JPH048778A - Paint composition and painted material - Google Patents

Abstract

PURPOSE:To obtain a paint composition giving a coating film with excellent wear resistance and adhesion containing a fixed ratio of a specific polyurethane, fluororesin, silicone oil, mercaptosilicone and halogenating agent. CONSTITUTION:The objective composition comprises (A) 100 pts.wt. polyurethane composed of polyol, triethanolamine and polyisocyanate containing 1:(0.05-2.0) molar ratio of said polyol:triethanolamine and 1:(1.5-7) molar ratio of hydroxyl group (OH):isocyanate group (NCO), (B) 2-100 pts.wt. fluororesin such as tetrafluoroethylene resin, (C) 5-200 pts.wt. silicone oil, (D) mercaptosilicone in an amount of giving (0.7-1.3):1 molar ratio of mercapto group:isocyanate group and (E) 0.002-20 pts.wt. halogenating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides coating compositions suitable for coating rubber products such as glass runs, bait strips, double-sided adhesive tapes, synthetic resin products, etc. as automobile parts, and the like. The present invention relates to a painted body having a surface coated with a paint composition.

[Conventional technology]

Conventionally, natural rubber (NR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), inbutylene-isoprene copolymer rubber (IIR), chloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), Isoprene rubber (IR), ethylene-propylene-diene copolymer rubber (EPDM), ethylene-
Synthetic rubber such as propylene copolymer rubber (EPM), cotton,
For surface coating of rayon, ABS, PS, etc., nylon-based, epoxy-based, acrylic-based, acrylic-ethylene copolymer-based resin paints, or rubber-based paints such as BR, CR, SBR, etc. are used.

[Problem to be solved by the invention]

The conventional resin-based paints and rubber-based paints have problems in that they have poor adhesion to coated objects such as rubber, 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 polyol, triethanolamine, and polyisocyanate, the molar ratio of polyol:triethanolamine is 1:0.05 to 2.0, and the hydroxyl group (-O
H): The molar ratio of isocyanate groups (-NCO) is 1:
For 100 parts by weight of polyurethane having a polyurethane content of 1.5 to 7,
2 to 100 parts by weight of fluororesin, 5 parts of silicone oil
~200 parts by weight, mercapto silicone in an amount such that the molar ratio of mercapto group (-8H): isocyanate group (-NCO) is 0.7 to 1.3:1, and halogenating agent to 0°0
02 to 20 parts by weight 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), and propylene oxide adduct of 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-tolylene diisocyanate (TDI), 65/35 (ratio of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hereinafter the same). ) Tolylene diisocyanate, 80/20
) lylene diisocyanate, 4,47-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 2,4-1-lylene diisocyanate, hydrogenated 65/35 tolylene diisocyanate, hydrogenated 80/20 Tolylene diisocyanate, isophorone diisocyanate (IPDI), 4.4', 4'
-triphenylmethane triisocyanate, tris(p
-isocyanate phenyl) thiophosphate, etc. are used.

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 of the resulting coating film to the object to be coated will be greatly reduced.

Further, the molar ratio of hydroxyl groups (-OH) in the polyol to isocyanate groups (-NCO) in the polyisocyanate is 1:1.5 to 7, and the isocyanate groups are blended in excess to the hydroxyl groups.

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.

Fluororesins include tetrafluoroethylene resin,
Tetrafluoroethylene-hexafluoropropylene copolymer resin, trifluorochloroethylene resin, vinylidene fluoride resin, etc. are used. The blending ratio of this fluororesin is in the range of 2 to 100 parts by weight per 100 parts by weight of the polyurethane. If the proportion is less than 2 parts by weight, the abrasion resistance will not improve, and if it exceeds 100 parts by weight, it will be difficult to apply the coating composition.

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. .

Mercapto silicone is a polymer having a mercapto group and a siloxane bond, and for example, one having the following structural formula can be used.

This mercapto silicone functions as a curing agent for the polyurethane and also contributes to improving wear resistance. The molar ratio of mercapto groups in the mercapto silicone to isocyanate groups in the polyurethane 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.

As a halogenating agent, N-promsuccinimide (N
BSI), acid imide halogen compounds such as N-bromphthalimide, isocyanuric acid halides such as trichloroin cyanuric acid (TCIA) and dichloroisocyanuric acid, halogenated hydantoins such as dichlorodimethylhydantoin, alkyl hypohalides, and the like.

The above-mentioned alkyl hypohalides are normal, secondary or tertiary alkyl hypohalides, particularly stable tertiary alkyl chlorides and bromides, such as tertiary butyl hypobromide, tertiary amyl hypobromide, etc. is preferred, and halogen-substituted alkyl hypochlorides such as dichloro, trichloro or fluoromethyl hypochloride can also be used.

The halogenating agent is used in an amount of 0.002 to 20 parts by weight per 100 parts by weight of the polyurethane.

If the blending ratio is less than 0.002 parts by weight, the degree of halogenation is small, so there is little improvement in adhesion, and if it exceeds 20 parts by weight, the stability of the coating composition deteriorates.

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

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 same 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 at 80° C. for 3 hours in dry nitrogen gas to prepare a polyurethane having isocyanate groups.

Next, with respect to 100 parts by weight of this polyurethane, 2 to 100 parts by weight of fluororesin, 5 to 200 parts by weight of silicone oil, mercapto silicone in an amount such that mercapto group and isocyanate group = 0.7 to 1.3: 1, and halogenation. Agent 0. A coating composition is obtained by adding 2 to 20 parts by weight of OO and further adding a solvent to adjust the viscosity to a level suitable for coating. In this case, a part of the fluororesin may be replaced with molybdenum disulfide, glass fiber, carbon fiber, polyethylene, silicon oxide, calcium carbonate, magnesium carbonate, clay, or the like.

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 rubber, ethylene-propylene-diene ternary copolymer rubber (EPDM), ethylene-propylene copolymer rubber (EPM), etc. are used.

[Effect]

By adopting the above means, the coating composition of the first invention improves the abrasion resistance of the resulting coating film surface due to the lubricity of silicone oil and mercapto silicone and the low coefficient of friction of fluororesin. At the same time,
A halogenating agent halogenates the coated material to improve mutual intermolecular force, and is composed of polyol, triethanolamine, and polyisocyanate in a predetermined proportion, and has a specific structure having isocyanate groups by blending an excess of isocyanate groups. Adhesion to the object to be coated is improved due to effects such as hydrogen bonding caused by the polyurethane.

Moreover, 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 abrader (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Test conditions: Wear wheel, H-22, load, Ikg Wear rotation speed: 60 rpm Sample size: 10100 mm x 100 Number of wear, 1000 times Next, the following Polyol (PO), triethanolamine (TEA), polyisocyanate (PI) shown in Table-1
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 number average molecular weight 3000 PPG 1000 Polyoxypropylene glycol PPG 2000 with number average molecular weight 1000: Polyoxypropylene glycol TG 3000 with number average molecular weight 2000: Triethylene glycol TG 1000 with number average molecular weight 3000: Triethylene glycol TG 2000 with a number average molecular weight of 1000: Triethylene glycol with a number average molecular weight of 2000 MDI: 4.4'-diphenylmethane diisocyanate NDI: 1,5-naphthalene diisocyanate XDI:
Xylylene diisocyanate IPDI: Isophorone diisocyanate Next, based on 100 parts by weight of the solid content of the above various polyurethanes, Table 2 below
A coating composition was obtained by blending predetermined amounts of the fluororesin, silicone oil, mercapto silicone (MSi), and halogenating agent 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.

The abbreviations in Table-2 represent the following meanings.

Fluororesin refers to tetrafluoroethylene resin.

DMSi stands for dimethyl silicone oil.

(1): Viscosity of 10,000 centistokes (cSt) (
2): Viscosity of 60,000 cSt (3): Viscosity of 100,000 cSt Mercapto silicone has the following hydroxyl value.

(a) Viscosity 150 centistokes (cS) (25°C
), sulfur content 1.7 (X ) (b) viscosity 2oo
(cs), sulfur content 1.9 (%), (c) viscosity 18
0 (C3), sulfur content 1.8 (%), (d) viscosity 1
45 (cs), sulfur content 1.6 (%) The halogenating agent represents the following.

TCIA: I-lichloroisocyanuric acid NBSI:
N-promsuccinimide t-BHC: tertiary butyl hypochloride In addition, as a comparative example, a coating composition as shown in Table 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 3 The meanings of the abbreviations in Table 3 above are the same as those in Table 2 above.Table 4 As can be seen from Table 4 above, the coating compositions of each example had abrasion loss of 3.0% even after 1000 abrasion tests.
It is extremely small at 1-5.1 mg. The reason why the coating compositions of each example exhibit such excellent wear resistance without impairing the material properties of the object to be coated is the lubricity of silicone oil and mercapto silicone, and the low coefficient of friction of fluororesin. It is presumed that this is based on characteristics, etc.

In addition, the coating composition of each example is composed of a predetermined amount of polyol, triethanolamine, and polyisocyanate, and the halogenating agent halogenates the coated object to improve mutual intermolecular force. It exhibits excellent adhesion to vulcanized rubber, which is the object to be coated, due to hydrogen bonding caused by polyurethane.

On the other hand, as can be seen from Table 5, the coating compositions of each comparative example either gelled or the abrasion loss was 632.8 to 3951.
It is large at 6 mg and has poor wear 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, the
The paints shown in Comparative Examples 1 to 13 and Comparative Examples 1 to 6 were applied, and the following abrasion resistance test was conducted to evaluate the performance of the glass runs coated with the paints, 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 Abrasion element: Glass (thickness 5 mm) Load, 3 kg Abrasion element cycle: 60 times/min Stroke of abrasion 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.

Table 6 Table 7 In Table 7 above, the ratio of mercapto group/isocyanate group of mercapto silicone in the coating composition is 0.4 in Comparative Example 7, 1.5 in Comparative Example 8, and 0.0 in Comparative Example 9. 4. Comparative Example 10 is 1.5.

As seen from Table-6 and Table-7 above, Examples 13-
In Comparative Examples 7 to 12, the wear amount was 20 to 1350 mg, whereas in Comparative Examples 7 to 12, the abrasion resistance test result was passed in all cases.
/30,000 times or the coating composition gelled.

[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.

Weather strips made of synthetic rubber or synthetic resin are used to seal car window frames and window glass. This weather strip is particularly required to have abrasion resistance because it slides when opening and closing window glass and doors. As the base material of the weather strip, polyolefin vulcanized rubber such as EPDM, EP, M, etc. is used. In contrast to these polyolefin-based vulcanized rubbers, natural rubber (NR)
, polybutadiene rubber (BR), acrylonitrile-
Rubbers containing butadiene copolymer rubber (NBR), polyisoprene rubber (■R), chloroprene rubber (CR), isobutylene-isoprene copolymer rubber (IIR), etc. in an amount of 1/2 or less may also be used.

The above-mentioned vulcanization comb contains the commonly used formulations, namely sulfur, morpholine, disulfide, dicumyl peroxide as vulcanizing agents, 2-mercaptobenzothiazole, zinc dimethyldithiocarbamate, tetramethylthiuram disulfide as vulcanization accelerators. 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 a foaming agent for rubber, N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, azodicalphonamide, azobisisobutyronitrile, pensene sulfonyl Hydrazide, p,p-oxybis(pensene sulfonyl hydrazide), toluenesulfonyl hydrazide, etc., and foaming aids such as urea, salicylic acid, etc. are suitably blended depending on the amount of foaming.

For the base material of this weather strip, Examples 1 to 1
The coating compositions of No. 2 and Comparative Examples 7 to 12 were 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 glass e-soji 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.

Abrasion element: glass (thickness 5 mm) Abrasion element cycle: 60 times/min Stroke of abrasion element: 70 mm Abrasion number: 50,000 times The specific test method is the same as in Examples 13 to 24 above.

Table 9 From the results in Tables 8 and 9 above, Examples 25 to 36 all passed the wear resistance test, while Comparative Example 13
~18, the wear amount is 490~5660mg 150,000 times,
Or the coating composition gelled.

In addition to weather strips, the coated body of the second invention can also be applied to members such as rubber seals and O-rings that require wear resistance, adhesion, etc.

[Examples 37 to 46 and Comparative Examples 19 and 201 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 adhesive area and tensile shear strength Each test piece was heated at room temperature of 23°C using gasoline (G) as a solvent,
After being immersed in the wax rim (W) for 1 hour, the adhesive area and tensile shear strength were measured at a bowing speed of 50 mm/min. The results are shown in Table-10.

Table 10 From the results in Table 10 above, in Examples 37 to 46, 97 to 99% of the adhesive area was secured even when immersed in gasoline or wax remover, and the tensile shear strength was 8.3.
It can be seen that it shows a high value of ~8.7 Kg/crj. On the other hand, in Comparative Examples 19 and 20, the adhesive area was 31
~35%, with a tensile shear strength as low as 1.5 Kg/car.

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, in the present invention, it can also be used as an adhesive tape for use in chemical equipment to which solvents such as toluene and xylene may adhere, members to which kerosene may adhere, and the like.

〔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 very good abrasion resistance and the adhesion between the coating film and the object to be coated is excellent.

Further, the coated body of the second invention has the effect of exhibiting excellent performance such as abrasion resistance and water repellency due to 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,
2 to 100 parts by weight of fluororesin, 5 parts of silicone oil
~200 parts by weight, mercapto silicone in an amount such that the molar ratio of mercapto group (-SH):isocyanate group (-NCO) is 0.7 to 1.3:1, and 0.0 part of halogenating agent.
A coating composition containing 02 to 20 parts by weight. 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.