JPS5849775A - Glass run for automobile use - Google Patents

Abstract

PURPOSE:To prepare a glass run for automobile use, having high abrasion resistance and low friction to glass, and excellent weather resistance and sealing characteristics, by forming a composition composed of a partially crosslinked vinyl chloride resin and a plasticizer. CONSTITUTION:The objective glass run is manufactured by forming a composition consisting of a vinyl chloride resin partially crosslinked with a crosslinking agent comprising a 1,2-polybutadiene having a molecular weight of 1,000- 5,500[especially the compound of formulaI (m is 2-100; n is 1-80; X and Y are H, OH or COOH) or formula II (X and Y are H, -CH2CH2OH, or COOH)] and a plasticizer such as di-(2-ethylhexyl)phthalate, etc. The preferable amount of the crosslinking agent is 0.001-35pts.wt per 100pts.wt. of the charged vinyl chloride monomer, and that of the plasticizer is 40-200pts.wt. per 100pts.wt. of the above resin. EFFECT:The stainproofing property to the automobile body can be also improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a glass run for vehicles, and more specifically, it has excellent sealing properties, low sliding resistance with the glass, and high abrasion resistance with the glass. This provides a good glass run for vehicles.

Glass runs for vehicles have a channel-like shape that is inserted into the window frame of passenger cars, luggage cars, and other vehicles, and come in contact with the edge of the window glass to prevent wind and air from entering the vehicle interior when the window glass is closed. This is a part for vehicles that prevents rainwater etc. from entering, and prevents the suction noise and chatter noise that occurs when driving. Since it is used in the part where the window glass slides to open and close the window, there are extremely strict requirements such as good sealing properties, abrasion resistance with the glass, and low sliding resistance with the glass. At the same time, since some of the parts are exposed to sunlight, they must be weather resistant, and because they are used in contact with the vehicle body, they are required to be non-contaminating to the vehicle body. However, conventional glass runs for vehicles are 1)
2) Those made of rubber with synthetic or natural fibers flocked to the sliding part with the glass, or those made of rubber with abrasion-resistant paint applied to the sliding part with the glass, or those made of synthetic or natural fibers. A material made of flocked soft polyvinyl chloride resin is used.

However, rubber glass runs have poor weather resistance due to the characteristics of rubber, and when used in particularly hot and cold environments, the elastic properties decrease in a short period of time, and the sealing performance deteriorates extremely. The drawback is that the body is significantly contaminated by the carbon black mixed in it.

There is also a glass run made of soft polyvinyl chloride, which is made by adding a plasticizer to polyvinyl chloride. In order to give such a glass run made of soft polyvinyl chloride the wear resistance necessary for a glass run, it is necessary to a) make it relatively hard by reducing the amount of plasticizer blended, and b) make it relatively hard using polyvinyl chloride. Use a material with a high degree of polymerization, or c).

It is possible to fill and blend fluororesin, but a
Method (a) impairs the sealing properties of the glass run 8, method (b) is disadvantageous in terms of processability and cost, and method (c).
This method is significantly disadvantageous in terms of cost. In addition, short fibers are flocked to the sliding part of the glass run,
When the flocked short fibers are used by repeatedly opening and closing the glass window, the short fibers fall off and the base material is exposed, increasing the sliding resistance of the glass and reducing the sealing performance.

In view of this situation, the present inventors have conducted extensive research and have completed a glass run that satisfies the above performance and does not require flocking or surface coating.

The present invention provides a glass run for vehicles that has low sliding resistance and good abrasion resistance and is molded from a resin composition comprising a partially crosslinked vinyl chloride resin and a plasticizer.

A partially crosslinked vinyl chloride resin composition generally has a small compression set and significantly improves sealing properties. Part 1: Furthermore, it was discovered that the abrasion resistance due to friction with glass is good, and the sliding resistance with glass is extremely small, and the present invention was completed.

The partially crosslinked vinyl chloride resin used in the present invention is, for example, JP-A-56-79141 or JP-A-54-80.
854, it can be obtained by polymerizing vinyl chloride monomer in the presence of a crosslinking agent, and it can also be obtained by partially copolymerizing vinyl acetate, ethylene or propylene with vinyl chloride. Good too. As a crosslinking agent, polyfunctional monomers having two or more ethylenic double bonds in the molecule, diallyl esters of phthalic acid such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate; diallyl maleate, diallyl Diallyl esters of ethylenically unsaturated dibasic acids such as fumarate and diallylitaconate; diallyl esters of saturated dibasic acids such as diallyl adipate, diallyl acetate and diallyl sebacate; diallyl ether, triallyl cyanurate,
triallyl isocyanurate, triallyl trimellitate, and divinyl ethers such as ethylene glyfur divinyl ether, n-butanediol divinyl ether, and octadecane divinyl ether; ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dimethylene glycol diacrylate, Dimethacrylic esters or diacrylic esters of polyhydric alcohols such as triethylene glycol diacrylate; Trimethacrylic esters or diacrylic esters of polyhydric alcohols such as trimethylolpropane trimethacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate; Esters; and polyethylene glycol diacrylate (the number of ethylene glycol chains is 4 or more), polyethylene glycol dimethacrylate (the number of ethylene glycol chains is 4 or more)
, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diallyl ether, polypropylene glycol diallyl ether, ■, 2-polybutadiene, epoxidized 1.2-polybutadiene (epoxidation rate 0 to 30%),
Examples include oligomers having a molecular weight of 5,500 or less, such as acrylate-modified polybutadiene, epoxy acrylate prepolymers, urethane acrylate prepolymers, spiroacecool acrylate prepolymers, and bisphenol A-modified acrylate prepolymers. Among the above-mentioned, particularly preferred crosslinking agents are 1, 2-polybutadiene, epoxidized 1,2-polybutadiene, f-on, and acrylate-modified polybutadiene.
500 1,2-polybutadienes. The amount of these crosslinking agents added to the polymerization system is not particularly limited, but is preferably 0.001 to 35 parts by weight, more preferably 0.01 to 35 parts by weight, based on 100 parts by weight of the vinyl chloride monomer charged. 1
0 parts by weight is more preferred.

If the amount added is too small, the balance between compression set and tensile strength will be lost, and if the amount added is too large, processing productivity will deteriorate, which is not preferable.

The partially crosslinked vinyl chloride resin of the present invention is produced by polymerizing a vinyl chloride monomer, or a vinyl chloride monomer and a monomer copolymerizable with vinyl chloride, in the presence of a crosslinking agent as described above. However, it is also possible to add and blend an ordinary non-crosslinked vinyl chloride resin to the partially crosslinked vinyl chloride resin obtained in this way. The purpose of using these ordinary vinyl chloride resins is to improve processability, and the types thereof are not particularly limited, but examples include vinyl chloride homopolymers with an average degree of polymerization of 400 to 40.00, and copolymers of vinyl chloride and vinyl acetate. Polymers, copolymers of vinyl chloride and ethylene, copolymers of vinyl chloride and propylene, etc. are used. Especially average degree of polymerization 400-400
When a vinyl chloride homopolymer of 0 is blended and used, not only the processability during molding improves, but also the abrasion resistance as a glass run becomes good.

In the present invention, the plasticizer is used to soften the resin composition, and the amount used is not particularly limited, but
The hardness required for glass run is 45~90Hs (JI
6801 for S-, spring type hardness test type A), and in order to obtain a hardness in this range, the plasticizing effect varies depending on the type of plasticizer, but 40 parts by weight for 100 parts by weight of the resin It is preferable to mix it in a range of 200 parts by weight. As the type of plasticizer, commonly used plasticizers can be used. For example, phthalate ester compounds such as di-1-ethylhexyl phthalate, dibutyl phthalate, di-isodecyl phthalate, and capril phthalate; adipic ester compounds such as dibutyl adipate, dioctyl adipate, didecyl adipate, butylbenzyl adipate; dibutyl sebacate,
Sebacate ester compounds such as dioctyl sebacate and butylbenzyl sebacate 9 Phosphate ester compounds such as tributyl phosphate, tricresyl phosphate, triphenyl phosphate, and trioctyl phosphate; Other trimellitic acid ester compounds Examples include compounds and polyester-based epoxy compounds. These plasticizers can be used alone or in combination of two or more.

When molding the glass run of the present invention, in addition to adding a plasticizer to the resin or the blended composition of the resin, heat stabilizers, antioxidants, lubricants, ultraviolet absorbers, rubbers, processing aids, etc.
Fillers, pigments, etc. can be blended and used, and their types and amounts can be combined in various ways.

The glass run of the present invention is manufactured by injection molding or extrusion molding, and the molding conditions can be those for molding ordinary soft polyvinyl chloride resin, and the preferred molding temperature is 11.0 to 220°C. It is C. Furthermore, in the case of extrusion molding, one or more mesh filters may be installed in front of the die section of the extruder in order to make the molded product more uniform.

Furthermore, the glass run of the present invention can also be manufactured by profile extrusion molding, similar to the molding of other conventional composite window frames made of thermoplastic resin and metal. The shape of the glass run can be varied by changing the shape of the injection mold or extrusion die.

As mentioned above, the glass run of the present invention is a glass run formed by molding a composition comprising a partially crosslinked vinyl chloride resin and a plasticizer, and has excellent sealing properties and good glass abrasion resistance. Rubber glass runs exhibit low sliding resistance against glass, and are highly productive because they do not require flocking or surface treatment unlike conventional glass runs.They are also weather resistant and non-contaminating to vehicle bodies. significantly improved.

Next, the present invention will be further explained by examples.

The characteristic values were measured as follows.

■Measurement of characteristic values (1) This shows the practical sealing characteristics of compression set glass run.
Compliant with IS-6:ll 01, test temperature 70°C
The test was conducted at a compression ratio of 25% and a compression time of 22 hours. As a glass run, it is necessary that the content is -70% or less, and the lower the better.

(2) Abrasion resistance The sample was mounted in a predetermined position using a KI type abrasion tester, the load was 3 kg, the cycle of the abrasion element was 60 times/min, the stroke of the abrasion element was 145 mm, and the abrasion element was transparent with a thickness of 5 mm. A glass plate was used. Judgments were made as follows depending on the depth of wear.

Deep voice of wear 0 to 0.2 ◎ 〃0. z・〜0.5〃 〃0.5〜0.7〃 △ 〃0.7〜1. O〃× // 1. (1 or more ×× (3) Sliding resistance Toyo Sokki ■ Tensilon U'l'M-115000-W
Fit the glass plate into a glass run of the desired shape using a
The glass run was pulled at a speed of 1/min, and the sliding resistance value at that time was measured.

(4) Hardness Measured using JIS-6801 spring type hardness test type A.

CB) Production Example 1 of Partially Crosslinked Vinyl Chloride Resin 200 parts of ion-exchanged water (parts by weight, same hereinafter), 0.2 part of partially saponified polyvinyl acetate, 0.06 part of diisopropyl peroxide, di-2-ethylhexyl peroxide 0.06 part of oxydicarbonate, 0.1 part of diallyl phthalate, and 100 parts of vinyl chloride monomer were charged into a reactor, and 35 parts of
Polymerization was carried out at °C for 15 hours to obtain a partially crosslinked vinyl chloride resin containing 5% by weight of a portion insoluble in hot tetrahydrofuran.

Example 2 The same procedure as in Example 1 was carried out except that 0.2 part of epoxidized 1,2-polybutadiene was used instead of 0.1 part of diallyl phthalate. A partially crosslinked vinyl chloride resin containing 45% by weight of hot tetrahydrofuran insoluble portion was obtained.

Example 3 To 80 parts of the partially crosslinked vinyl chloride resin obtained in Example 2, 20 parts of a normal vinyl chloride resin (Kanevinyl 81008, manufactured by Kanefuchi Kagaku Kogyo ■) was added.

Example 4 To 60 parts of the partially crosslinked vinyl chloride resin obtained in Example 2, 40 parts of Kanevinyl 81008 was added.

Example 5 60 parts of Kanevinyl 81008 was blended into 4 (l) of the partially crosslinked vinyl chloride resin obtained in Example 2.

Example 6 80 parts of Kanevinyl 81008 was blended with 20 parts of the partially crosslinked vinyl chloride resin obtained in Example 2.

Comparative Example 1 Normal vinyl chloride resin (Kanevinyl 5tooa) h
was used.

By adding the plasticizer (di(2-ethylhexyl) phthalate 1- + +30.1.1) and additives shown in Table 1 to the resins or resin blends of Examples 1 to 6 and Comparative Example 1, A glass run, the cross-sectional view of which is shown in Figure 2, was formed by extrusion molding. Furthermore, a glass run obtained using the resin composition of Comparative Example 1 was coated with acrylic on the surface, and this was designated as Comparative Example 2. Comparative Example 8 was prepared by electrostatically flocking short nylon fibers on the sliding portion of the glass run obtained with the resin composition of Comparative Example 1.

Table 2 shows the characteristics of the glass runs obtained in Examples 1 to 6 and Comparative Examples 1 to 8.

From the results shown in Table 2, it can be seen that the glass run of the present invention is excellent in all aspects of wear resistance, sliding resistance, and sealing performance.

[Brief explanation of drawings]

FIGS. 1 and 2 are cross-sectional views showing an example of a glass run fitted into a window frame. (1)...Window glass, (2)...Glass run, (3
)...Window frame, (4)...Sliding part with glass. Patent applicant Makoto Asano, agent of Kanebuchi Chemical Industry Co., Ltd. Patent attorney - Procedural amendment (Iro et al.) 2nd Director General of the National Register of Japan Kazuo Wakasugi Case 1982 Patent Application No. 148105 Title of the invention
Date of amendment order (1) The scope of claims is revised in the attached document. (2) Detailed Description of the Invention in the Specification Column (A) Page 2 of the specification, lines 5-6, ``Sucking noise, chattering noise, etc.'' is corrected to ``1 Various types of noise.'' Page 2, line 6, "Window glass" is replaced by "This product is window glass."
Correct to. C. Correct page 2, line 8, "Abrasion resistance, glass" to "Good abrasion resistance, glass." 2. 8th line from the bottom of the second page of the same page [Resin-made items 1 is corrected to ``Resin-made items, etc.'' E. On page 3 of the same page, "filling and blending fluororesin" is corrected to "blending with fluorine-containing lubricant." To page 4, lines 10 to 11, "It becomes smaller, and the sealing properties are significantly improved. Part 1: Furthermore, due to friction with the glass" has been changed to "It has been confirmed that the size becomes smaller, and the sealing properties are significantly improved." .Moreover, it is based on friction with the glass.”
Correct to. G, page 6, lines 12-15 “oxylation rate (0-30%),
...Cetal acrylate prepolymer,
is corrected to "oxygenation rate (80% or less)." H. Delete 2 to the last line from the bottom of page 6 of the same page, "and acrylate-modified polybutadiene." Add the following sentence between "l,2-polybutadienes" and "ko" on page 7, line 1. [1 and 2 that produce particularly favorable results in the present invention
-Polybutadines are compounds having the structural formula shown in the following general formula (1) or (2). (Tatashi, m is 2~100Sn is 1~8o1X, Y is H
Atom, OH group, C0oH group are selected. ) (However, m is selected from 2 to 100, X, Y (d, H atom, -CH20H20H group, C0OH group.)
”nu Delete “0.1 part” in the 7th line from the bottom of page 12 of the same year, “0.2 parts” in the 7th line from the bottom of the same page 12 ”, 5 lines from the bottom “
5% by weight will be corrected to 128% by weight. E. Delete the two lines "0.1 copy" from the bottom of page 12. Page 16, lines 1 to 8, "From the results shown in Table 2, it can be seen that the present invention is superior to the old one."
From the results shown in Figure 1, the glass run of the present invention has significantly lower compression set, which is a substitute for sealing properties, and its abrasion resistance is several orders of magnitude better than that of the comparative example, and its sliding resistance is equal to or higher than that of flocked products. It turns out to be better. ” is corrected. Attachment Claims (1) A glass run for vehicles having low sliding resistance and good abrasion resistance molded from a composition comprising a partially crosslinked vinyl chloride resin and a plasticizer. (2) The glass run for a vehicle according to claim 1, wherein the beer chloride resin is a vinyl chloride copolymer partially crosslinked with 1,2-polybutadiene.

Claims (3)

[Claims] (1) A glass run for vehicles that has low sliding resistance and good wear resistance and is molded from a composition consisting of a partially crosslinked vinyl chloride resin and a plasticizer. (2) The glass run for a vehicle according to claim 1, wherein the vinyl chloride resin is a vinyl chloride copolymer partially crosslinked with 1,2-polybutadiene. (3) 1.2-polybutadiene has a molecular weight of 250
The glass run according to claim 2, which is a partially epoxidized 1,2-polybutadiene oligomer with an epoxidation rate of 0 to 5,500% and an epoxidation rate of 0 to 10%.