixed solvent of two or more. The functional hydrocarbon polymer containing a saturated aliphatic ring used in the present invention is
This is a polymer as disclosed in Japanese Patent Application Laid-open No. 71391/1983. Particularly preferred is τ'! having a conjugated diene compound and a vinyl group! ,S. Z-→species M magazine=V usually 500
~50,000 preferably 1,000~30,000
belongs to.

This functional hydrocarbon polymer is obtained by hydrogenating a functional hydrocarbon polymer having an aromatic ring in the presence of a hydrogenation catalyst. can be obtained by polymerizing an aromatic monomer alone or together with other comonomers according to a conventional method. Typical examples of production methods include a method in which a monomer is polymerized until it becomes a suitable low molecular weight polymer, and a method in which a high molecular weight polymer is oxidized and decomposed. An example of their manufacturing method is published in Japanese Patent Publication No. 378190.
No. 38-342, Japanese Patent Publication No. 22048-1972, Japanese Patent Publication No. 5993-1973, Japanese Patent Publication No. 14747-1974, and Japanese Patent Publication No. 36273-1973.
Examples of the above-mentioned conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-/<ntazinine, 2,3-dimethylbutadiene, etc., and examples of the above-mentioned aromatic compounds having a vinyl group include styrene. , vinyltoluene, vinylnaphthalene, phenylbutadiene, methylstyrene, divinylbenzene, coumaron, indene, cinnamic acid, vinylphenol, vinylbenzoic acid and the like.
These can be used alone or as a mixture. The aromatic monomer content in the above-mentioned functional hydrocarbon polymer having an aromatic ring is 1 to 10% relative to the polymer.
0% by weight, preferably 5-70%. As a method for hydrogenating a functional hydrocarbon polymer having an aromatic ring, noble metals such as palladium, platinum, rhodium, osmium, and ruthenium are used alone as a catalyst, or carbon,
There is a method of hydrogenation using carriers such as anolemina, silica anolemina, diatomaceous earth, barium carbonate, and calcium carbonate (see JP-A-51-76387). The hydrocarbon polymer containing a saturated aliphatic ring in the present invention has a hydroxy group, a carboxy group, etc. as a functional group, and the content of these functional groups is preferably one or more per molecule of the polymer. is 1.5 or more. For example, a copolymer obtained by placing 1,3-butadiene and styrene in arbitrary proportions in an autoclave and polymerizing them with 60% hydrogen peroxide in isopropyl alcohol in argon is then polymerized in cyclohexane. Hydrogenation with a carbon-supported ruthenium catalyst gives the corresponding functional hydrocarbon polymer.

Next, the adhesive to be used is a one-component urethane prepolymer having an isocyanate group at the end, which is made of polyol and polyisocyanate.

(Refer to Japanese Patent Application Laid-Open No. 50-25865). In the electrostatic flocking product for automobiles of the present invention, since a functional hydrocarbon polymer containing a saturated aliphatic ring as described above is used as a primer, the adhesion between the base material and the urethane adhesive is improved. This has significantly improved the wear resistance, resulting in superior wear resistance not seen in conventional products.

The above-mentioned vulcanized rubber, which is the base material of the product of the present invention, may contain other rubber components, such as natural rubber, styrene- Butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile butadiene (NBR), polyisoprene (IR
), chloroprene rubber (CR), butyl rubber (IIR)
It may also contain other resin components such as polyethylene (PE), polypropylene (PP), ethylene monovinyl acetate copolymer (EVA), etc.

The amount is usually 1/2 or less of the ethylene-propylene terpolymer or ethylene-propylene polymer. To produce the automotive electrostatic flocking product of the present invention, a substrate is treated with the primer described above, and then coated with the urethane prepolymer adhesive described above, such as nylon, polyethylene phthalate, rayon, cotton, etc. Short fibers are electrostatically flocked, and then the adhesive layer is cured in hot air or steam.

The obtained product may be coated with silicone or the like to further improve wear resistance. EXAMPLES Below, the present invention will be explained with reference to Examples and Comparative Examples.

Details of the wear tests described in the examples are as follows.

Testing machine: KI type wear test Test conditions: Wear element: Glass (thickness: 5 mm) Load: 3 kg Friction element cycle: 60 times/min Friction element stroke: 145 mm Test method: The sample was mounted on the above testing machine, and the conditions were as described above. Rub the electrostatic flocking surface with the bottom.

The adhesion test was conducted using a peel test (JISDO2O2).

The base material used in the examples was prepared as follows.

Rubber compound containing 100 parts of ethylene-propylene ether polymer, 67.5 parts of carbon black, 35 parts of mineral oil, 5 parts of zinc white, 1 part of stearic acid, 2.0 parts of vulcanization accelerator, and 1.5 parts of sulfur. was vulcanized at 160° C. for 30 minutes to obtain an ethylene-propylene terpolymer vulcanized rubber.

Furthermore, the functional hydrocarbon polymer containing a saturated aliphatic ring used as a primer in the examples was produced as follows.

Manufacturing method A: Polymerize 75 g of 1,3-butadiene, 25 g of styrene, 70 g of isopropyl alcohol, and 10 g of 60% hydrogen peroxide in an autoclave at 90°C for 5 hours in argon, then use carbon-supported ruthenium and hydrogen gas in cyclohexane. This was then hydrogenated to obtain a functional hydrocarbon polymer.

Manufacturing method B l. A functional hydrocarbon polymer was produced in the same manner as in Production Method A except that 64 g of 3-butadiene and 36 g of styrene were used.

Example 1 A functional hydrocarbon polymer containing a saturated aliphatic ring obtained by production method A is heated and melted at 100°C, and a base material is dipping therein, followed by a urethane adhesive having a viscosity of 1000 CPS. The urethane adhesive was adjusted as follows, roll coated, and then electrostatically flocked, and the urethane adhesive was cured at 150° C. for 18 minutes to obtain an electrostatic flocked product for automobiles.

Example 2 10 parts of the same saturated aliphatic ring-containing hydrocarbon polymer as in Example 1 was dissolved in 90 parts of cyclohexane, and the solution was applied to a base material to produce electrostatic flocking for automobiles in the same manner as in Example 1. Got the product.

Example 3 5 parts of the same saturated aliphatic ring-containing hydrocarbon polymer as in Example 1 was dissolved in 95 parts of n-hexane, and applied to a base material. I got a hair transplant product.

Example 4 5 parts of the functional hydrocarbon polymer containing a saturated aliphatic ring obtained by Production Method B was dissolved in 95 parts of toluene, and applied to a base material. I got an electro-flocked product.

Example 5 10 parts of the same functional hydrocarbon polymer containing a saturated aliphatic ring as in Example 4 was dissolved in 90 parts of toluene, and applied to a base material. I got an electro-flocked product.

Example 6 5 parts of the same saturated aliphatic ring-containing functional hydrocarbon polymer as in Example 4 was dissolved in 95 parts of tetrahydrofuran, and applied to a base material to produce an electrostatic charger for automobiles in the same manner as in Example 1. I got a hair transplant product.

Control example 1 "Ester Resin 20" (product name: Toyobo saturated polyester) was mixed with methyl ethyl ketone and toluol.
9 was dissolved in a mixed solvent and applied to a base material, and an electrostatic flocking product for automobiles was obtained in the same manner as in Example 1.

Comparative Example 2 "Vinyrite VMCH" (trade name: manufactured by Union Carbide, vinyl chloride monovinyl acetate copolymer resin) was dissolved in a mixed solvent of methyl ethyl ketone and triol 1:1 and applied to the base material. An electrostatic flocking product for automobiles was obtained in the same manner.

Control example 3 "Eslec BM-2" (trade name: Petitral resin manufactured by Sekisui Chemical Co., Ltd.) was dissolved in a 1:1 mixed solvent of butanol and xylene and applied to a base material, and then applied to an automotive static coating in the same manner as in Example 1. I got an electro-flocked product.

Control example 4 “Oresta M55-80A” (Product name:
A moisture-curing polyurethane resin (manufactured by Mitsui Toatsu) was dissolved in toluene and applied to a base material to obtain an electrostatic flocking product for automobiles in the same manner as in Example 1.

Control example 5 "Dismofen 100" (product description: manufactured by Bayer AG,
100 parts of polyhydroxy compound) and 100 parts of Desmodyur L
150 parts of polyisocyanate (product name: manufactured by Bayer) were mixed and dissolved in a mixed solvent of methyl glycol acetate, butyl acetate, ethyl acetate, and triol, and applied to a substrate. I got a hair transplant product.

Control Example 6 "Betsukosol J-534" (trade name: manufactured by Dainippon Ink & Chemicals, linseed oil-modified long oil alkyd resin) was dissolved in Minera Space, applied to the substrate, and treated in the same manner as in Example 1. A flocked product for automobiles was obtained.

Control example 7 "Betsukosol J-524" (trade name: Dainippon Ink & Chemicals, linseed oil-modified short oil alkyd resin) 80 parts,
20 parts of "Super Betsukamine J-820" (trade name: Dainippon Ink & Chemicals, butylated melamine resin) was mixed and dissolved in xylene, applied to a substrate, and heated to 120°C for 30 minutes.
After drying for a minute, a flocked product for an automobile was obtained in the same manner as in Example 1.

Control example 8 "Acryloid C-110V" (trade name: Calm Haas thermoplastic acrylic resin) 99 parts and 1 part of nitrocellulose were mixed and dissolved in toluene and applied to the substrate,
A flocked product for automobiles was obtained in the same manner as in Example 1.

Control example 9 80 parts of "Acridik 47-712" (product name: Dainippon Ink Chemical Co., Ltd., thermosetting acrylic resin) and "Supervetsucomin 47-508" (product name: Dainippon Ink Chemical Co., Ltd., butylated melamine resin) Dissolve 20 parts in a 2:1 mixed solvent of toluene and butyl acetate and apply it to the substrate.
After drying at 50° C. for 30 minutes, a flocked product for automobiles was obtained in the same manner as in Example 1.

The physical property test results of Examples 1 to 6 and Control Examples 1 to 9 are shown in the table below.

The test results show that the electrostatic flocking product of the present invention has excellent adhesion between the base material and the urethane adhesive, and has significantly better abrasion resistance than conventional products.

Claims (1)

[Claims] 1. In an electro-flocked product for automobiles obtained by applying an adhesive to a base material, electrostatically flocking short fibers thereto, and then curing the adhesive layer, the base material is ethylene-propylene-terpolymer vulcanized rubber or Using ethylene-propylene polymer vulcanized rubber, as a primer for the base material,
Using a functional hydrocarbon polymer containing saturated aliphatic rings,
An electrostatic flocking product for automobiles characterized in that a urethane adhesive made of a urethane prepolymer having an isocyanate group at the end made of polyol and polyisocyanate is used as an adhesive.