JPH048779A - Paint composition and painted material - Google Patents

Abstract

PURPOSE:To obtain a paint composition having excellent wear resistance on the surface of coating film and adhesion between the coating film and a material to be coated by mixing polyurethane comprising polyol, triethanolamine and polyisocyanate with a fluororesin and polyether silicone, etc. CONSTITUTION:The objective paint composition is composed of (A) 100 pts.wt. polyurethane containing 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, (C) polyether silicone in an amount giving (0.7-1.3):1 molar ratio of OH/NCO and (D) 0.002-20 pts.wt. halogenating agent. Said paint composition is applied on the surface of a resin or a substrate material to afford the objective painted material.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a coating composition suitable for coating automobile parts such as rubber products such as raslan, weather strips, and double-sided adhesive tapes, and synthetic resin products. be.

[Conventional technology]

Conventionally, natural rubber (NR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isobutylene-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 objects to be coated such as rubber, synthetic resins, fibers, etc., 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, the coating composition of the first invention comprises a 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, hydroxyl group (-OH): isocyanate group (-
NCO) molar ratio is 0.7. A method is adopted in which the ratio is 1.3:1 and the halogenating agent is blended in an amount of 2 to 20 parts by weight of O, OO.

The coated body of the second aspect of the invention employs a method in which the coating composition according to claim 1 is coated on 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 80
A value in the range of 0 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, for example 2. i-tridene diisocyanate (
TD I), 65/35 (Ratio of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, the same applies hereinafter) Tolylene diisocyanate, 80/20
Tolylene 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-tolylene diisocyanate, hydrogenated 65/35 tolylene diisocyanate,
Hydrogenated 80/20 tolylene diisocyanate, isophorone diisocyanate (IPDI), 4.4', 4'-1 rifhenylmethane triisocyanate, tris(p-isocyanate phenyl) thiophosphate, etc. are used.

The molar ratio of the polyol:triethanolamine is 1:
It is 0.05 to 2.0. When 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 becomes thick (decreased).

Further, the molar ratio of hydroxyl group (-0H) 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.

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.

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

This polyether silicone is made by reacting a copolymer of ethylene oxide and propylene oxide with silicone, but it may also be made by reacting a homopolymer of ethylene oxide or propylene oxide with silicone ( As the polyether silicone, one having a hydroxyl 19 value of about 45 to 60 is suitable, and this polyether silicone functions as a curing agent for the polyurethane and also contributes to improving wear resistance. The molar ratio of hydroxyl groups in the polyether silicone to isocyanate groups in the polyurethane is in the range of 0.7 to 1.3:1. If this molar ratio is less than 0.7, the resulting coating film The adhesion of the coating film to the object to be coated decreases, and the abrasion resistance cannot be improved.Furthermore, when it exceeds 1.3, the adhesion of the coating film to the object to be coated decreases.

As a halogenating agent, N-promsuccinimyl”
(NBS I), acid imide halogen compounds such as N-bromphthalimide, trichloroisocyanuric acid (TCI),
A), isocyanuric acid halides such as dichloroisocyanuric acid, halogenated hydantoins such as dichlorodimethylhydantoin, alkyl hypohalides, etc. are used.

The above-mentioned alkyl hypohalides are normal, secondary or tertiary alkyl hypochlorides, particularly stable tertiary alkyl chlorides and bromides, such as tertiary butyl/S ibobromide, tertiary amyl hypohalides, etc. Bromide and the like are preferred, and halogen-substituted alkylhypochlorides such as dichloro, trichloro or fluoromethylhypochloride can also be used.

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

The same blending ratio is 0. If the amount is less than 2 parts by weight of OO, the degree of /S halogenation will be small, resulting in little improvement in adhesion, and if it exceeds 20 parts by weight, the stability of the coating composition will deteriorate.

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, -0-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 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 necessary solvent are appropriately selected and mixed, and this is reacted with 808C for 13 hours in dry nitrogen gas.
A polyurethane having isocyanate groups is prepared.

Next, to 100 parts by weight of this polyurethane, 2 to 100 parts by weight of a fluororesin, polyether silicone in an amount such that the ratio of hydroxyl group to isocyanate group is 0.7 to 1.3:1, and 0.002 to 20 parts by weight of a halogenating agent are added. A coating composition is obtained by adding a solvent and adjusting the viscosity to a suitable level for coating. In this case, a part of the fluororesin is replaced with molybdenum disulfide, glass fiber, carbon fiber,
It can also be replaced with polyethylene, silicon oxide, calcium carbonate, magnesium carbonate, clay, etc.

Further, the base material constituting the coated body of the second invention is a resin or rubber, for example, the resin is vinyl chloride resin, polyethylene, polypropylene, polyurethane, or a foam thereof, and the rubber is ethylene-propylene-diene triplet. Original 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 characteristics such as the lubricity of polyether silicone and the small friction coefficient of fluororesin. , the halogenating agent halogenates the coated material to improve mutual intermolecular forces, and is composed of polyol, triethanolamine, and polyisocyanate in a predetermined ratio, and has incyanate groups by blending an excess of isocyanate groups. The adhesion to the object to be coated is improved due to hydrogen bonding and other effects caused by polyurethane having a specific structure.

In addition, since the coated body of the second invention has the coating composition applied to its surface, it exhibits performance such as abrasion resistance and water repellency based on the characteristics of the coating composition of the first invention. Ru.

[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, 1 kg 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%.

Table-1 The abbreviations in Table-1 represent the following meanings.

PPG 3000 Polyoquine propylene glycol with a number average molecular weight of 3000 PPG 1000/Polyoquine propylene glycol with a number average molecular weight of ■000 PPG 2000: Polyoxypropylene glycol TG 3000 with a number average molecular weight of 2000/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/4,4'-diphenylmethane diisocyanate NDI with a number average molecular weight 2000: 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, polyether silicone (PESi), 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.

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

Fluororesin refers to tetrafluoroethylene resin.

Polyether silicones have the following hydroxyl numbers:

(a) 56, (b) 48, (c) 47
, (d) 59, (e) 46, ge) 52, (
g) 5 1, (h) 5 0, (i)
4 9 Halo saponification agent represents the following.

TCIA:) Lichloroisocyanuric acid NBS, N-promsuccinimide t-BHC, tertiary butyl hypochloride. Also, as a comparative example, a coating composition as shown in Table 3 was prepared, and applied to the coated object in the same manner. After coating and drying, a wear resistance test was conducted, and the results are shown below.
Same as 2.

Table 4 As can be seen from Table 4 above, the coating compositions of each example had an abrasion loss of 8.0% even after 1000 abrasion tests.
It is a very small amount of 3 to 15.3 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 due to the lubricity of polyether silicone, the low coefficient of friction characteristic of fluororesin, etc. It is estimated that this is based on the following.

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 852.9 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 in which the second invention is embodied in a glass run coated with a coating composition will be described.

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 coating compositions 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 run coated with the coating, and the results are shown in Table 6 and Table 6. -7
It was shown to.

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: ■ 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) Attach the above test piece to the above test machine, The painted surface was worn 30,000 times and its condition 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.

In Table 7 above, the ratio of hydroxyl group/isocyanate group of polyether silicone in the coating composition is 0.4 in Comparative Example 7, 1.5 in Comparative Example 8, and 0.4 in Comparative Example 9.
, Comparative Example 1O is 1.5.

As can be seen from Table-6 and Table-7 above, Examples 13-
In Comparative Examples 7 to 12, the abrasion amount was 20 to 1680 mg, whereas in Comparative Examples 7 to 12, the wear 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 will be described in which the invention is embodied in a Unisa strip coated with a coating composition.

Synthetic rubber and synthetic resin weather strips are used for car window frames and window glass seals. This Unisa strip is particularly required to be abrasion resistant because it slides when opening and closing window glass and doors. As the base material of the weather strip, polyolefin-based vulcanized rubber, such as the aforementioned EPDM, EPM, etc., is used. In contrast to these polyolefin-based vulcanized rubbers, natural rubber (NR
), polybutadiene rubber (BR), acrylonitrile butadiene copolymer rubber (NBR), polyisoprene rubber (IR), chloroprene rubber (CR), isobutylene rubber
A material containing 1/2 or less of isoprene copolymer rubber (IIR) or the like 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.

Foaming agents for comb include N, N'-dinitrosopentamethylenetetramine, N, N'-dimethyl N, N'-dinitron terephthalamide, azodicarbonamide, azobisisobutyronitrile, benzenesulfonyl hydrazide, p , p-oxybis(benzenesulfonylhydrazide), toluenesulfonylhydrazide, 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 edge abrasion tester, which is an improved version of the Gakushin abrasion tester, an 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 Abrasion element stroke: 70 mm Abrasion number: 50,000 times The specific test method is the same as in Examples 13 to 24 above.

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 amount of wear was 490 to 3370 rng, 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 20:] Next, 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 The coating composition shown in Table 10 was applied to the side edge of a double-sided adhesive tape, and then left for -1 week to be used for testing.

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 After immersing each of the above test pieces in gasoline (G) and wax remover (W) as solvents for 1 hour at room temperature of 23°C, adhesive area and tensile speed of 50 mm were determined. The tensile shear strength was measured under the condition of /min. The results are shown in Table-10.

Table 10 From the results in Table 10 above, in Examples 37 to 46, 91 to 97% of the adhesive area was secured even when immersed in gasoline or wax remover, and the tensile shear strength was 8.0.
It can be seen that a high value of ~8.5 Kg/ci is shown. On the other hand, in Comparative Examples 19 and 20, the adhesive area was 31~
35%, the tensile shear strength is as low as 1.5 Kg/crl.

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. .

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,
2 to 100 parts by weight of fluororesin, hydroxyl group (-OH): isocyanate group (-
A coating composition containing 0.002 to 20 parts by weight of a halogenating agent and a molar ratio of 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.