JPS6021702B2 - A method of forming a wear-resistant film on the surface of a member made of rubber or synthetic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a wear-resistant film on the surface of a member made of rubber or synthetic resin.

Components made of rubber or synthetic resin are used in all fields, but in particular, components that are placed directly in the natural environment have high heat resistance, weather resistance, and abrasion resistance after experiencing abnormal temperatures and weather. is required. The present invention aims to prevent such abnormal temperatures from occurring on the surface of a section made of rubber or synthetic resin.
The purpose of the present invention is to provide a method for forming a film for imparting special and exceptional wear resistance such as heat resistance and weather resistance against abnormal weather.

Taking automotive glass runs as an example of the above-mentioned rubber or synthetic resin members, automotive glass runs have various characteristics such as heat resistance and weather resistance that can be used under harsh conditions in special atmospheres. However, glass run applied to automobile windows is generally made of materials with low abrasion resistance when supporting the window glass and window frame, especially when the glass can be slidably opened and closed. A glass presser made of glass is required.

In automobiles, a weather strip made of rubber or synthetic resin is used to secure the window glass and the window frame, and paint is applied to the parts where the glass slides, where it makes contact with the sliding glass. Glass run coated with is used. By the way, the conventional method of imparting wear resistance to the surface of such glass run is to form a film with paint, but depending on the conventional technology, it is not possible to obtain special and exceptional wear resistance on the surface of such products. It has not been done.

The present inventors have conducted various studies on methods of imparting special abrasion resistance as described above to the surface of a member made of rubber or synthetic resin.
A terminal synthesized from a saturated low-molecular diol of C3 to C6, an organic dicarboxylic acid of C4 to C6, and a low-molecular trifunctional polyol of 1% by weight or less based on the total weight of this saturated low-molecular diol and organic dicarboxylic acid. A polyester having a hydroxyl group and a diisocyanate are combined into NCO:OH
Urethane prepolymer 1 having hydroxyl groups at the terminals obtained by reacting at a molar ratio of =0.6 to 0.95:1
0 parts by weight, 'B- parts by weight of urethane prepolymers 1 to 15 having isocyanate groups at the terminals obtained by reacting a low-molecular trifunctional polyol and a diisocyanate at a molar ratio of NCO:OH = 3:1, and 'C) A coating composition consisting of 2 to 20 parts by weight of silicone oil is applied, and then further added with the general formula 'D' (wherein M represents each atom of silicon, titanium, germanium, zirconium, or tin). RI is C3~C,
8 aliphatic saturated hydrocarbon group, R2 represents a C3-C,8 aliphatic saturated hydrocarbon group or a C,7CO- group,
m represents an integer of 1 to 10.

It has been found that by applying a solution of the compound represented by ) and drying it, a film having extremely poor wear resistance can be formed on the treated surface of the member.

The present invention has been made based on this knowledge. The present invention will be explained in detail below.

In the urethane prepolymers of ■ and [B' above,
Examples of C3-C6 saturated low-molecular diols include propylene glycol, butanediol, bentanediol, hexanediol, etc.
Examples of the saturated organic dicarboxylic acid include adipic acid and succinic acid, and examples of the low molecular weight Mitokuma polyol include glycerin and trimethylolpropane.

Examples of the diisocyanate include 4,4'-diphenylmethane diisocyanate and 4,4'-diphenyl ether diisocyanate. Regarding the above urethane prepolymer (■), if the polyester polyol with hydroxyl groups has 2 or more moles of OH groups per 1 mole of 0COO per day, the paint coating will be hard and brittle, resulting in poor wear resistance. .

If the amount of OH groups is less than 1.04 mol per 1 mol of COO, the paint film will have poor abrasion resistance in a high-temperature atmosphere. Regarding urethane prepolymer ■, OH
0.6 mole of NCO group per mole of group, or 0
．． Both urethane polymers obtained by reacting with a molar ratio of more than 95 moles have poor abrasion resistance in a high-temperature atmosphere of the coating film (as mentioned above). Examples include silicone oils such as diene silicone oil, methylphenyl silicone oil, and fluorosilicone oil.

As an example of the compound represented by the above item (XI), an organic titanium compound represented by the formula, R: one CQC2CH2CH2 group, m: 1 to 10, and the formula, R: is 5C, 7 one group m: ・An organic zirconium compound represented by ~10; an organic germanium compound represented by the formula: Examples include metal compounds.

An organic solvent can be used when preparing the coating composition consisting of the components (2), 'B}, and (q) above.

Such organic solvents include acetone, methyl ethyl ketone, methyl isoptyl ketone, benzene, toluene, xylene, methyl acetate, ethyl acetate, isopropyl acetate, trichlorethylene, 1,1,1-trichloroethane, dimethylformamide, cyclohexathone, etc. can be exemplified. Further, the amount of such an organic solvent to be used can be arbitrarily selected depending on the desired viscosity of the coating composition. The above coating composition may optionally include fluororesins such as 4-fluoroethylene resin, 4-fluoroethylene-6-fluoropropylene copolymer resin, 3-fluoroethylene Q secondary hyethylene resin, and pinylidene fluoride resin, and carbon. You can add black etc.

The above-mentioned blood metal compounds may be used as they are or, if desired, as a solution dissolved in an organic solvent.

Examples of organic solvents used in this case include isopropanol, n-butanol, n-hexane, benzene, toluene, and methylchloroform. Examples of methods for applying the coating composition and metal compound solution include dip coating, spray coating, and brush coating, but are not specified.

Examples are listed below, and all "parts" in the examples are parts by weight.

Note that the base material used in the examples was prepared as follows. 10 parts by weight of polyvinyl chloride, 75 parts by weight of dioctyl phthalate, 2 parts by weight of barium stearate
A mixture of 1 part by weight of zinc stearate and 1 part by weight of dibutyltin dilaurate was extruded from an extruder at 150 to 17030 to produce a glass run base material.

Moreover, the urethane prepolymers in Examples were prepared as follows.

Polymer A Polyester was synthesized by reacting 99 parts by weight of 1,4-butanediol, 2.45 parts by weight of trimethylolpropane, and 148 parts by weight of adipic acid at 15 pi for 1q hours.

240 parts by weight of the obtained polyester, 20 parts by weight of 4,4-diphenylmethane diisocyanate, 20 parts by weight of toluene, and 20 parts by weight of cyclohexanone were reacted in dry nitrogen gas at 80°C for 3 hours to produce a urethane prepolymer. did. Polymer B 10 parts by weight of trimethylolpropane, 553 parts by weight of 4,4'-diphenylmethane diisocyanate, and 480 parts by weight of butyl taacetate were reacted in dry nitrogen gas at 80 oo for 3 hours to synthesize a urethane polymer.

Example 1 100 parts of urethane prepolymer of polymer A, 7 parts of dimethylsilicone oil (viscosity approximately 100,000 Cst), 13 parts of urethane prepolymer of polymer B, 3 parts of carbon black
．． A paint was prepared by mixing three parts.

Apply this paint to Motomura and apply the formula, (n-Bu:
A liquid organic titanate represented by CH3CH2CH (- group) (manufactured by Nippon Soda Co., Ltd.: TBT Polymer B2) was applied and dried at room temperature to produce a glass run for automobiles.

Example 2 100 parts of urethane prepolymer of polymer A, 1 base of dimethyl silicone oil (viscosity approximately 100,000 Cst), 1 base of urethane prepolymer of polymer B, 3 parts of carbon black
．． 5 parts were mixed to prepare a paint.

This paint was applied to a base material, and an organic titanate liquid represented by the formula (manufactured by Nippon Soda Co., Ltd.: TPT Polymer A4) was applied thereon and dried at room temperature to produce a glass run for automobiles.

Example 3 100 parts of urethane prepolymer of polymer A, 7 parts of dimethyl silicone oil (viscosity approximately 100,000 Cst), 15 parts of 4-fluoroethylene resin, 13 parts of urethane prepolymer of polymer B, 3 parts of carbon black A paint was prepared by mixing 3 parts.

This paint is applied to the base material, and the formula (n-Bu:
Liquid of organic titanate represented by - group from CH3CH2CH (manufactured by Nippon Soda Co., Ltd.: TBT Polymer BIO)
was applied and dried at room temperature to produce a glass run for automobiles.

Example 4 100 parts of urethane prepolymer of polymer A, 7 parts of dimethyl silicone oil (viscosity about 10 Cst), polymer 8
1 part of urethane prepolymer, 3 parts of carbon black.
Three parts were mixed to prepare a paint.

The obtained paint is applied to a base material, and an organic zirconate liquid represented by the formula (manufactured by Nippon Soda Co., Ltd.:
TSZR polymer) was applied and dried at room temperature to produce an automotive glass run. Example 5 100 parts of urethane prepolymer of polymer A, 1 part of dimethyl silicone oil (viscosity approximately 100,000 Cst), 1 part of urethane prepolymer of polymer B, 3 parts of carbon black
．． A paint was prepared by mixing 5 parts.

This paint is applied to Motomura, and an organic zirconate liquid represented by the formula (manufactured by Nippon Soda Co., Ltd.: TSZR) is applied on top of it.
Polymer) was applied and dried at room temperature to produce a glass run for automobiles.

Example 6 100 parts of urethane prepolymer of polymer A, 7 parts of dimethyl silicone oil (viscosity approximately 100,000 Cst), 15 parts of 4-fluoroethylene resin, 13 parts of urethane prepolymer of polymer B, carbon black 3.3 parts were mixed to prepare a paint.

This paint is applied to the base material, and an organic zirconate liquid represented by the formula (manufactured by Nippon Soda Co., Ltd.: TSZR) is applied on top of it.
A glass run for automobiles was manufactured by applying a polymer) and drying it at room temperature.

Example 7 100 parts of urethane prepolymer of polymer A, 7 parts of dimethyl silicone oil (viscosity approximately 100,000 Cst), polymer B
13 parts of urethane prepolymer, 3 parts of carbon black.
A paint was prepared by mixing three parts.

This paint is applied to the base material, and the formula, R, :CH3
Shows 2 CH2CQC units per day.

A glass run for automobiles was manufactured by applying an organic germanate solution represented by (GEBSTA-200, manufactured by Nippon Soda Co., Ltd.) and drying at room temperature. Example 8 100 parts of urethane prepolymer of polymer A, 1 part of dimethyl silicone oil (viscosity approximately 100,000 Cst), 1 part of urethane prepolymer of polymer B, 3 parts of carbon black
．． A paint was prepared by mixing 5 parts.

This paint is applied to the base material, and the formula, R, :CH3
Indicates one CH2CH2CH2 group.

An organic germanate solution represented by (manufactured by Nippon Soda Co., Ltd.: GEBSTA-600) was applied and dried at room temperature to produce a glass run for automobiles. Example 9 100 parts of urethane prepolymer of polymer A, 7 parts of dimethyl silicone oil (viscosity approximately 100,000 Cst), 15 parts of 4-fluoroethylene resin, 13 parts of urethane prepolymer of polymer B, 3.3 parts of carbon black A paint was prepared by mixing the two parts.

This paint is applied to the base material, and then an organic germanate liquid (manufactured by Nippon Soda Co., Ltd.: GE Spot TA-1000) represented by the formula (R,:C ratio CH2C ratio CH2 group) is applied. The mixture was dried at room temperature to produce a glass run for automobiles.

Control example 1 100 parts of urethane prepolymer of polymer A,
7 parts of dimethyl silicone oil (viscosity approximately 100,000 Cst), 15 parts of 4-fluoroethylene resin, 13 parts of urethane prepolymer of polymer B, 3. Parts were mixed to prepare a paint.

The resulting paint was applied to a base layer and dried at room temperature to produce a glass run for automobiles. The automotive glass run obtained in the above Examples and Control Examples was subjected to the following abrasion test.

The test results are shown in the table. 5 Abrasion Test Testing Machine KI Abrasion Testing Machine Test Conditions Abrasion element Glass (5 ribs thick) Load 3k9 0 Abrasion element cycle 6 sub/minute stroke of the friction element Attach the 145 side sample to the above testing machine and apply the painted surface under the above conditions. wear out.

'11 Abrasion test after heat aging test The sample was placed in an 8000° thermostat and allowed to stand for 200 hours, and then abrasion was performed at room temperature.

■ Abrasion test after weather test After being exposed to a sunshine weatherometer using two carbon arc lamps for 20 hours, a wear test was performed at room temperature.

'31 Wear test in high temperature atmosphere The sample is rubbed in a 60CO atmosphere.

Table *1 Abrasion was performed up to 30,000 times, but no base material was exposed.

The wear test was stopped after 30,000 cycles. (The number of wear is 300
0 m or more) *2 The base material began to curl at each wear count, so the wear test was stopped at that point.

For example, in the case of “wear after heat resistance test” in Control Example 1, 700
Since the base material was exposed after 0 cycles, abrasion stopped after 700 cycles.

Claims (1)

[Claims] 1. On the surface of a member made of rubber or synthetic resin, (A)C
Hydroxyl at the terminal synthesized from saturated low-molecular diols from _3 to C_6, organic dicarboxylic acids from C_4 to C_6, and low-molecular trifunctional polyols in an amount of 1% by weight or less based on the total weight of the saturated low-molecular diols and organic dicarboxylic acids. A polyester having a group and a diisocyanate are NCO:
100 parts by weight of a urethane prepolymer having a hydroxyl group at the end obtained by reacting at a molar ratio of OH=0.6 to 0.95:1, (B) a low-molecular trifunctional polyol and a diisocyanate, and NCO:OH=3 A coating composition consisting of 1 to 150 parts by weight of a urethane prepolymer having an isocyanate group at the end obtained by reacting at a molar ratio of 1 to 1 and 2 to 200 parts by weight of silicone oil (C) is applied, and then, further, (D) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, M represents each atom of silicon, titanium, germanium, zirconium, or tin, and R^1 is C_3 to C
_1_8 aliphatic saturated hydrocarbon group, R^2 is C_3-C
_1_8 aliphatic saturated hydrocarbon group or H_3_5C_1
_7 represents a CO- group, and m represents an integer of 1 to 10. ) A method for forming an abrasion-resistant film on the surface of a member made of rubber or synthetic resin, which method comprises applying a liquid of the compound represented by the formula and drying it.