JPH05156206A - Treating agent for preventing abnormal noise - Google Patents

Abstract

PURPOSE:To obtain a treating agent for coating to an oscillating part to prevent the generation of abnormal noise caused by the friction of the oscillating part with other part by including fine particles of a urethane resin in a silicone- copolymerized curable urethane resin. CONSTITUTION:The objective treating agent for suppressing abnormal noise is produced by uniformly mixing (A) a silicone-copolymerized curable urethane resin obtained by reacting a reactive silicone (e.g. hydroxypolydimethylsiloxane) with an isocyanate compound (e.g. tolylene diisocyanate) and a polyol (e.g. polyester polyol), (B) 1-50wt.% (in terms of solid component) of fine particles of a urethane resin having particle diameter of 0.1-40mum (preferably 0.5-20mum) and composed of cross-linked urethane polymer, etc., obtained by the urethanization reaction of a polyisocyanate compound with various hydroxy compounds and (C) a solvent and optionally a catalyst, a cure accelerator, etc. When an interior trim of automobile is treated with the treating agent, the variation range of the kinetic friction coefficient of the treated part to the counter part is decreased to prevent the generation of abnormal noise.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an abnormal noise preventing treatment agent coated on the surface of a component in order to prevent abnormal noise caused by friction of a vibrating component with other components.

[0002]

2. Description of the Related Art Skin materials made of PVC (polyvinyl chloride) are widely used for instrument panels, doors, ceilings, seats and the like of automobiles. This skin material produces an abnormal noise such as a squeak noise when rubbed with other parts such as a plastic part having no skin material or a skin material of the same or different kind in a relatively different movement. As an effective means for preventing or reducing this abnormal noise, a coating treatment is applied to the surface of the skin material to reduce the friction coefficient of the skin material.
Known coating compositions for surface treatment for lowering the coefficient of friction (increasing lubricity) include PVC, polyacrylic acid ester mixture-based and urethane resin-based coating compositions. Things to use are getting more and more attention.

A coating composition containing the silicone copolymer urethane curable resin as a main component is disclosed in JP-A-63-3.
No. 17514 and Japanese Patent Laid-Open No. 61-138636. The composition disclosed in JP-A-63-317514 contains a copolymer obtained by reacting a reactive silicone, a polyol and an isocyanate.
The composition disclosed in JP-A-138636 contains a curable polyurethane composed of a combination of a polyvalent isocyanate and a polyol and a curable silicone as a coating film forming element, but the nature of the cured coating film formed is Both are urethane copolymers having a siloxane bond or silicone-urethane copolymers.

Further, it is also known to incorporate fine particles into the above coating composition in order to enhance the properties of the cured coating film. For example, Japanese Patent Laid-Open No. 63-317514 mentioned above discloses a composition containing carbon black, polytetrafluoroethylene (trade name: Teflon) powder, and the like, and Japanese Patent Laid-Open No. 6-317514.
Japanese Patent Application Laid-Open No. 61-138636 described in JP-A-1-138636.
JP-A No. 1994-242242 discloses a composition obtained by adding nylon powder or fluororesin powder to the composition of No.

[0005]

The effect improved by the above-mentioned conventional coating composition is the angle of slid.
e) That is, as shown by the fact that the inclination angle at which a solid material starts to slip from a stationary state becomes small, the friction coefficient in question in the conventional coating composition is not the static friction coefficient that determines the sliding angle. I won't. Figure 2
According to the test in which the device under test 2 is slid on the device under test 1 as shown in FIG. 1, the friction coefficient generally varies as shown in the graph of FIG. Reducing the static friction coefficient A, which corresponds to the maximum friction coefficient immediately after the start of sliding, is effective in preventing abnormal noise that occurs at the moment when parts rub against each other. It is more effective to reduce the fluctuation width BC of the dynamic friction coefficient (see FIG. 1) in order to prevent the abnormal noise generated by the parts that are frictioned by the continuous minute vibration. Therefore, surface treatment with a coating composition that reduces the static friction coefficient A as disclosed in JP-A-61-138636 and JP-A-63-317514 should sufficiently prevent abnormal noise generated by automobile parts. I can't. In addition, in the composition containing carbon black, polytetrafluoroethylene powder, nylon powder, etc.,
The microscopic adhesive force between these powders and the coating film forming resin is weak and the abrasion resistance of the coating film is insufficient.

The present invention has been made for the purpose of solving the above problems, and the problem to be solved by the present invention is due to continuous micro-vibration such as squeaking noise generated by interior parts of a running automobile. It is an object of the present invention to provide a coating composition that is particularly effective in preventing abnormal noise that constantly occurs due to friction, that is, an abnormal noise preventing agent that can narrow the fluctuation range of the dynamic friction coefficient.

[0007]

The noise preventing agent of the present invention is characterized in that the silicone copolymer urethane curable resin contains fine particles of urethane resin as a solid content of 1 to 50% by weight. To do.

As a kind of urethane resin which is a material of fine particles, polyisocyanate compound and various hydroxy compounds (polyhydric alcohol, polyester polyol, polyether, polyol, polycarbonate polyol or polypentadiene polyol, etc.) are subjected to urethane reaction. The resulting crosslinked urethane polymer may be mentioned. If the amount of fine particles is less than 1% by weight, the effect of preventing abnormal noise is insufficient. On the other hand, if the amount is more than 50% by weight, it is impossible to form a coating film or the abrasion resistance of the coating film. Therefore, the content of the fine particles in the solid content of the treating agent is preferably 1 to 50% by weight, and more preferably 1 to 30% by weight. The particle size of the fine particles is preferably about 0.1 to 40 μm, and particularly preferably 0.5 to 20 μm. If the particle size is too large, the fluctuation range of the dynamic friction coefficient cannot be narrowed. Conversely, if it is too small, the fluctuation range of the dynamic friction coefficient cannot be narrowed. The shape of the fine particles is spherical, preferably spherical. Fine particles having a desired particle size and shape can be produced by selecting a dispersant according to the non-aqueous emulsion polymerization method. Further, urethane fine particles commercially available for use in suede paints and cosmetics may be used.

The above-mentioned silicone copolymer urethane curable resin, which is the main component of the treating agent, is a urethane copolymer or silicone having a siloxane bond obtained by reacting a reactive silicone, an isocyanate compound and a polyol.
It means a urethane copolymer or a prepolymer mixture which becomes the copolymer. When the curable resin is the former urethane copolymer having a siloxane bond or silicone-urethane copolymer, the treating agent of the present invention forms a cured coating film by volatilization of the solvent. On the other hand, when the curable resin is the latter prepolymer mixture, the treating agent of the present invention contains a low molecular weight "urethane copolymer having a siloxane bond or a silicone-urethane copolymer" as a film forming element. A composition, a composition containing a curable polyurethane and a reactive silicone, or a composition containing a silicone-isocyanate copolymer and a polyol; having an isocyanate terminal functional group in the polymer component , Moisture curing, or heating when the isocyanate functionality is blocked, results in a finished coating when the curing reaction occurs.

The silicone copolymer urethane curable resin used in the present invention may be one known in the art, or can be produced by a known method.
The ratio of reactive silicone to be copolymerized: isocyanate compound: polyol is usually 2 to 60 parts by weight: 10 to 6
0 parts by weight: 10 to 70 parts by weight, preferably 3 to 2
0 parts by weight: 30 to 50 parts by weight: 30 to 70 parts by weight. The final copolymer may be a random polymer.

The reactive silicone is a carbinol group, an amino group, a thiol group, which reacts with an isocyanate compound,
It means a polyorganosiloxane having at least two functional groups selected from epoxy groups and the like. Examples include hydroxypolydimethylsiloxane, aminopolydimethylsiloxane, hydroxypolydiethylsiloxane, polydimethylpolyepoxide polysiloxane, hydroxypolydiphenylsiloxane, aminopolydiethylsiloxane, and the like. The molecular weight of reactive silicone is about 200
1 to 10,000, preferably 300 to 9000, and more preferably 1000 to 5000.

Examples of the isocyanate compound include tolylene diisocyanate, phenylene diisocyanate, methylene bis (4-phenyl isocyanate), methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, ethylene diisocyanate, propylene diisocyanate, hexamethylene diisocyanate, hexamethylene diamine urea-polyisocyanate, lysine. Examples thereof include diisocyanate, dicyclohexylpropane diisocyanate, metaphenylene diisocyanate, naphthylene diisocyanate, triphenylmethane triisocyanate, trimethylpentane diisocyanate and polymerizable methylene poly (phenyl isocyanate), and those blocked with a known blocking agent. Of these, tolylene diisocyanate, methylene bis (4-phenyl isocyanate), methylene bis (cyclohexyl isocyanate), and isophorone diisocyanate are preferable.

Polyols that can be used include polyester polyols, polyether polyols, polyurethane polyols, acrylic polyols, nitrogen-containing polyols (amine-based polyols), castor oil derivatives, polybutadiene polyols and the like. Even if these are used alone,
Alternatively, two or more kinds may be used in combination. Polyester polyols include adipic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, succinic acid,
Compounds having a polybasic acid such as fumaric acid, hexahydrophthalic acid, methylhexahydrophthalic acid and tetrahydrophthalic anhydride and at least two or more hydroxyl groups in one molecule, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene Synthesized by conventional methods from glycol, neopentyl glycol, hydrogenated bisphenol A, glycerin, butanediol, 1,3-pentanediol, hexanediol, trimethylpentanediol, hexanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, etc. The things that are done are listed. As the polyether polyol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polyoxypropylene triol, polyoxypropylene quadrol and the like can be used. As the polyurethane polyol, a compound having a terminal hydroxy group obtained from a polyhydroxy compound and a polyvalent isocyanate compound is used. Acrylic polyols include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, trimethylolpropane acrylic acid monoesters, their corresponding methacrylic acid derivatives, and hydroxyl group-containing monomers such as polyhydroxyalkyl maleate and fumarate. ,
Acrylic acid or methacrylic acid methyl, ethyl,
Obtained by copolymerization with an acrylic monomer such as butyl, propyl, hexyl, 2-ethylhexyl, hydroxyethyl ester or a monomer having an α, β-ethylenically unsaturated double bond such as styrene, vinyltoluene or vinyl acetate Is mentioned. As the castor oil derivative, triglyceride of ricinoleic acid or the like can be used, and as the polybutadiene polyol, 1, 2
-Types having a hydroxyl group at the terminal such as polybutadiene and 1,4-polybutadiene can be used.

The abnormal noise preventing agent of the present invention is used in the form of a coating material containing a solvent and, if necessary, a catalyst and a curing accelerator. As a solvent component that can be used, for example, xylene,
Hydrocarbons such as toluene and solvent naphtha, ketones such as methyl isobutyl ketone and cyclohexanone, esters of acetic acid and ethylene glycol monoethyl ether or diethylene glycol monoethyl ether, esters such as 3-methoxybutyl acetate and dibasic acid esters Is mentioned. They may be used alone or in a mixture of two or more, and generally 2% of all coating ingredients are used.
It is blended so as to occupy 0 to 50% by weight. As the catalyst, organic compounds such as dibutyltin diacetate, dibutyltin laurate, dibutyltin octoate, dioctyltin oleate, mercaptan tin, zinc octylate, tin octylate, which are usually used for promoting dissociation of blocked urethane prepolymers. It is also possible to use a metal compound, triethylenediamine, triethylamine, an amine catalyst such as diazacyclooctane together. The composition further includes a drying regulator, a water stabilizer, a filler, a coloring pigment, an anti-cratering agent, a leveling improver, an antifoaming agent, a surfactant, an antistatic agent, a pigment dispersant, a flow improver, and a thickener. Conventional additives such as

In order to prepare a treating agent, each component of the treating agent of the present invention, together with a solvent and necessary additives, is dispersed, three rolls, ball mill, pot mill, steel mill, pebble mill, attritor, sand mill, sand grinder, It may be charged in a mixing and dispersing machine such as a roll mill or a high-speed stirrer with blades to uniformly mix and disperse. The part to be coated is a part that vibrates and rubs against other parts to generate an abnormal noise, for example, an automobile interior part, and of course a part having a skin material, the surface of the skin material is coated with a treating agent. The material of the surface to be coated is not limited, and may be plastic, natural rubber, synthetic rubber, metal, leather, woven fabric, glass, ceramics, etc., but PVC (polyvinyl chloride) is particularly prone to produce abnormal noise due to slight friction. , PP
(Polypropylene), ABS resin (acrylonitrile-
It is used as a skin material made of butadiene-styrene copolymer). The coating on the object to be processed is
Depending on the state of the skin material, brush coating, roller coating, dipping,
Air spray, electrostatic air spray, airless spray,
A coating method selected from hot airless spray can be adopted.

[0016]

Although the mechanism of action of fine particles is unknown, when a treating agent containing fine particles is used, the fluctuation range of the dynamic friction coefficient with the counterpart material of the treated product becomes small. This means that the treated product is ABS, P
It appears clearly in the case of P and PVC skin materials. Therefore, when parts such as automobile interior parts that are subjected to continuous micro-vibration are treated with the treating agent having the above-mentioned configuration, abnormal noise caused by friction between parts (especially skin materials) is prevented. The abrasion resistance of the coating film of the treating agent is secured by the silicone copolymer urethane cured resin.

[0017]

【Example】

Example 1 Each component was mixed in the following proportions to manufacture an abnormal noise preventing agent. Ingredient parts by weight A) 1,6-hexamethylene adipate 15.0 [Dainippon Ink Co., Ltd./OD×2068] Alcohol-modified silicone oil ^{* 1} 1.5 [Shin-Etsu Chemical Co., Ltd./KF6003] 1,4-butane Diol 0.2 Diphenylmethane diisocyanate (MDI) 2.3 Methyl ethyl ketone 44.1 (9 hours reaction at 70 ° C) B) Trimethylolpropane 2.9 Diphenylmethane diisocyanate (MDI) 8.1 (10 hours reaction at 60 ° C) C) Methyl ethyl ketone (for dilution) 25.9 (total 100.0 or more) D) Urethane fine particles ^{* 2} (solid content concentration 50%) 15.0 [Nippon Polyurethane Co., Ltd./HE687] [Note] ^{* 1} Average of polysiloxane segment Molecular weight 56
00 ^{* 2} Average particle size 5 μm; content of urethane fine particles in solid content 20.0% by weight

Comparative Example 1 An abnormal noise preventing agent was produced by mixing the components in the following proportions. Component parts by weight PVC (average molecular weight 700) 6 Polyacrylic acid ester 2 [Mitsubishi Rayon Co., Ltd./BR60] HSB (half-second butyrate) 0.5 Silica (average particle size 3 to 4 μm; solid content 25%) 12 Methyl ethyl ketone 61 Anone 8 Xylene 10.5 (above total 100.0)

Comparative Example 2 A treating agent having the same composition as in Example 1 was produced except that an ordinary urethane curable resin was used in place of the silicone copolymer urethane curable resin and no urethane fine particles were added.

Comparative Example 3 A treating agent having the same composition as in Example 1 was produced except that urethane fine particles were not added.

Test Example In order to compare the noise-preventing effect of each treating agent of Example 1 and Comparative Examples 1 to 3, each of the above treating agents was spray-coated on each PVC sheet used as a skin material to obtain a coating film. After curing
A leather sheet (leather-like pattern) was embossed to prepare a test sheet. A general PVC skin material was used as the friction counterpart material of each test sheet thus obtained, and the static friction coefficient A and the dynamic friction coefficient width BC (see FIG. 1) were measured for each test sheet. The results are shown in Table 1.

[Table 1] From Table 1, it can be seen that the treatment agent containing the urethane fine particles has a smaller dynamic friction coefficient width.

Further, each test sheet was examined for occurrence of abnormal noise, and further examined for occurrence of abnormal noise after being subjected to a predetermined number of abrasion tests. The results are shown in Table 2.

[Table 2] It can be seen from Table 2 that the treating agent containing the urethane fine particles is superior in terms of abrasion resistance and noise prevention after the abrasion test.

Further, by using the test sheets treated with the treatment agents of Examples and Comparative Examples 1, the static friction coefficient and the dynamic friction coefficient width were determined when the ABS skin material and the PP skin material were used as friction mating materials. Examined. The results are shown in Table 3.

[Table 3] From Table 3, it can be seen that the treatment agent of the present invention is more effective than the conventional treatment agent against the abnormal noise generated by the skin material that rubs against the ABS skin material or the PP skin material.

[0022]

EFFECTS OF THE INVENTION The noise preventing agent of the present invention lowers the coefficient of friction in friction between the article to be treated and other parts, and particularly reduces the fluctuation range of the dynamic friction coefficient, and therefore has a close relationship with this fluctuation range. The present invention can be applied to the surface of a part that generates a certain abnormal sound, for example, the surface of an automobile interior part that generates a strange noise due to friction with other members due to continuous microvibration during traveling to prevent the generation of the abnormal noise.

[Brief description of drawings]

FIG. 1 is a graph showing a relationship between a moving distance and a friction coefficient obtained in a test for examining a change in the friction coefficient.

FIG. 2 is an explanatory diagram of the above test.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Teruyoshi Takeda 1876 Higashimachi, Hamamatsu City, Shizuoka Prefecture Kyowa Leather Co., Ltd.

Claims (1)

[Claims] 1. A silicone copolymer urethane curable resin containing fine particles of urethane resin as a solid content of 1 to 50.
An abnormal noise preventing agent characterized by being contained in a weight percentage.