JPS6031668B2 - 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 flocking product itself, electrostatic flocking products for automobiles also have
Performance such as soundproofing, anti-fouling properties, and abrasion resistance is also required. Conventionally, chloroprene rubber, styrene-butadiene copolymer rubber, and the like have been used as rubber base materials for electrostatic flocking products.

However, these synthetic rubbers have poor aging resistance, aging resistance, and ozone resistance, and in recent years, EPDM rubber (ethylene-propylene-dienter polymer rubber) has been developed that covers these physical properties.
and EPR (ethylene.propylene rubber) have come to be used as base materials for electrostatic flocking products for automobiles. However, in these conventional flocked products, it has been difficult to obtain satisfactory abrasion resistance because of the 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, ■ polishing the surface with a wire brush, sandpaper, etc. ■ irradiating the surface with ultraviolet rays ■ soaking in concentrated sulfuric acid ■ treating with a mixture solution of organic monocarboxylic acid and phosphoric acid ■ treating with aldehydes ■ chlorinated polypropylene and Paint a mixture of ethylenediamine ■ Treat with iodinated isocyanate ■ Expose to ozone to oxidize the surface ■
Methods such as treating with alkyl hypohalite (2) painting with epoxy resin are known. However, with these conventional processing methods, uneven polishing tends to occur in the case of (1), and there are hygiene problems due to the generation of dust.
In the case of , the vulcanized part deteriorates, and in the case of ■, it is dangerous to handle the treatment agent, and in the cases of ■, ■, ■, and ■, the treatment agent is special and the treatment process is complicated; , ■, ■ had disadvantages such as high equipment costs. Furthermore, even if these treatments were performed, the adhesion between the adhesive and the EPDM rubber or EPR rubber was not necessarily sufficient. 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, and as the base material, an ethylene-propylene terpolymer or , using ethylene-propylene-polymer, and using polyhydroxypolybutanene with hydrogenated double bonds of 98% or more as a primer for the base material, and as an adhesive,
The present invention provides an electrostatic flocking product for automobiles that is characterized by using a one-component urethane polymer having an isocyanate group at the end, which is made of polyol and polyisocyanate, and has excellent wear resistance. The invention will be explained in detail below.

In the electrostatic flocking product of the present invention, the base material is ethylene-propylene terpolymer or ethylene-propylene polymer, and the primer used therein is
This is polyhydroxypolybutadiene in which at least % of double bonds are hydrogenated, or it is dissolved in an organic solvent.

(Examples of organic solvents in this case include n-hexane, cyclohexane, benzene, toluene, xylene, dichloroform, carbon tetrachloride, trichlorethylene, tetrahydrofuran, carbon disulfide, etc. (However, it can also be used as a mixed solvent of two or more types.) What is the polyhydroxypolybutadiene in which 98% or more of the double bonds are hydrogenated?
-142695, but briefly, one or more molecules per molecule, preferably 1.8
It has ~5.0 polyhydroxy groups and has an average molecular weight of
Usually 500-50000, preferably 1000-200
A hydrogenated product obtained by hydrogenating polyhydroxypolybutadiene of No. 00 to 98% or more, preferably 99% or more, and more preferably substantially close to 100% of its double bonds in the presence of a hydrogenation catalyst. It is.

Next, the adhesive to be used is a one-component urethane prepolymer having an isocyanate group at the end and consisting of polyol and polyisocyanate. (Refer to Hakama Seki No. 50-25865) In the electrostatic flocking product for automobiles of the present invention,
As mentioned above, polyhydroxypolybutadiene in which 98% or more of the double bonds are hydrogenated is used as the primer, so the adhesion between the base material and the above urethane adhesive is significantly improved, which is different from that seen in conventional products. It has excellent wear resistance.

In the base material of the product of the present invention, other rubber components may be added, of course, in amounts within a range that does not impair the properties of the ethylene-propylene terpolymer or ethylene-propylene polymer.
For example, Fumen rubber, styrene-butadiene copolymer rubber (
SBR), polybutadiene rubber (BR), acrylonitrile butadiene (NBR), polyisoprene (IR),
Chloroprene rubber (CR), butyl rubber (11R) and other resin components such as polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), etc. may be contained. The amount is usually no more than 1'a amount of 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;
Next, the above-mentioned urethane polymer adhesive is applied thereto, short fibers such as nylon, polyethylene terephthalate, rayon, cotton, etc. are electrostatically flocked thereto, 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 abrasion test Test conditions: Wear element Glass (5 legs thick) Load 3 [9 Lacquer resistance cycle 60 times/min Friction element stroke 145 Chest test method: Mount the sample on the above testing machine, and Rub the electrostatic flocking surface under the following conditions.

The adhesion test was conducted using the Haku IJ test (JISD0202).

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

ethylene. A rubber compound of 10 parts of propylene terpolymer, 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, Vulcanization was performed at 160 qo for 30 minutes to obtain an ethylene-propylene terpolymer vulcanizate.

Example 1 Polyhydroxypolybutadiene in which double bonds are hydrogenated by pseudo% or more is heated and melted to 60 qo, and a base material is dipinked to this, and then urethane adhesive is added to 100 qo to make it a PS viscosity. Adjust, roll apply, then electrostatic flocking 1
The urethane adhesive was cured at 50° C. for 18 minutes to obtain an electrostatic flocking product for automobiles.

Example 2 Same as Example 1, 1 part of polyhydroxypolybutadiene hydrogenated product was dissolved in 9 parts of cyclohexane, and it was applied to the base material. I got a hair transplant product.

Multiple Example 3 Polyhydroxypolybutadiene hydrogenated product 5 same as Example 1
1 part was dissolved in 95 parts of n-hexane, and the solution was applied to a substrate to obtain an electrostatic flocking product for automobiles in the same manner as in Example 1.

Example 4 Same polyhydride as Example 1.

An electrostatic flocking product for automobiles was obtained in the same manner as in Example 1 by adding 5 parts of xypolyptadiene hydrogenated product to 95 parts of toluene and applying it to a base material. Example 5 Polyhydroxypolybutadiene hydrogenated product 5 same as Example 1
1 part was dissolved in 95 parts of tetrahydrofuran, and the solution was applied to a substrate to obtain an electrostatic flocking product for automobiles in the same manner as in Example 1.

Control example 1 "Ester Resin 20" (product name: Toyobo saturated polyester) was mixed with methyl ethyl ketone and toluene in a ratio of 1:9.
The mixture was dissolved in a mixed solvent and applied to a base material, and the same procedure as in Example 1 was carried out to obtain an electrostatic flocking product for automobiles.

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

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

Control Example 4 "Orestar M55-80A" (trade name: manufactured by Mitsui Tosho, moisture-curing polyurethane resin) was dissolved in toluene and applied to the base material, and an electrostatic flocking product for automobiles was produced in the same manner as in the example. Obtained.

Control example 5 "Desmophen 100" (product name: Bayer, polyhydroxy compound) 10 Etsuro and "Desmodur L" (
15 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 the base plate. An electrostatic flocking product was obtained.

Control Example 6 "Betsukosol J General 4" (trade name: manufactured by Dainippon Ink and Chemicals, linseed oil-modified long oil alkyd resin) was dissolved in Mineral base, applied to the base material, and manufactured in the same manner as in Example 1 for automobiles. An electrostatic flocking product was obtained.

Control example 7 "Betsukosol 1-524" (trade name: Dainippon Ink Chemical Industry, linseed oil modified short oil alkyd resin) 8 base part, "
Example 1: Mix and dissolve 2 parts of "Supervecamine J-820" (trade name: manufactured by Dainippon Ink and Chemicals, butylated melamine resin) in xylol, apply it to Motomura, and dry it at 120 ° C. for 30 minutes. In the same manner as above, an electrostatic flocking product for automobiles was obtained.

Comparative Example 8 9 parts of "Acryloid C-110V" (trade name: thermoplastic acrylic resin manufactured by Rohm & Haas) and 1 part of nitrocellulose were mixed and dissolved in toluene, and the mixture was applied to a substrate, and the mixture was prepared as in Example 1. Using the same machine, we obtained electrostatic flocking products for automobiles.

Control example 9 "Acrydik 47-712" (product name: Dainippon Ink Chemical Co., Ltd., thermosetting acrylic resin) 8 anchors and "Super Beckamine 47-508" (product name: Dainippon Ink Chemical Co., Ltd., butylated) Dissolve melamine resin) 2 in a 2:1 mixed solvent of toluene and butyl acetate and apply it to the base material for 15 minutes.
After drying at 0qo for 3 minutes, an electrostatic flocking product for automobiles was obtained in the same manner as in Example 1.

The physical property test results of the above Examples 1 to 5 and Control Examples 1 to 9 are shown in Attached Table 11. 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.

Attached table-1

Claims (1)

[Claims] 1 Electrostatic flocking products for automobiles obtained by applying an adhesive to a base material, electrostatically flocking short fibers thereon, and then curing the adhesive layer, in which ethylene-propylene-terpolymer or ethylene is used as the base material. -Propylene-polymer is used, and for the base material, polyhydroxypolybutadiene in which 98% or more of double bonds are hydrogenated is used as a primer, and as an adhesive, a polyol and polyisocyanate having an isocyanate group at the end is used.
An electrostatic flocking product for automobiles that uses a liquid type urethane prepolymer.