JPS6021653B2 - automotive glass run - Google Patents

Description

[Detailed description of the invention] The present invention relates to a glass run for automobiles.

More specifically, the present invention provides an automobile that has significantly improved performance such as abrasion resistance after a heat resistance test under high load, abrasion resistance after a film resistance test, and abrasion resistance in a high-temperature atmosphere, as well as sliding resistance. Regarding grass runs.

Glass runs for automobiles are required to have a variety of performances under harsh conditions, such as heat resistance under high loads, film resistance, and abrasion resistance in high-temperature atmospheres, as well as products with low sliding resistance. There is. Generally, glass runs applied to automobile windows require a glass holder made of a material with low frictional resistance when supporting the window glass and window frame, especially when the glass can be slidably opened and closed. Conventional glass run for automobiles has particularly poor wear resistance after heat aging, wear resistance after weathering tests,
It has poor abrasion resistance in high-temperature atmospheres, and has high swamp resistance between the glass and glass run during vertical movement of the glass.
Improving these performances has been a challenge in this technical field. When examining the condition of automotive glass runs through abrasion resistance tests, it is found that the coating itself may wear out, the coating itself may crack, and in some cases, the coating may peel off from the base material at the interface.

The inventors of the present invention, As a result of these studies, in automotive glass lazers, the paint applied to the base material is the biggest factor in determining the quality of its abrasion resistance and anti-dragging resistance. Through these measurements, we succeeded in significantly improving the performance of automotive glass runs.

In other words, the paints conventionally used for glass run include various paints such as polyacrylic acid ester, polyvinyl acetate, epoxy, polyvinyl acetal, and polyvinyl chloride. It had the disadvantage of poor abrasion resistance after heat aging, abrasion resistance after weathering tests, and abrasion resistance in high-temperature atmospheres, and at the same time, high sliding resistance between the glass and the glass run due to vertical movement of the window frame glass. . As a result of repeated research on the above-mentioned topic, the present inventors used polyvinyl chloride resin as a base material and coated it with a paint prepared from the components of ``B'', ``Q'', and ■ described later. By doing so, we have been able to provide a glass run for automobiles that not only eliminates the above-mentioned drawbacks of conventional products but also has extremely excellent workability during manufacturing.

The automotive glass run according to the present invention will be described in detail below.

The glass run for automobiles of the present invention uses PVC (polyvinyl chloride) resin as a base material, and after cleaning the surface of the base material as desired, coating it with the paint described in detail below.
The coating composition used in the present invention is cured at a temperature in the range of 0.000 Celsius, and the coating composition used in the present invention contains A C3 to C6 saturated low molecular diol, C4 to C6 organic dicarboxylic acid, and this saturated low molecular diol and organic dicarboxylic acid. A polyester having a hydroxyl group at the terminal synthesized from a low-molecular trifunctional polyol of 1% by weight or less based on the total weight of the acid and a diisocyanate at a molar ratio of NCO:OH = 0.6 to 0.95:1. A urethane polymer having a hydroxyl group at the terminal obtained by the reaction and this urethane prepolymer 1
0, parts by weight of urethane prepolymers 1 to 15 having terminal isocyanate groups obtained by reacting B low-molecular tri-enriched polyol and diisocyanate at a molar ratio of NCO:OH=3:1. , C 3 to 4 parts by weight of nylon powder, and 4D 5 to 20 parts by weight of silicone oil are dissolved in an organic solvent.

In the above urethane prepolymer A, if the polyester polyol having hydroxyl groups has more than 2 moles of OH groups per 1 mole of COO, the paint film will be hard and brittle, resulting in poor abrasion resistance. .

Furthermore, if the content 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, and at the same time the product will have a high scratch resistance value. For example, in such a product, it is difficult to move the glass up and down, to the extent that it becomes impossible to open and close the glass after repeating the up and down movement several thousand times. In the urethane polymer of the legs, 0.6 mole or less of NCO group and 0.95 mole of NCO group per mole of OH group.
In the case of a urethane prepolymer obtained by reacting at a molar ratio of more than 1 mol, the sliding resistance value is high and the abrasion resistance in a high-temperature atmosphere is also poor.

The above-mentioned C3-C6 saturated low-molecular-weight diols include propylene glycol, butylene glycol, bentanediol, hexanediol, etc., and the C4-C6 saturated organic dicarboxylic acids include adipic acid, succinic acid, etc. Low-molecular trifunctional polyols include glycerin, trimethylolpropane, and the like.

The diisocyanate includes 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, and the like. The nylon powder used in the present invention includes nylon 6, nylon 60, nylon 610, nylon 12, nylon 11, and nylon 9.
, nylon powder such as nylon 1*.

Further, examples of the silicone oil include dimethyl silicone oil, methyl chloride silicone oil, and the like.
These silicone oils preferably have a viscosity of 10,000 to 200,000 Cst. For the above-mentioned coating composition used in the present invention, 1 to 15 parts by weight of component B to 10 parts by weight of component A, preferably 4 to 6 parts by weight of component B to 10 parts by weight of component A. used in proportion. If the amount of component B is 15 parts by weight or more relative to 10 parts by weight of component A, the resulting coating film will be very hard and brittle, and its adhesion to the PVC resin base material will be extremely poor.
For example, in the case of such products, the paint peels off after only a few dozen cycles of vertical movement of the glass, and the sliding resistance value rapidly increases, making it difficult to open and close the window glass, and at the same time, the wear resistance deteriorates. It gets very bad. In addition, if the amount of component B is 1 part by weight or less per 100 parts by weight of component A, the resulting coating film will be sticky, and in glass run manufactured with such a coating, the glass and the coated surface will stick together, and the top and bottom of the glass will stick together. Exercise becomes impossible. Furthermore, the wear resistance in a high temperature atmosphere is also very poor. The proportion of nylon powder to be used is 3 to 4 parts by weight, preferably 10 to 3 parts by weight, based on 10 parts by weight of component A.

When the amount of nylon powder is 3 parts by weight per 10 parts by weight of component A, the abrasion resistance is very poor, and when the sliding resistance of a glass run manufactured using a paint with this composition is measured, it shows a significantly high value. show. Furthermore, if more than 4 parts by weight of nylon powder is used per 10 parts by weight of component A, the nylon powder will be exposed on the surface of the product, resulting in a very poor appearance and extremely poor wear resistance. descend. If the proportion of silicone oil used is less than 5 parts by weight, the abrasion resistance of the product after weathering will be poor.

If more than 20 parts by weight is used, the stability of the solution will deteriorate. When preparing the above-mentioned urethane prepolymer, catalysts such as dibutyl acetate, dibutyltin dioctoate, dibutyltin dilaurate, etc., which generally promote the urethanization reaction, may be used as necessary.

Further, carbon black may be added if necessary.
The coating method used for manufacturing the automotive glass run of the present invention includes dip coating, spray coating,
Brush coating, knife coating, roll coating, etc. are exemplified, but are not specified.

The characteristic advantage of the glass run for automobiles of the present invention is that it can be left at room temperature for several hours or heated for several minutes at a temperature of 180 pm or less, resulting in low sliding resistance on the PVC base material surface and high abrasion resistance. It is possible to form an excellent paint film.

Here, room temperature refers to the indoor 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 preferable 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 the heat treatment is 180°C or less. A temperature of 18,000 or higher is undesirable because there is a concern that the base material will deteriorate. Preferably, the heat treatment is performed at a temperature of 100 pm or less. Any suitable means may be adopted as the above-mentioned heating means.

The present invention will be explained below with reference to Examples.

All parts in the examples are by weight. The PVC base material and polymer (urethane prepolymer) used in the examples were prepared as follows.

(A) 10 parts by weight of PVC Motomura polyvinyl chloride, 9 parts by weight of dioctyl phthalate
A mixture of 1.5 parts by weight of barium dilaurate, 2 parts by weight of zinc laurate, and 1 part by weight of dibutyltindimalate was extruded from an extruder at 150 to 17,000 to produce a base material.

(b) Polymer A: 10 parts by weight of 1,4-butanediol, 14 parts by weight of 1,6-hexanediol. Tortoise parts by weight, trimethylolpropane 2
15,000 parts by weight, using 163.9 parts by weight of adipic acid.
The reaction was carried out for one holding period to synthesize polyester.

Using 100 parts by weight of the obtained polyester, 8 parts by weight of 4,4'-diphenylmethane diisocyanate, 150 parts by weight of cyclohexanone, and 50 parts by weight of ethyl acetate, the mixture was heated at 80° C. for 3 hours in dry nitrogen gas. The reaction was carried out to produce a urethane prepolymer. (c) Polymer B Using 100 parts by weight of trimethylolpropane, 553 parts by weight of 4,4-diphenylmethane diisocyanate, and 48 parts by weight of butyl acetate, the mixture was heated to 3 at 8,000 in dry nitrogen gas.
A urethane prepolymer was synthesized by a time reaction.

Example 1 A coating material was prepared by mixing polymer AIOO, 25 parts of dimethyl silicone oil (viscosity: approximately 100,000 Cst), 15 parts of nylon 6 powder, polymer BI base material, and 3 parts of carbon black.

The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Example 2 Part of polymer AIOO, 25 parts of dimethyl silicone oil (viscosity approximately 10 Cst), 15 parts of nylon 6 & f powder,
Polymer BI Shikabe and 3 parts of carbon black were mixed to prepare a paint.

The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Example 3 Part of polymer AIOO, 25 parts of dimethyl silicone oil (viscosity approximately 100,000 Cst), 15 parts of nylon 12 powder,
A coating material was prepared by mixing the polymer BI base material and 3 parts of carbon black.

The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Control example 1 Dimethyl silicone oil (viscosity approximately 10 Cst) 10
The mixture was mixed with 100 parts of toluene, applied to a PVC substrate, and dried at room temperature to produce a glass run for automobiles.

Control Example 2 A coating material was prepared by mixing part of polymer AIOO, 25 parts of dimethyl silicone oil (viscosity: approximately 100,000 Cst), part of polymer BI Isobe, and 3 parts of carbon black.

The resulting paint was applied to a PVC base material and dried at room temperature to produce a glass run for automobiles. Control Example 3 A coating material was prepared by mixing a part of polymer AIO, 15 parts of nylon 6 powder, a part of polymer BIO, and 3 parts of carbon black.

The obtained paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Control Example 4 A urethane paint was prepared by mixing polymer AIO, polymer BI, and 3 parts of carbon black.

The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Control example 5 10 parts of polyester obtained during the preparation of polymer A, 8 parts of 4,4'-diphenylmethane diisocyanate,
Urethane prepolymer F was produced by reacting 200 parts of trichloroethylene at 80° C. for 3 hours in dry nitrogen gas.

The obtained urethane polymer FIO anchor, 25 parts of dimethyl silicone oil (viscosity: about 100,000 Cst), 15 parts of nylon 6 powder, polymer BI base, and 3 parts of carbon black were mixed to prepare a paint. The obtained paint is PV
It was coated on C-based 4 material and dried at room temperature to produce a glass run for automobiles. Control example 6 10 parts of polyester obtained during the preparation of polymer A, 8 parts of 4,4'-diphenylmethane diisocyanate,
Urethane prepolymer G was produced by reacting dimethylformamide 20% in dry nitrogen gas at 80°C for 3 hours.

The obtained urethane prepolymer GIO, 25 parts of dimethyl silicone oil (viscosity of about 10 Cs), N.
A paint was prepared by mixing 15 parts of Polymer B 6 powder, 3 parts of carbon black, and 3 parts of carbon black. The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Using the automotive glass runs obtained in Examples and Control Examples, sliding resistance measurements and abrasion resistance tests were conducted under the following conditions.

The test results are shown in the table. ■ To measure the sliding resistance, use TENS YamaON/UTM-1/5000 manufactured by Toyo Saiki Co., Ltd.
Using -W, glass (thickness: 5 broadsides) was tied to the glass run, a load of 3k9 was applied to the glass, the glass run was pulled (pulling speed: 20 broadsides/min), and the resistance value at that time was measured.

■ The abrasion resistance test was conducted as follows.

Testing machine: KI type abrasion tester Test conditions: Abrasion element: Glass (thickness: 5 mm) Load
3k9 wear child cycle
60 times/min friction element stroke
145 side test method A sample is attached to the above testing machine and the painted surface is abraded under the above conditions.

The abrasion resistance test sample after the '11 heat resistance test was placed in a thermostat at 80°C and left for 20 hours, and then abrasion was performed at room temperature.

■ Abrasion resistance test after film resistance test Abrasion was carried out at room temperature after being exposed to a Sunshine Weatherometer using two carbon arc lamps for 200 hours.

'3l Wear resistance test in high temperature atmosphere The sample is abraded in a 60qo atmosphere.

Table * When the handle operation load exceeded 8&, it became impossible to move the glass up and down.

Claims (1)

[Claims] 1. In an automobile glass run made of a polyvinyl chloride resin base material, (A) saturated low-molecular-weight diols of C_3 to C_6, organic dicarboxylic acids of C_4 to C_6, and the total weight of these saturated low-molecular-weight diols and organic dicarboxylic acids A polyester having a hydroxyl group at the terminal synthesized from 1% by weight or less of a low-molecular trifunctional polyol and a diisocyanate are combined with NCO:OH=0.6-0.
A urethane prepolymer having terminal hydroxyl groups obtained by reacting at a molar ratio of 95:1 and 100 parts by weight of this urethane prepolymer were mixed with (B) a low-molecular trifunctional polyol and a diisocyanate in an NCO:OH=3:
1 to 150 parts by weight of a urethane prepolymer having isocyanate groups at the terminals obtained by reacting at a molar ratio of 1 to 150 parts by weight, (C
A glass run for automobiles, characterized in that a coating composition prepared by dissolving 3 to 40 parts by weight of nylon powder and 5 to 200 parts by weight of (D) silicone oil in an organic solvent is applied and cured.