JPS6411238B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a glass run for automobiles. More specifically, the present invention relates to an automotive glass run with significantly improved wear resistance. In recent years, glass runs for automobiles are strongly required to have various performances under severe conditions in special atmospheres, including heat resistance and weather resistance. Generally, for glass runs applied to automobile windows, a glass holder made of a material with low frictional resistance is required when supporting the window glass and window frame, especially when the glass can be slidably opened and closed. shall be. In automobiles, weather strips made of rubber or resin are used to secure the window glass and the window frame. A glass run coated with paint is used. When examining the condition of this automotive glass run through wear resistance tests, it is found that the coating film itself may wear out, the coating film itself may crack, and depending on the object, the coating film may peel off from the base material at the interface. . In order to improve the abrasion resistance of glass runs for automobiles, the present inventors have previously conducted research on various paints applied to glass sliding surfaces, and found that the following components (A) to (E): That is, (A) a polyester polyol with a molecular weight of 1000 to 3000 having a hydroxyl group at the terminal synthesized from a C ₂ to C ₆ saturated diol and a C ₄ to C ₆ organic dicarboxylic acid and an organic diisocyanate at NCO:OH=0.6 to
A urethane prepolymer having a hydroxyl group at the end obtained by reacting at a molar ratio of 0.95:1, and 100 parts by weight of this urethane prepolymer (A), (B) 10 to 60 parts by weight of castor oil polyol (C) low molecular weight A coating consisting of 25 to 70 parts by weight of a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyol and an organic diisocyanate (D) 2 to 100 parts by weight of a fluororesin (E) 5 to 100 parts by weight of silicone oil. , it was discovered that by coating at least the sliding surface and curing it, it was possible to provide a product with significantly superior wear resistance than conventional products, and in that case, they (A), (B ), (C),
We have succeeded in providing a glass run for automobiles characterized by using a coating composition comprising 0.5 to 3 parts by weight of talc in addition to components (D) and (E) (Patent Application No. 58 −200084). Furthermore, in addition to the above components (A), (B), (C), (D), and (E), 0.5 to 3 parts by weight of at least one selected from silica, clay, and calcium carbonate is used. The company also provided a glass run for automobiles characterized by using a paint composition consisting of
No. 16964). The present invention was achieved as a result of the above-mentioned research conducted by the present inventors. That is, the present invention provides a glass run for automobiles made of a polymeric material as a base material, at least on the glass sliding surface of (A) a _C2 - _C6 saturated diol, a _C4 - _C6 organic dicarboxylic acid. The synthesized polyester polyol with a molecular weight of 1,000 to 3,000 having a hydroxyl group at the terminal and an organic diisocyanate are combined with NCO:OH=0.6 to
A urethane prepolymer having a hydroxyl group at the end obtained by reacting at a molar ratio of 0.95:1, and 100 parts by weight of this urethane prepolymer (A), (B) 10 to 60 parts by weight of castor oil polyol (C) low molecular weight 25 to 70 parts by weight of urethane prepolymer having an isocyanate group at the end obtained by reacting a polyol and an organic diisocyanate (D) 2 to 100 parts by weight of fluororesin (E) 5 to 100 parts by weight of silicone oil (F) Carbon The present invention provides a glass run for automobiles, which is coated with a coating composition consisting of 0.5 to 3 parts by weight of at least one selected from black and chlorinated polypropylene and cured. Hereinafter, the automotive glass run according to the present invention will be described in detail. The glass run for automobiles of the present invention uses a polymeric material as a base material, and after cleaning the surface of the base material as desired, the following paint is applied to it, and the temperature is increased from room temperature to 180°C.
The glass run for automobiles of the present invention is manufactured by curing at a temperature of
The above-mentioned coating composition used has the above-mentioned (A),
It is characterized by containing the components (B), (C), (D), (E), and (F). In the above urethane prepolymer (A), NCO
In the case of a urethane prepolymer reacted with a molar ratio of less than 0.6 mole of groups or a molar ratio of more than 0.95 mole, the abrasion resistance of the coating film in a high-temperature atmosphere is poor. The above-mentioned _C2 - _C6 saturated diols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, etc., and the _C4 - _C6 organic dicarboxylic acids include:
These include adipic acid and succinic acid. The castor oil polyol (B) above is composed of a copolymer of castor oil, phthalic anhydride, and glycerin, and by changing the molar ratio of these monomer components, the molecular weight of this castor oil polyol can be changed.
The number of OH groups can be changed. Examples of the low-molecular polyol in component (C) include glycerin, trimethylolpropane, etc., and examples of the organic diisocyanate include 4,4'-diphenylmethane diisocyanate,
Examples include 4,4'-diphenyl ether diisocyanate. In addition, examples of the fluororesin of the component (D) include 4-fluorinated ethylene resin, 4-fluorinated ethylene-6-fluorinated propylene copolymer resin, 3-fluorinated chlorinated ethylene resin, vinylidene fluoride resin, etc. be done. Examples of the silicone oil of component (E) include dimethyl silicone oil, methyl chloride silicone oil, methylhydrogen silicone oil, methylphenyl silicone oil, and fluorosilicone. Examples of the carbon black of component (F) include channel black, furnace black, acetylene black, and thermal black. Examples of chlorinated polyolefins include polymers obtained by randomly chlorinating polyethylene, polypropylene, etc. with a molecular weight of tens of thousands to hundreds of thousands to a chlorine content of about 30 to 50%. To explain the parts by weight of each of the above components, for 100 parts by weight of component (A), component (B) is as follows:
It is used in a proportion of 10 to 60 parts by weight. If component (B) exceeds 60 parts by weight per 100 parts by weight of component (A), the wear resistance of the product will be poor;
If the amount of component (B) is less than 10 parts by weight, the wear resistance will still be poor. Also, the ratio of component (C) is 100% of component (A)
If it exceeds 70 parts by weight, the wear resistance of the product will be poor, and if it is less than 25 parts by weight, the wear resistance will also be poor. The proportion of component (D), fluororesin, is 2 to 100 parts by weight, preferably 10 to 60 parts by weight, per 100 parts by weight of component (A). (A) Component
If the amount of fluororesin is less than 2 parts by weight per 100 parts by weight, the abrasion resistance will still be poor, and if it exceeds 100 parts by weight, the stability of the solution will deteriorate and significant precipitation of the fluororesin will be observed. The ratio of component (E), silicone oil, is 5 to 100 parts by weight of component (A).
The amount is 100 parts by weight, preferably 10 to 50 parts by weight. If the amount of silicone oil is less than 5 parts by weight, the wear resistance of the product will be poor. Moreover, if it exceeds 100 parts by weight, the solution quality will be poor and the silicone oil will separate as in the case of fluororesins. The proportion of carbon black and chlorinated polyolefin used as component (F) is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of component (A). If it is less than 0.5 parts by weight, the effect of improving wear resistance will be small, and if it exceeds 10 parts by weight, wear resistance will deteriorate. When preparing the above-mentioned urethane polymer, if necessary, catalysts that generally promote the urethanization reaction, such as dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diesterate, tributyltin acetate, tri-butyltin octoate, and tributyltin, are used. Laurate, dioctyltin diacetate,
Dioctyltin dilaurate, diethyltin oleate, monomethyltin dioleate, etc. may also be used. Examples of organic solvents used as diluents include acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, methyl acetate, ethyl acetate, isopropyl acetate, trichloroethylene, 1,1,1-trichloroethane, dimethylformamide, etc. be done. The amount of such an organic solvent to be used can be appropriately selected depending on the desired viscosity of the composition used for treatment. The coating methods used for producing the automotive glass run of the present invention include dip coating, spray coating, brush coating, knife coating,
Roll coat etc. are exemplified, but are not specified. The coating composition is used in the form of a solution diluted with an organic solvent as described above. The characteristic advantage of the present invention in manufacturing glass run for automobiles is that the base material surface can be made to have wear resistance, non-adhesion, and A paint film with excellent water repellency and slipperiness is formed.
Here, room temperature refers to the room temperature that can be obtained in normal climate without using heating means such as a dryer or heating furnace. A method of curing at room temperature is preferred because it does not require a heating device and is easy to work with, but if there is a requirement such as large-scale processing, it is also possible to use heating means. The temperature during heat treatment shall be 180°C or less. This is because there is a concern that the base material will deteriorate at a temperature of 180°C or higher. 100 depending on the item
It may soften at temperatures above ℃, so preferably
It is better to heat treat at a temperature below 100℃. Any suitable means may be adopted as the above heating means. The present invention will be specifically explained below using Examples and Comparative Examples. In Examples and Comparative Examples, all parts are by weight. To explain the base material used in each example, in Examples 1, 2, 4 and comparative example, EPDM rubber (hardness JIS A80 degrees) was used,
In Example 3, a mixture of 100 parts by weight of polyvinyl chloride, 75 parts by weight of dioctyl phthalate, 2 parts by weight of barium stearate, and 1 part by weight of dibutyltin dilaurate was extruded from an extruder at 130 to 140°C. Comparative example: 25.0 parts of urethane prepolymer (A), castor oil polyol (Toxinol 2310-50T, Tokushima Essential Oil Co., Ltd.)
) 8.0 parts, urethane prepolymer (C) 10 parts, 4-
Fluorinated ethylene resin 8.0 parts, silicone oil 8.0 parts
0.5 parts carbon black, 0.065 parts dibutyltin dilaurate, 0.065 parts phenol salt of 1,8-diaza-bicycloundecene-7, solvents (1.3 parts toluene, 3.0 parts cyclohexanone, 15.0 parts tetrachlorethylene, 118.9 parts trichlorethylene)
A coating composition was prepared. This coating composition was applied to a substrate and cured to produce a glass run for automobiles. The abrasion resistance of this product was tested by the abrasion test described below. The results were as shown in Table 1. Examples 1 to 4 were carried out using the component formulations shown in Table 1 by the same operation as in the above comparative example.
The test results were as shown in Table 1. Urethane prepolymer (A) used in each of the above examples
and urethane prepolymer (C) were prepared as follows. Urethane prepolymer (A): Polyester polyol synthesized from 1,4-butanediol and adipic acid (hydroxyl value
56.0) 1000 parts by weight of 4,4'-diphenylmethane diisocyanate (MDI) and 2000 parts by weight of toluene were reacted in dry nitrogen gas at 80°C for 3 hours to obtain a prepolymer having terminal hydroxyl groups. . Urethane prepolymer (C): 100 parts by weight of trimethylolpropane, 4,
4'-Diphenylmethane diisocyanate 553
487 parts by weight of ethyl acetate were reacted in dry nitrogen gas at 80°C for 3 hours to form terminal NCO
We obtained a prepolymer with a group. The glass run for automobiles according to the present invention is extremely excellent in that it has remarkable wear resistance, as is clear from the results shown in Examples below.

【table】

[Table] The paints used in Examples 1, 2, 3, and 4 have a long pot life, and for example, the time required to reach the sprayable limit of 400 cps is 25°C.
In Examples 1 and 2, 10 hours (initial 150 cps),
Examples 3 and 4 were for 9 hours (initial 140 cps).

Claims (1)

[Scope of Claims] 1. In a glass run for automobiles made of a polymeric material as a base material, at least the sliding surface of the glass contains (A) a saturated diol of C ₂ to _{C 6} or an organic dicarboxylic acid of C ₄ to C ₆ . The synthesized polyester polyol with a molecular weight of 1,000 to 3,000 and having a hydroxyl group at the terminal and an organic isocyanate are mixed with NCO:OH=0.6-0.95:
(B) 10 to 60 parts by weight of castor oil polyol (C) Low-molecular-weight polyol and organic 25 to 70 parts by weight of a urethane prepolymer having an isocyanate group at the end obtained by reacting with diisocyanate (D) 2 to 100 parts by weight of fluororesin (E) 5 to 100 parts by weight of silicone oil, (F) Carbon black and An automobile glass run characterized by being coated with a coating composition consisting of 0.5 to 10 parts by weight of at least one selected from chlorinated polyolefins and curing the coating composition.