JPH0425580A - Coating composition and coated body - Google Patents

Abstract

PURPOSE:To improve the wear resistance of coating film surface and adherence between coating film and an object by blending a specific polyurethane with a silicone oil and siliconediol. CONSTITUTION:Polyurethane (A) is obtained by reacting a polyol (a), triethanolamine (b), the molar ratio of the component (a) to the component (b) being 1:(0.05-2.0), and a polyisocyanate (c), the molar ratio of -OH in the component (a) to -NCO in the component (c) being 1:(1.5-7). The title composition is obtained by blending 100 pts.wt. component (A), 5-200 pts.wt. silicone oil (B), siliconediol (C) that is a polymer having OH groups and siloxane bonds, the molar ratio of -NCO in the component (A) to -OH in the component (C) being (0.7-1.3):1, and, if necessary, a solvent (D) in an amount of 10-90 pts.wt. for 100 pts.wt. of the total of the components (A) to (D).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a coating composition and the same coating suitable for coating automotive parts such as glass runs, weather strips, double-sided adhesive tapes, synthetic resin products, etc. It relates to a painted body having a composition applied to its surface.

[Conventional technology]

Conventionally, natural rubber (NR), styrene-butanene copolymer comb (SBR), butadiene comb (BR), isobutylene-isoprene copolymer comb (IIR), chloroprene rubber (CR), acrylonitrile butadiene copolymer rubber (
NBR), isoprene comb (IR), ethylene-propylene-diene copolymer comb (EPDM), ethylene-propylene copolymer rubber (EPM), and other synthetic rubbers, cotton, rayon, ABS, PS, etc., are coated with nylon. system,
Epoxy-based, acrylic-based, acrylic-ethylene copolymer-based resin paints, or rubber-based paints such as BR and CR1SBR are used.

[Problem to be solved by the invention]

The above-mentioned conventional resin-based paints and rubber-based paints have problems in that they have poor adhesion to coated objects such as combs, synthetic resins, and fibers, and the resulting paint films have poor abrasion resistance.

The purpose of the present invention is to solve the above-mentioned problems, and to provide a coating composition that provides excellent abrasion resistance on the surface of the resulting coating film and good adhesion between the coating film and the object to be coated, and the characteristics of this coating composition. The object of the present invention is to provide a coated body exhibiting properties such as abrasion resistance and water repellency.

[Means to solve the problem]

In order to achieve the above object, in the first invention of the present invention,
It consists of a polyol, triethanolamine, and polyisocyanate, with a molar ratio of polyol:triethanolamine of 1:0.05 to 2.0, and a hydroxyl group (
-OH): molar ratio of isocyanate group (-NCO) is 1
: 5 to 200 parts by weight of silicone oil and silicone diol to 100 parts by weight of polyurethane having a molar ratio of isocyanate groups (-NCO) to hydroxyl groups (-OH) of 0.7 to 1. A method of blending the ingredients in an amount of 3:1 is adopted.

In the second invention, the coating composition according to claim 1 is applied to the surface of a base material made of resin or rubber.

[Detailed explanation of means]

First, the polyurethane used in the present invention will be explained.

Polyols include polyoxypropylene glycol (PPG), propylene oxide adduct of glycerin, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of pentaerythritol, triethylene glycol (TG), addition of propylene oxide to sucrose. Examples include compounds such as The above polyoxypropylene glycol has a number average molecular weight of 8
A value in the range of 00 to 6000 is preferred.

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, such as 2,4-tolidene diisocyanate (TD I), a ratio of 65/35 (2,4-tolylene diisocyanate to 2,6-)lylene diisocyanate, or the following: Similar) Tolylene diisocyanate, 80/2
0) lylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), dianisidine diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, 1. 5-naphthalene diisocyanate (NDI),
Hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 2,4-)lylene diisocyanate, hydrogenated 65/35 tolylene diisocyanate, hydrogenated 80/20 tolylene diisocyanate, isophorone diisocyanate (IPDI), 4 .4', 4'
4rifenylmethane triisocyanate, tris(p
Isocyanate (phenyl) thiophosphate, etc. are used.

The molar ratio of the polyol:triethanolamine is l
: 0.05 to 2.0. If this ratio is less than 0.05 or more than 2.0, the adhesion of the resulting coating film to the object to be coated will be greatly reduced.

Further, the molar ratio of hydroxyl group (-0)() in the polyol to isocyanate group (NCO) in the polyisocyanate is 1:1.5 to 7, and the isocyanate group is blended in excess with respect to the hydroxyl group.

When this ratio is less than 1.5 or more than 7, the adhesion of the resulting coating film to the object to be coated decreases, and may not adhere properly.

As the silicone oil, dimethyl silicone oil, methyl chloride silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, fluorosilicone oil, etc. are used. The blending ratio of this silicone oil is 5 parts by weight based on 100 parts by weight of the polyurethane.
~200 parts by weight. If the blending ratio is less than 5 parts by weight, it is impossible to improve the abrasion resistance, and even if it is blended in an amount exceeding 200 parts by weight, the effect of improving the abrasion resistance does not change, but instead the adhesion deteriorates. .

Next, the silicone diol can be a polymer having a hydroxyl group and a siloxane bond, and has, for example, the following structural formula.

(CH2),.

CH3=CH31 1: 1.

SiO, S 10 1 : : CH3CH3n CH3 Sl (CH2). OH CH3 However, n is 1 to 20, hydroxyl value is 10 to 450,
The average molecular weight is 500-11,200.

This silicone diol is a curing agent for the polyurethane,
It functions as a chain extender and also contributes to improving wear resistance. The molar ratio of isocyanate groups in the polyurethane to hydroxyl groups in the silicone diol is in the range of 0.7 to 1°3=1. When this molar ratio is less than 0.7, the adhesion of the resulting coating film to the object to be coated decreases, and it is also impossible to improve the abrasion resistance. Moreover, when it exceeds 1.3, the adhesion of the coating film to the object to be coated decreases.

In the present invention, a solvent may be added if necessary. Examples of this solvent include Hensen, toluene, xylene, ethylbenzene, trichloroethylene, ethylene chloride, dimethylformamide, dimethyl sulfoxide,
Methyl ethyl ketone, athene, methyl isopropyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate-n-butinopeacetate, anisole, tetrahydrofuran, etc. are used.

The blending ratio of this solvent is 10 parts by weight in 100 parts by weight of the coating composition.
A range of 90 parts by weight is preferred. If the blending ratio is less than 10 parts by weight, the solid content will be relatively high and the viscosity of the coating composition will increase, making coating work difficult and likely resulting in a decrease in adhesion; if it exceeds 90 parts by weight, On the contrary, the proportion of solids becomes low and the film thickness of the coating composition becomes thin, which is not preferable as a coating material.

The coating composition of the present invention is prepared, for example, as follows. First, the polyol, triethanolamine, polyisocyanate, and a necessary solvent are appropriately selected and mixed, and the mixture is reacted in dry nitrogen gas at 80°C for 13 hours.
A polyurethane having isocyanate groups is prepared.

Next, 5 to 200 parts by weight of silicone oil and silicone diol are added to 100 parts by weight of this polyurethane to form isocyanate groups and hydroxyl groups of -0.7 to 1.3.
A coating composition can be obtained by adding an amount of 1 and then adding a solvent to adjust the viscosity to be suitable for coating.

Further, the base material of the coated body of the second invention is a resin or rubber, and examples of the resin include vinyl chloride resin, polyethylene, polypropylene, polyurethane, or foams thereof;
As the com, the aforementioned EPDM, EPM, etc. are used.

[Effect]

By employing the above means, the coating composition of the first invention improves the abrasion resistance of the resulting coating film surface due to the lubricity and other properties of the silicone oil and silicone diol, and also improves the abrasion resistance of the resulting coating film surface. It is composed of ethanolamine and polyisocyanate, and by blending an excess of isocyanate groups, the adhesion to the coated object is improved due to effects such as hydrogen bonding due to polyurethane with a specific structure having isocyanate groups.

In addition, in the second invention, since the above-mentioned coating composition is applied to the surface of the painted body, performance such as abrasion resistance and water repellency is exhibited based on the characteristics of the coating composition of the first invention. .

[Examples 1 to 12 and Comparative Examples 1 to 6] Examples embodying the first invention will be described below in comparison with comparative examples. In addition, on each side, parts represent parts by weight.

First, the object to be coated is a vulcanized product as shown below.

That is, the vulcanizate contains 100 parts of EPDM, 70 parts of carbon black, 35 parts of mineral oil, 7 parts of zinc oxide, and 2 parts of stearic acid.
1 part of sulfur, 2 parts of vulcanization accelerator, and 1.5 parts of sulfur.
It was vulcanized at 60°C for 30 minutes.

In addition, the wear resistance test was conducted by the following method, and the wear resistance was evaluated based on the amount of wear loss.

That is, Test machine: Taper type rotary abrasion saucer (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Test conditions: Wear wheel: H-22, load, 1 kg Wear rotation speed: 60 rpm Sample size: 10100 mm x 100 Number of wear, 1000 times Next, Polyol (PO), triethanolamine (TEA), polyisocyanate (PI) shown in Table 1 below
) were mixed in trichlorethylene and reacted at 80° C. for 3 hours in a nitrogen gas atmosphere to synthesize polyurethane. The obtained polyurethane had a solid content of 83% and a trichlorethylene content of 17%, and the abbreviations in Table 1 have the following meanings.

PPG 3000: Polyoxypropylene glycol with a number average molecular weight of 3000 PPG 1000: Polyoxypropylene glycol with a number average molecular weight of 1000 PPG 2000: Polyoxypropylene glycol with a number average molecular weight of 2000 TG 3000: Triethylene glycol TG 1000 with a number average molecular weight of 3000: Triethylene glycol TG 2000 with a number average molecular weight of 1000/triethylene glycol MDI with a number average molecular weight 2000: 4.4'-diphenylmethane diisocyanate ND, I: 1. 5-Naphthalene diisocyanate
A coating composition was obtained by blending prescribed amounts of the silicone oil and silicone diol shown in . The same coating composition was applied to the object to be coated and dried at 80° C. for 20 minutes, and then the abrasion resistance test was conducted. The results are shown in Table 4 below.

table The abbreviations in Table-2 represent the following meanings.

DMSi stands for dimethyl silicone oil.

(1): Viscosity of 10,000 centistokes (cSt) (
2): One with a viscosity of 60,000 cSt (3) Two: One with a viscosity of 100,000 cSt The silicone diol represents the following.

(a) Hydroxyl number 112, average molecular weight 1000 (b
) Hydroxyl number 62, average molecular weight 1800 (C) Hydroxyl number 35, average molecular weight 3200 (d) Hydroxyl number 20, average molecular weight 5600 Also, as a comparative example, Table -
A coating composition as shown in No. 3 was prepared, applied to the object to be coated in the same manner, dried, and then subjected to an abrasion resistance test. The results are shown in Table 5 below.

table Above table The meaning of the abbreviation 3 is as shown in the table above. same as 2 be.

As can be seen from Table 4 above, the coating compositions of each example had an abrasion loss of 40% even after 1000 abrasion tests.
．． It is a small amount, 0 to 61.5 mg. The reason why the coating compositions of each example exhibit such excellent wear resistance without impairing the material properties of the coated object is presumed to be based on the lubricity and other properties of silicone oil and silicone diol. be done.

Further, the coating composition of each example contained a predetermined amount of polyol,
It is composed of triethanolamine and polyisocyanate, and exhibits excellent adhesion to the vulcanized rubber to be coated due to hydrogen bonding due to polyurethane having isocyanate groups.

On the other hand, as can be seen from Table 5, the paint compositions of each comparative example had a large abrasion loss of 2005.9 to 5980.1 mg, and were inferior in abrasion resistance.

[Examples 13 to 24 and Comparative Examples 7 to 12] Next, examples will be described in which the second invention is embodied in a glass run coated with a coating composition.

A glass run is a member made of synthetic rubber or synthetic resin that is installed to seal the edge of a window glass when the window glass is opened or closed.
In particular, wear resistance is required.

Therefore, on the surface of the base material of the glass run (similar to the above-mentioned Examples 1-12), the above-mentioned Examples 1-13 and Comparative Example 1
The paints shown in 6 to 6 were applied, and the following abrasion resistance test was conducted to evaluate the performance of the glass run coated with the paint composition, and the results are shown in Table 6.

Abrasion resistance test: The abrasion resistance was evaluated by abrading the painted surface of the base material coated with the coating composition under the following test conditions.

Testing machine, KI type abrasion tester Wear element: Crow (thickness 5 mm) Load, 3 kg Wear element cycle: 60 times/min Stroke of wear element: 145 mm (Test method) The above test piece was attached to the above test machine and painted. The surface was worn 30,000 times and the condition after that was examined. Those in which the base material was not exposed were determined to be acceptable, and those in which the base material was exposed were determined to be failed.

In addition, in the comparative example, the amount of wear was measured.

As seen from Table-6 and Table-7 above, Examples 13-
In Comparative Examples 7 to 12, the abrasion loss was 20 to 15110 m.
The wear resistance was poor at g/30,000 times.

[Examples 25 to 36 and Comparative Examples 13 to 18] Next, the second
An example in which the invention is embodied in a weather strip coated with a coating composition will be described.

Synthetic combs and synthetic resin weather strips are used to seal automobile window frames and window glass. This Unisa strip is particularly required to be abrasion resistant since the window glass and door slide when these are opened and closed. As the base material of the Unisa strip, polyolefin vulcanized rubber such as EPDM, EPM, etc. is used. In contrast to these polyolefin-based vulcanized rubbers, natural rubber (NR), polybutadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), and polyisoprene rubber (IR
) Compounds containing chloroprene rubber (CR), isobutylene-isoprene copolymer rubber (IIR), etc. in an amount of 1/2 or less may also be used.

The above vulcanized rubber contains commonly used formulations, namely sulfur, morpholine, disulfide, dicumyl peroxide as a vulcanizing agent, 2-mercaptobenzothiazole, zinc dimethyldithiocarbamate, tetramethylthiuram disulfide as a vulcanization accelerator. etc., phenyl-α-naphthylamine, 2.6-t-butyl-p-cresol, etc. as antiaging agents, antioxidants, and ozone deterioration inhibitors, carbon black, hydrous silicic acid, magnesium carbonate, clay, etc. as fillers, Dioctyl sebacate, mineral oil, etc. are used as plasticizers.

As foaming agents for rubber, N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl N,N'-
dinitrosoterephthalamide, asodicarbonoamide,
Azobisisobutyronitrile, benzenesulfonyl hydrazide, p, p'-oxybis(benzenesulfonyl hydrazide), toluenesulfonyl hydrazide, etc., and foaming aids such as urea and salicylic acid are suitably blended depending on the amount of foaming.

For the base material of this weather strip (similar to the above-mentioned Examples 1-12), the above-mentioned Examples 1-12 and Comparative Examples 1-1
The coating composition No. 6 was applied, and the following abrasion resistance test was conducted to evaluate the abrasion resistance.

The results are shown in Table-8 and Table-9.

Abrasion resistance test: Using an abrasion resistance test using a Karasuji abrasion tester, which is an improved version of the Gakushin abrasion tester, the abrasion resistance test was conducted under normal conditions under the following test conditions.

Wearing element Nigarasu (thickness 5 rnm) Wear cycle: 60 times/min Stroke of wear element: 70mm Wear count: 50,000 times The specific test method is as described in the above example. The same is true.

3-24 Isocyanate groups in the coating composition in Table 9 above:
The molar ratio of hydroxyl groups was 0.4 in Comparative Example 13, 1.5 in Comparative Example 14, 0.4 in Comparative Example 15, and 1 in Comparative Example 16.
．． It is 5.

From the results in Tables 8 and 9 above, Examples 25 to 36 all passed the wear resistance test, while Comparative Example 13
-18 had a wear amount of 490 to 9,690 mg, 150,000 times, and lacked abrasion resistance.

In addition to the weather strip, members such as rubber seals and O-rings that require wear resistance, adhesion, etc. can also be used as base materials for forming the coated body of the second invention.

[Examples 37 to 46 and Comparative Examples 19 and 20:] Examples will be described in which the second invention is embodied in a double-sided adhesive tape whose side surface is coated with a coating composition.

Side moldings are attached to the sides of the car body using double-sided adhesive tape. Assuming this case, a test piece was prepared as follows, and the adhesive area and tensile shear strength were measured.

(1) Preparation of test piece After coating the coating composition shown in Table-IO on the side edge of a double-sided adhesive tape, it was left for -1 week and subjected to a test.

Then, a painted steel plate was adhered to one side coated with an adhesive of 8 times expanded polyethylene foam, which is the base material of the double-sided adhesive tape, and the other side coated with adhesive was adhered to a vinyl chloride resin plate. It was used as a test piece. In addition, Comparative Example 19.2
0 was a test piece to which no coating composition was applied.

(2) Measurement of adhesion area and tensile shear strength After immersing each of the above test pieces in gasoline (G) and wax remover (W> as solvents for 1 hour each at room temperature of 23°C, adhesion area and tensile speed of 50 mm) The tensile shear strength was measured under the condition of /min.The results are shown in Table-IO.

From the results in Table 0 above, in Examples 37 to 46, 86 to 92% of the adhesive area was secured even when immersed in gasoline or wax remover, and the tensile shear strength was 7.7 to 8.1 kg/crl. It can be seen that this shows a high value. On the other hand, in Comparative Examples 19 and 20, the adhesive area was 31 to 35%, and the tensile shear strength was L 5 kg/
It is a low value of ct.

Therefore, if a side molding is attached to the side surface of an automobile body using an adhesive tape with the paint composition of each example applied to the side edge, even if gasoline or wax remover adheres to the side edge of the adhesive tape, the side molding will be removed. The molding is held to the body with sufficient bonding strength.

In addition, the present invention can also be used as an adhesive tape for use on members in chemical factories and the like where solvents such as toluene and xylene may adhere.

〔Effect of the invention〕

The coating composition of the first aspect of the present invention has the effect that the resulting coating film surface has excellent abrasion resistance and also has good adhesion between the coating film and the object to be coated.

Furthermore, the coated body of the second invention exhibits excellent performance such as abrasion resistance and water repellency based on the characteristics of the coating composition of the first invention.

Claims (1)

[Claims] 1. Consisting of polyol, triethanolamine and polyisocyanate, the molar ratio of polyol:triethanolamine is 1:0.05 to 2.0, and hydroxyl group (
-OH): molar ratio of isocyanate group (-NCO) is 1
:1.5-7 for 100 parts by weight of polyurethane,
A coating composition comprising 5 to 200 parts by weight of silicone oil and silicone diol in an amount such that the molar ratio of isocyanate groups (-NCO) to hydroxyl groups (-OH) is 0.7 to 1.3:1. 2. A coated body obtained by applying the coating composition according to claim 1 onto the surface of a base material made of resin or rubber.