JPS6215344B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an electrostatic flocking product that has excellent heat abrasion resistance, weather abrasion resistance, abrasion resistance in high-temperature atmospheres, etc. In recent years, electrostatic flocking products have been used in various fields, but depending on the usage, various performances are required, and conventional flocking products do not necessarily fully meet these demands. I wasn't there. For example, as shown in FIG. 1, a glass run 2 attached to a window frame (lunch channel) 1 of an automobile
consists of a pair of seal lips 4 that seal both sides of the glass 3, and a groove bottom 5 on which the end surface of the glass 3 slides, and an electrostatic flocked portion 6 is formed in each portion where the glass surfaces come into sliding contact. ing. At this time,
In particular, the groove bottom 5 has a large frictional resistance because it makes line contact with the end surface of the glass 3, and since the glass run 2 is used outdoors for a long time, the flocked surface of the glass run 2 is likely to deteriorate. For this reason, the abrasion resistance of the flocked surface of the groove bottom 5 deteriorates and hair loss occurs, the skin of the flocked surface is exposed, the sliding resistance of the glass increases rapidly, and in extreme cases, the glass It becomes impossible to slide. In addition, in order to improve the abrasion resistance of this flocked surface, paints such as polyacrylic ester and polyvinyl acetate are applied to the flocked surface, but it is still not possible to obtain sufficient abrasion resistance under harsh usage conditions. I couldn't help it. In view of the above, this invention has the advantage that even under severe usage conditions, the abrasion resistance of the flocked surface from the viewpoint of preventing hair loss does not decrease over a long period of time, the product has a long lifespan, and furthermore, the application workability is good. The aim is to provide electrostatic flocking products that can significantly expand the field of application. The gist of this invention is to provide a coating composition comprising 10 to 40 parts of non-reactive silicone oil mixed with 100 parts (solid content) of a urethane prepolymer having terminal isocyanate groups obtained by reacting a polyol and a polyisocyanate. is applied to the flocked surface of an electrostatic flocking product and dried, resulting in an electrostatic flocking product that can be used under severe usage conditions. Hereinafter, the structure of the electrostatic flocking product of the present invention will be explained in detail. First, a method for preparing the coating composition used in this invention will be explained. Here, non-reactive silicone oil is a term for reactive silicone oil into which reactive groups such as carboxyl groups, amino groups, alkoxy groups, hydroxyl groups, etc. refers to non-reactive silicone oil. Add a solvent to polyol (including low-molecular-weight polyol if necessary) and polyisocyanate, mix, and react in dry nitrogen gas at 50 to 130°C for 60 to 360 minutes to synthesize a urethane prepolymer with isocyanate groups at the ends. After that, add 10~10 parts of silicone oil to 100 parts (solid content) of this urethane prepolymer.
Add 40 parts and further add carbon black and solvent as appropriate to adjust the viscosity to a suitable level for coating. If the amount of silicone oil is outside the range of 10 to 40 parts, the wear resistance is likely to be adversely affected in various ways. In this case, molybdenum disulfide, glass fiber, carbon fiber, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, silicon oxide, etc. can be added as required. Here, examples of polyols, polyisocyanates, silicone oils, and solvents that can be used in this coating composition are listed. Polyether polyols: polyoxypropylene glycol, polyoxyethylene glycol, polytetramethylene oxide glycol, propylene oxide adduct of glycerin, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of pentaerystol. Polyester polyols: polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polydiethylene adipate, adipic acid ester of 1,6-hexanediol/diethylene glycol, etc. Low molecular polyols: ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol,
Octanediol, diethylene glycol, triethylene glycol, dithioglycol, dipropylene glycol, neopentyl glycol, 2
-ethyl-2-n-butyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, triethanolamine, glycerin, trimethylolpropane, etc. Polyisocyanate: 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,5-naphthalene diisocyanate, toluene diisocyanate, etc. Silicone oil: dimethyl silicone oil, methyl chloride silicone oil, methyl phenyl silicone oil, fluorosilicone, etc. Solvent: benzene, toluene, xylene, ethylbenzene, trichloroethylene, ethylene chloride,
Dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate,
Anisole, tetrahydrofuran, etc. Next, a method for manufacturing the electrostatic flocking product of the present invention will be explained. The surface of the flocked area of the base material is coated with toluene, xylene,
After cleaning with a solvent such as trichlorethylene, an adhesive is applied to the area, and charged short fibers are dropped vertically from above using electrostatic attraction, and then the adhesive is cured and the short fibers are removed. Hair is transplanted using a fixed method. The short fibers used here include nylon, polyethylene terephthalate, rayon,
Examples of the adhesive include cotton, and examples of the adhesive include urethane-based, polyacrylic ester-based, synthetic rubber-based, and polyvinyl acetate-based adhesives. Next, the prepared coating composition is applied to the flocked surface of the electrostatic flocking product and dried at room temperature to 180°C. Drying is preferably carried out at room temperature to 150°C. If the temperature is 150°C or higher, there is a risk of thermal aging of the short fibers, base material, adhesive, and coating film. As shown in the examples below, the electrostatic flocking product of the present invention thus obtained has a coating film that strongly adheres to the flocking surface, even under harsh usage conditions such as outdoor exposure and high temperature atmosphere. , the abrasion resistance from the viewpoint of preventing hair loss on the flocked surface does not deteriorate, and the product life is significantly extended. Note that silicone oil is sometimes used as a smoothing agent and as a foam stabilizer when foaming urethane, but in either case, the amount of silicone oil added is very small. It is generally said that coating compositions to which a large amount of silicone oil is added, such as the coating composition used in the present invention, do not have adhesive properties. It has excellent adhesion and wear resistance. The reason for the above improvement in wear resistance is that the silicone oil blended into the urethane prepolymer is non-reactive and is blended in a large amount, so the silicone oil gradually migrates from inside the coating film to the surface (so-called bleed). It's for a reason. In addition, if silicone oil is reactive, even if it is blended in a large amount into the paint as in the present invention, it will have good compatibility with the urethane polymer, and most of it will react with the isocyanate groups of the urethane, making it difficult to paint. Since the silicone oil is only uniformly dispersed in the film, bleeding to the electrostatic flocking surface does not occur, and improvement in abrasion resistance as in the present invention cannot be expected. Hereinafter, the effects of the present invention will be confirmed with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, used in these Examples and Control Examples,
The base material of the electrostatic flocking product is a vulcanizate under the following conditions. 100 parts of styrene-butadiene rubber, 5 parts of zinc oxide
100 parts carbon black, 70 parts calcium carbonate
A styrene-butadiene rubber vulcanizate made by vulcanizing a rubber compound of 80 parts of mineral oil, 2 parts of vulcanization accelerator, and 2 parts of sulfur at 160°C for 15 minutes. The short fibers used were 6-nylon, and the adhesive used was urethane adhesive. Further, abrasion resistance was evaluated using the following testing machine under the following conditions after heat aging, after a weather resistance test, and in an atmosphere of 60°C, and was evaluated by the number of wears at which hair loss occurred. Testing machine: KI type abrasion tester, Test conditions: Wear element: Glass (thickness: 5 mm) Load: 3 kg, Wear element cycle: 60 times/min, Wear element stroke: 145 mm. Test method: A sample is attached to the above testing machine and the flocked surface is rubbed under the following conditions. 1 Wear test after heat aging This heat aging test is based on air heating aging. Heat aging tester: Gear type aging tester or similar equipment Heat aging conditions: Heat aging temperature 80±1°C Heat aging time 200 hours Test method: The sample was suspended in the tank of the heat aging tester described above. Heat and age under conditions. After aging the sample for the above time, it was removed from the testing machine.
Leave it at room temperature and attach it to the above abrasion tester within 24-96 hours to abrade the electrostatic flocking surface under the above conditions. 2 Wear test after weathering test Weathering tester: Comparing to JIS-D0205 accelerated weathering test Weathering test time: 200 hours Test method: After weathering the sample under the above conditions, leave it at room temperature and test it within 24 to 96 hours. It is attached to the above abrasion tester, and the electrostatic flocking surface is rubbed under the above conditions. 3 Abrasion test in 60℃ atmosphere Abrasion tester: The above abrasion tester Temperature inside the abrasion tester: 60±1℃ Test method: The sample was attached to the abrasion tester in the above atmosphere, and the electrostatic flocking surface was tested under the above conditions. to rub. Example 1 Polypropylene oxide glycol (molecular weight approx.
2000) 100 parts, propylene oxide glycol adduct of pentaerythol (molecular weight approximately 400) 2
part, 4,4'-diphenylmethane diisocyanate
75 parts of trichlorethylene and 35 parts of trichlorethylene were reacted in dry nitrogen gas at 80°C for 3 hours to obtain a urethane prepolymer. This obtained urethane prepolymer
100 parts, 30 parts of carbon black, polydimethylsiloxane (dimethyl silicone oil) (viscosity approx.
10000cSt) were mixed to prepare a paint. This paint was applied to the flocked surface and dried at room temperature to obtain an electrostatic flocked product. Example 2 A paint was prepared by mixing 100 parts of the urethane prepolymer prepared in the same manner as in Example 1, 10 parts of carbon black, and 30 parts of polydimethylsiloxane (viscosity: approximately 100,000 cSt). Apply this paint to the flocked surface
It was dried at 80°C for 3 minutes to obtain an electrostatic flocked product. Example 3 Polypropylene oxide glycol (molecular weight approx.
2000) 100 parts, 1,4-butanediol 0.9 parts,
4,4'-diphenylmethane diisocyanate 60
A urethane prepolymer was synthesized using the same method as in Example 1 using 40 parts of trichlorethylene. 100 parts of the obtained urethane prepolymer, 10 parts of carbon black, polydimethylsiloxane (viscosity approximately 6
A paint was prepared by mixing 35 parts (10,000 cSt). This paint was applied to the flocked surface and dried at room temperature to obtain an electrostatic flocked product. Example 4 100 parts of glycerin propylene oxide adduct (molecular weight approximately 3000), triethanolamine 4
part, 4,4'-diphenylmethane diisocyanate
A urethane prepolymer was synthesized in the same manner as in Example 1 using 75 parts of trichlorethylene and 45 parts of trichlorethylene. 100 parts of this obtained urethane prepolymer, 30 parts of carbon black, polydimethylsiloxane (viscosity approx.
100,000 cSt) was mixed and the paint was applied to the flocked surface and dried at room temperature to obtain an electrostatic flocked product. Example 5 A paint was prepared by mixing 100 parts of the urethane prepolymer prepared in the same manner as in Example 4, 30 parts of carbon black, and 30 parts of polydimethylsiloxane (viscosity: approximately 30,000 cSt). This paint was applied to the flocked surface and dried at room temperature to obtain an electrostatic flocked product. Example 6 A paint was prepared by mixing 100 parts of the urethane prepolymer prepared in the same manner as in Example 4, 30 parts of carbon black, and 30 parts of polydimethylsiloxane (viscosity: about 60,000 cSt). This paint was applied to the flocked surface and dried at room temperature to obtain an electrostatic flocked product. Control example 1 "R-258, R-230" (Product name: Nippon B Chemical Co., Ltd., two-component urethane) R-258; 8
A paint was prepared by mixing 1 part of R-230, 1 part of polydimethylsiloxane (viscosity: about 50 cSt), and 2 parts of toluene. Apply this paint to the flocked surface and heat it to 100℃.
It was dried for 10 minutes to obtain an electrostatic flocked product. Control example 2 "Pu #60" (product name: Nippon B Chemical Co., Ltd., one-component urethane) Ru #60; 8 parts, polydimethylsiloxane (viscosity approximately 50 cSt) 1 part, and toluene 2 parts were mixed and a paint was applied. Prepared. This paint was applied to the flocked surface and dried at 100°C for 10 minutes to obtain an electrostatic flocked product. Control example 3 "R-142" (trade name; manufactured by Nippon B Chemical Co., Ltd., polyvinyl chloride) R-142; 8 parts, polydimethylsiloxane (viscosity approximately 50 cSt) 1 part, and toluene 2 parts were mixed to prepare a paint. did. This paint was applied to the flocked surface and dried at 100°C for 10 minutes to obtain an electrostatic flocked product. Comparative example 4 “Pollinate 955, Safaron 825” (Product name:
A paint was prepared by mixing 4 parts of Polynate 955 (a two-component urethane manufactured by Toyo Polymer Co., Ltd.), 4 parts of Saphalon 825, 1 part of polydimethylsiloxane (viscosity: approximately 50 cSt), and 2 parts of toluene. This paint was applied to the flocked surface and dried at 100°C for 10 minutes to obtain an electrostatic flocked product. Control example 5 "R-258, R-230" (Product name: Nippon B Chemical Co., Ltd., two-component urethane) R-258; 6
A paint was prepared by mixing 3 parts of R-230, 1 part of polydimethylsiloxane (viscosity: about 50 cSt), and 2 parts of toluene. Apply this paint to the flocked surface and heat it to 100℃.
It was dried for 10 minutes to obtain an electrostatic flocked product. The test results of the above Examples and Control Examples are shown in Table 1. The values in the table indicate the number of times the electrostatic flocking portion 6 in FIG. 1 was worn out and the groove bottom portion 5 was exposed.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a sectional view showing an example of an electrostatic flocking product.

Claims (1)

[Claims] 1. An adhesive is applied to a base material, staple fibers are electrostatically flocked thereto, and after the adhesive layer is cured, a polyurethane coating composition is applied on the flocked surface and dried. In the electrostatic flocking product obtained, the polyurethane coating composition comprises 100 parts (solid content) of a urethane prepolymer having terminal isocyanate groups obtained by reacting a polyol with a polyisocyanate, and 10 parts of a non-reactive silicone oil. An electrostatic flocking product characterized by containing ~40 parts.