JPH01278849A - Weather strip - Google Patents

Abstract

PURPOSE:To make improvements in abrasion resistance on a weather strip surface by applying a halide agent to a urethane coat being formed on the weather strip surface. CONSTITUTION:Polyol (PO), triethanolamine (TEA) and polyisocyanate (PI) shown in table-1 are mixed in tricholoethelene, and reacted as long as three hours at a temperature of 80 deg.C in a nitrogen gas atmosphere, thus polyurethane is synthesized. Next, a coating constituent made up of mixing a halide agent (weight part) shown in table-2 in a solid portion 100wt part of erethane is se cured, while this constituent is applied to a base material made of EPDM, and a weather strip for an automobile is manufactured. With this constitution, such a weather strip that is excellent in surface coating adhesion to polyolefine vulcanized rubber or the like and very good in abrasion resistance, besides no loss of flexibility and bendability is securable.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides an automotive weathering material with improved wear resistance and adhesion.
It's about strips.

[Prior Art] Rubber or synthetic resin base materials are used in automobile weather strips.

The automobile weather covers 1 to 1-rip are required to have a wide variety of performances such as soundproofing, weather resistance, and especially abrasion resistance.

Conventionally, methods of imparting wear resistance to weatherstrips include providing a chloroprene rubber coating coated with urethane paint on the surface, providing a silicone coating layer, and the like.

However, the formation of the chloroprene rubber coating has the disadvantage of continuous molding and is also expensive.

Furthermore, silicone coatings have the disadvantage of poor weather resistance and abrasion resistance, and have not been able to satisfy the above-mentioned performance.

On the other hand, in recent years, polyolefin-based vulcanized rubbers, such as ethylene-propylene-diene terpolymer rubber (EPDM)
Ethylene-propylene copolymer rubber (EPM) has come to be used in many fields because it has superior weather resistance, aging resistance, and ozone resistance compared to conventional synthetic rubber.

[Problems to be Solved by the Invention] However, since the polyolefin vulcanized rubber described above has poor abrasion resistance, when it is used as a base material for automobile weather strips, it is necessary to coat the surface with urethane paint or the like. It won't happen.

However, since the vulcanized rubber does not contain unsaturated bonds or polar groups in the main chain of its constituent molecules, the resulting coating film is likely to peel off even when paint is applied. The current situation is extremely difficult.

The object of the present invention is to solve the above-mentioned conventional problems, to avoid impairing the flexibility and flexibility that are the characteristics of the polyolefin-based vulcanized rubber, and to provide a "-" densely compressed material for the vulcanized rubber. It is an object of the present invention to provide a weather strip having good abrasion resistance, which is formed by applying a coating composition having high strength to the surface of a base material.

[Means for Solving the Problem] In order to solve the above problems, the present invention provides polyol, 1
〜composed of triethanolamine and polyisocyanate, the molar ratio of polyol:triethanolamine is 0.
05 to 2.0, and the hydroxyl group of the polyol (-01
-1): Isocyanate Ei of polyisocyanate (
-NGO) to 100 Iffi parts of polyurethane with a molar ratio of 1=1.5-7, 0.00
A coating composition prepared by blending 1 part of 2-2Offffff and a solvent was applied to the surface of a base material made of vulcanized rubber or resin to form a lip.

[Detailed explanation of the means] First, let's talk about polyurethane.

Examples of polyols include polypropylene glycol, a compound obtained by adding propylene oxylide to glycerin, and a compound obtained by adding propylene oxylide to sucrose. preferable.

The amine is triethanolamine, and a crosslinking reaction occurs with monoethanolamine and jetanolamine.
It is unsuitable because polyurethane gels.

Polyisocyanate is a compound having a plurality of isocyanate groups, and examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), 1,5-no-phthalenedi-cyane 1-(NDI), and xylylene diisocyanate (XDI). , 4゜4-diphenylmethane diisocyanate (MDI>, 4.4", 4-"-triphenylmethane triisocyanate (TPM I>,
inphorone diisocyanate (IPDI), etc., 4,4'-methylene bis(cyclohexyl isocyanate) (H-MDI), hexahydroxylylene diisocyanate 1 to 1, etc. as aliphatic polyinsocyanate, 1,6 as aliphatic polyisocyanate -hexylylene diisocyanes 1 and the like.

The molar ratio of the polyol:triethanolamine is 1
:0.05 to 2.0. If this ratio is less than 0.05 or more than 2.0, the adhesion will be greatly reduced.

Also, hydroxyl I (-Of-1) in polyol
: Isocyanate group in polyisocyanate (-NCO
), the isocyanate group is blended in excess with respect to the hydroxyl group at a molar ratio of 1:1.5 to 7. This ratio is 1.
When it is less than 5 or more than 7, the adhesion strength decreases, and adhesion may not be achieved in some cases.

Polyurethane is synthesized by mixing the polyol, triethanolamine, and polyisocyanes 1 to 1, and reacting the mixture at 80'C for 3 hours in a nitrogen gas atmosphere.

Next, as a halogenating agent, for example, t-butylhypochloride (t-BHC) is used as an alkylhypohalide.
), sodium hypochlorite as hypohalite,
Potassium hypochlorite, compounds with 100NX-bonds (X is a halogen atom) in the molecule include N-bromo-1-tucdiimide (NBSI) and trichlorisocyanuric acid (TCI).
A>, isocyanuric dichloride (D i CIA)
On the other hand, examples include antimony fluoride, a mixed solution of sulfur fluoride and bromine, among which alkyl hypohalides, hypohalites or -C in the molecule are mentioned.
Compounds with ONX-bonds are preferred.

The blending ratio of this halogenating agent is in the range of 0.002 to 20 parts by weight based on 100 parts by weight of polyurethane. When the blending ratio is less than 0.002 parts by weight, the degree of halogenation is small, so that the adhesion is not improved much, and when it exceeds 20 parts by weight, the stability of the coating composition deteriorates.

In addition, as a solvent, for example, n-
He4 = San, n-hebutane, n-octane, cyclohexane, cyclooctane as alicyclic hydrocarbons, benzene, ethylbenzene, toluene, xylene as aromatic hydrocarbons, acetone, methyl butyl ketone as ketones , ethylpropylene, methyl butyl ketone, tetrahydrofuran as ethers, methyl acetate, ethyl acetate, isopropyl acetate as acetic esters, methylene chloride as halogenated hydrocarbon, 1,1゜1
Examples include -trichloroethane, 1-lychloroethylene, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and the like.

These solvents may be used alone or as a mixed solvent of two or more.

The blending ratio of this solvent is from 3 to 100 parts by weight of the coating composition.
A wide range of 95 debts is acceptable. If the ratio is less than 3 parts by weight, the solid content will be relatively high and the viscosity of the coating composition will reach its upper limit, making coating work difficult and likely resulting in a decrease in adhesion; if it exceeds 95 parts by weight, On the other hand, as the proportion of solids decreases, the film thickness of the coating composition becomes thinner, and adhesion tends to decrease.

The base material constituting the weather strip is polyolefin vulcanized rubber. Specific examples include ethylene-propylene-diene ternary copolymer rubber (PDM) and ethylene-propylene copolymer rubber (EPM).

Furthermore, examples include those containing other rubber components in amounts within a range that does not impair the properties of these copolymer rubbers. That is, natural rubber (NR>), styrene-butadiene copolymer rubber (
SBR), polybutadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), polyisoprene rubber (IR), chloroprene rubber (CR), or butyl rubber (IIR), etc. are 1/2 ffl suspension of the above polyolefin vulcanized rubber. You may use a mixture containing less than 1 part.

Additionally, thermoplastic elastomers and the like can also be used as the base material.

The above-mentioned various vulcanized rubbers contain commonly used compounds, i.e. sulfur, morpholine, disulfide, dicumyl peroxide, etc. are used as vulcanizing agents, 2-mercap-1 to benzothiazole, dimedyldithiolubamine, etc. are used as vulcanization accelerators. Zinc acid, tetramethylthiuram disulfide, etc. are used as anti-aging agents, antioxidants, and ozone deterioration inhibitors.
α-naphthylamine, 2,6-di-t-butyl-p-cresol, etc., and carbon black as a filler,
Hydrous silicic acid, magnesium carbonate, clay, etc. are used, and dioctyl sebacate, mineral oil, etc. are used as plasticizers.

Foaming agents for rubber include N,N--dinitrosopentamethylene 1-lamin, N,N--dimethyl-N.

N=-dinitrosoterephthalamide, azodicarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, p,p-oxybis(benzenesulfonylhydrazide), toluenesulfonylhydrazide, etc., and foaming aids include urea, V Lytic acid and the like are appropriately blended depending on the amount of foaming.

Moreover, the presence or absence of foaming is adjusted as appropriate depending on the application location.

[Function] By employing the above means, the urethane coating formed on the weatherstrip surface has extremely good adhesion to the base material due to the use of the halogenating agent, thus improving the wear resistance of the weatherstrip surface. performance is significantly improved.

Furthermore, it maintains excellent wear resistance even after heat resistance and weather resistance.

[Examples 1 to 6 and Comparative Examples 1 and 2] Examples embodying the present invention will be described below in comparison with comparative examples.

First, polyol (PO), 1-reethanolamine (TEA), and polyisocyanate (PI) shown in Table 1 are mixed in trichlorethylene, and reacted at 80°C for 3 hours in a nitrogen gas atmosphere to synthesize polyurethane. did.

The 1q polyurethane obtained had a solid content of 83% and a trichlorethylene content of 17%.

(Margin below) Table-1 The abbreviations in Table-1 represent the following meanings.

・TG 1000.2000, 3000: poly(1 to
Liethylene glycol)・PPG 1000,200
0,3000: Number average molecular weight 1000,200 respectively
0.3000 polypropylene glycol/MDI: 4.4--diphenylmethane diisocyanate
1~・NDI: 1.5-nanotale diisocyanate 1~・X
DI: xylylene diisocyanate IPDI: isophorone diisocyanate TDI = tolylene diisocyanate Next, a coating composition containing a halogenating agent (heavy ω parts) shown in Table 2 below per 100 wt ω parts of the solid content of the above polyurethane. The material was injected and applied to an EPDM base material to produce a sea urchin 1 earth strip for an automobile. It was subjected to a wear test of 50,000 times. The results are shown in Table-2.

The method for manufacturing the base material and the weather strip are as follows.

(1) Manufacturing method of EPDM base material 100 parts by weight of EPDM, 70 parts by weight of carhon flak,
After extrusion molding a rubber compound consisting of 35 parts by weight of mineral oil, 5 parts by weight of zinc white, 1 part by weight of stearic acid, 2 parts by weight of vulcanization accelerator, and 1.5 parts by weight of sulfur, it was heated to 30 parts by weight at 160°C. Vulcanized for minutes.

(2) Method for Preparing Unidace 1 to Lip After cleaning the surface of the EPDM substrate described above, a coating composition was applied according to a conventional method and dried at a temperature ranging from room temperature to 180°C. This drying temperature is preferably in the range of 80 to 150°C. 80℃
If the temperature is less than 150° C., the curing time becomes long, and if the temperature exceeds 150° C., there is a risk of thermal aging of the plugging material or the coating composition.

In addition, a glass edge abrasion tester, which is an improved version of the academic abrasion tester, was used for the abrasion resistance test. The test conditions and test method are described below.

(Test conditions) Friction element Nigarasu (thickness 5 mm) Friction element cycle: 60 times/min Friction element stroke near 0 mm (Test method) Normal friction Two base materials are attached to the above testing machine, and the base material is rubbed and normal Examine the abrasion properties of

(Margin below) The abbreviations in Table 2 have the following meanings.

・t-BHC: t-butylhybochloride ・NBS
I: N-Promolyximide/TCIA: Isocyanuric acid trichloride The numbers in parentheses in the halogenating agent column in Table 2 indicate the heavy ω parts of the halogenating agent per 1 part of 100 fflff solid content of the polyurethane.

Also, in Table 2, the ○ mark indicates that there is almost no wear, and the X mark indicates I! Indicates that the product is rejected due to significant wear.

Next, Weathers 1 to Lip, which had the coating composition applied to an EPDM base material, was bent 180 degrees to examine its followability, but the flexibility and bendability, which are the characteristics of polyolefin vulcanized rubber, were not impaired in any way. It showed good followability without any problems.

As can be seen from the above coating 2, the weather strips using the coating compositions of Examples 1 to 6 showed good results in the 50,000-cycle abrasion test. On the other hand, in Comparative Example 1 in which the halogenating agent content exceeds 20 uH parts, the coating composition gels, and the molar ratio of triethanolamine to polyol in the polyurethane composition is 2.0.
Comparative Example 2, which exceeds the above, has poor wear resistance.

The reason why the wells 1 to the lips of the above examples exhibit such excellent abrasion resistance is that the polyurethane employed in the present invention has extremely excellent abrasion resistance and has excellent flexibility and flexibility. In addition to being excellent, the halogen in the halogenating agent halogenates the surface of the FPDM base material to be treated, and also halogenates the polyurethane in the paint composition, thereby improving the surface of the base material and the paint composition. This is thought to be because the intermolecular forces between the two substances increase, and the adhesion of the coating composition to the substrate surface improves.

[Effects of the Invention] Weathers 1 to Lip of the present invention do not impair the flexibility and flexibility that are the characteristics of polyolefin vulcanized rubber, etc., and also improve the density of the surface coating film on the vulcanized rubber, etc. It has excellent effects such as extremely good wear resistance.

Claims (1)

[Claims] 1. Consisting of a polyol, triethanolamine, and polyisocyanate, the molar ratio of polyol:triethanolamine is 1:0.05 to 2.0, and the hydroxyl group (-OH) of the polyol: the isocyanate group (-NCO) of the polyisocyanate. ) to 100 parts by weight of polyurethane with a molar ratio of 1:1.5 to 7.
．． A weather strip made by applying a coating composition containing 0.002 to 20 parts by weight and a solvent onto the surface of a vulcanized rubber or resin base material.