JP2790972B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for imparting lubricity to a surface of an article, and more particularly to a coating composition at room temperature near a sliding surface of furniture such as a sliding door and a non-smooth surface such as a fastener. The present invention relates to a coating composition which is formed to impart lubricity.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION AND ITS PROBLEMS
In order to improve the sliding of aluminum to aluminum, wood to wood, iron to aluminum, plastic to iron, etc., methods of applying animal and vegetable oils, mineral oils, silicone oils, etc. have been adopted. In addition, there is a problem that the surface is soiled because oil adsorbs dust. As a method that does not have such a defect, a method of forming a film of a fluororesin or a method of attaching a plastic tape has been proposed. However, in the case of fluororesin, a high temperature of 200 ° C or more is required for film formation, so it can be used only for heat-resistant materials such as metal.Plastic tape is a flat article with a certain width. There is a problem that it cannot be used unless it is a certain one. In order to solve such a problem, a composition containing a product obtained by further reacting a silanol group-containing polydiorganosiloxane with a reaction product of an amino group-containing silane and an epoxy group-containing silane is used as an article. (See JP-B-62-52796), a silicone composition useful for surface treatment of a metal molded product blended with an aromatic amino group-containing organopolysiloxane (Japanese Patent Application Laid-Open No. JP-A-2-283765), block copolymers of resin-like organopolysiloxanes and linear organopolysiloxanes, and organosilanes, and various rubbers containing diorganopolysiloxanes having a hydroxyl group or an alkoxy group at the molecular terminal. Film-forming organopolysiloxane for imparting mold release and lubricity to material surfaces Compositions (see Japanese Patent Application Laid-Open No. 3-62855) have been proposed, but it takes a long time to obtain a stable sliding property after the surface treatment of the article, or a more favorable sliding property is maintained. For example, a coating composition having more excellent properties has been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a coating composition which imparts good lubricity, particularly a coating composition which maintains good lubrication for a long period of time, which solves the above problems. It is in.

[0004]

The present inventors have conducted intensive studies in order to achieve the above object. As a result, a specific amino group-containing polyorganosiloxane and a coating agent containing a specific polydiorganosiloxane have good lubricity on articles. Have been found, and the present invention has been accomplished. That is, the coating composition of the present invention has the following general formula (1)

[0005]

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Wherein R ¹ is —OH, —OR ³ (where R ³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms) and a monovalent hydrocarbon group. , R ² is a monovalent hydrocarbon group, A is a group selected from the group consisting of a monovalent hydrocarbon group and an amino group-containing group, m is an integer of 1 to 10,000,
n is an integer of 0 to 10,000), and 10 to 80% by weight of an amino group-containing polyorganosiloxane containing at least one amino group in one molecule. (2) The degree of polymerization is 10 to 1,000, It is characterized by containing a silicone mixture consisting of 20 to 90% by weight of a polydiorganosiloxane having a triorganosilyl group at a chain end.

The amino-containing polyorganosiloxane of component (1) of the present invention contains at least one amino group in one molecule. In the above formula, R ¹ is -OH,
—OR ³ and a group selected from the group consisting of monovalent hydrocarbon groups, wherein R ³ is a monovalent hydrocarbon group having 1 to 4 carbon atoms. Examples of the monovalent hydrocarbon group as R ¹ include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group; an alkenyl group such as a vinyl group and an allyl group; a phenyl group; a tolyl group; And a cycloalkyl group such as an aryl group, a cyclohexyl group and a cyclooctyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom. As the monovalent hydrocarbon group as R ¹ , an alkyl group is preferable, and a methyl group is particularly preferable, since the properties of the obtained composition are good.
R ² is a monovalent hydrocarbon group, examples of which are the same as the monovalent hydrocarbon group as R ¹ , and an alkyl group, particularly a methyl group, is preferred. A is a group selected from the group consisting of monovalent hydrocarbon group and an amino group-containing group, the monovalent hydrocarbon group is exemplified those similar to R ^1, preferable ones are also same. Examples of the amino group-containing group include a γ-aminopropyl group, an N- (β-aminoethyl) aminomethyl group,
(N- (β-aminoethyl) amino) propyl group and the like are exemplified. m is an integer of 1 to 10,000, and n is an integer of 0 to 10,000. As the amino group-containing polyorganosiloxane of the component (1), those having various degrees of polymerization and amino group content can be used, and two or more kinds can be used in combination. In the present invention, it is preferable to use one having a high degree of polymerization as a main component and further use one having a low degree of polymerization. Examples of those having a high degree of polymerization include those having m of 1,000 to 8,000 and n of 0 to 100, and those having an amino group at both ends of the molecular chain and having a monovalent hydrocarbon group in the side chain. preferable. Component such an amino group-containing polyorganosiloxane
By using it as the main component of (1), good slip properties can be obtained in combination with the component (2). As described above, in the coating composition of the present invention, it is preferable to further use an amino group-containing polyorganosiloxane having a low degree of polymerization, and as such a siloxane, m is 10 to 800, and n is 1 to 100 are exemplified.
In particular, those having a terminal trialkylsilyl group and having an amino group in the side chain are preferred. The cohesion of the resulting coating composition can be improved by using such a low polymerization degree. When a combination of a high polymerization degree and a low polymerization degree is used in the component (1), the high polymerization degree is preferably 50 to 80% by weight.

The amino group-containing polyorganosiloxane of the component (1) can be synthesized by a conventionally known method, for example, by hydrolyzing an amino group-containing alkoxysilane and a siloxane containing a silanol group at both molecular chain terminals. Examples thereof include a method of performing a condensation reaction and a method of performing an addition reaction between an amino group-containing alkenyl compound and a polyorganohydrogensiloxane. In particular, in the case of synthesizing a polymer having a high degree of polymerization used in the present invention, a method in which an amino group-containing alkoxysilane and a siloxane having a silanol group at both molecular chain terminals are subjected to a hydrolysis / condensation reaction is preferable. The amino group-containing alkoxysilane has a general formula

[0009]

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(Wherein Q is a hydrogen atom, —CH ₃ , —CH ₂ CH ₂ CH ₂
And -CH ₂ CH ₂ NHCH 1 monovalent group selected from ₂ CH ₂ group consisting of NH _2, R ⁴ is a divalent hydrocarbon group having 1 to 4 carbon atoms, R ⁵ is the
R ¹ and R ⁶ are the same substituents as those of R ³ described above, and q represents 0 or 1). Trialkoxysilane wherein q is 0 is preferably used. Examples of such amino group-containing alkoxysilanes include γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminomethyltrimethoxysilane, γ- (N- (β- Aminoethyl) amino) propyltrimethoxysilane, γ- (N- (β-aminoethyl) amino) propylmethyldimethoxysilane, N- (β-aminoethyl) aminomethyltributoxysilane, γ- (N- (β- (N- (β-aminoethyl) amino) ethyl) amino) propyltrimethoxysilane and the like are exemplified. As the siloxane containing a silanol group at both ends of the molecular chain, the polymerization degree is preferably
1,000 to 8,000, particularly preferably used those 3,000 to 6,000, the substituent is exemplified the same groups as R ^1, preferably a methyl group or a phenyl group, particularly preferably those of only methyl groups.

The amino group-containing polyorganosiloxane of the component (1) of the present invention can be obtained by subjecting the above-mentioned amino group-containing alkoxysilane and silanol group-containing siloxane to hydrolysis and condensation by a known method. For example, these can be obtained by adding a hydrolysis catalyst such as an organic acid and an inorganic acid, and further, an organic solvent, and mixing and stirring them, if necessary, in the presence of water. Even if not, the reaction proceeds even if the amino group-containing alkoxysilane and the silanol group-containing siloxane are mixed and heated and stirred. When a polymer having a high degree of polymerization is synthesized as the component (1), the amino group-containing alkoxysilane is used in an amount of 1 to 100 parts by weight, particularly 5 to 30 parts by weight, based on 100 parts by weight of the siloxane having silanol groups at both molecular chain terminals. Partial reaction is preferred. The unreacted material can be used as it is mixed with the component (1). If necessary, the unreacted material can be used by removing the unreacted material by distillation under reduced pressure.

The component (2) of the present invention is a polydiorganosiloxane having a triorganosilyl group at the terminal of the molecular chain and containing no amino group in the molecule, and substantially having a hydroxyl group and a hydrolyzable group in the molecule. Is not contained. Examples of the substituent include a substituted or unsubstituted monovalent hydrocarbon group, and the same groups as those described for R ¹ include, for example, an alkyl group such as a methyl group, an ethyl group, a hexyl group, an octyl group, and a dodecyl group; And a fluoro-substituted alkyl group such as a 3,3,3-trifluoropropyl group is preferable, and among them, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
Further, the degree of polymerization is 10 to 1,000, and if it is less than 10, the coating of the formed coating agent becomes brittle and the adhesion becomes insufficient, and if it exceeds 1,000, the slipperiness decreases. The preferred degree of polymerization is from 20 to 100. Component (2) includes polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, polymethyl (3,3,3
-Trifluoropropyl) siloxane and the like are exemplified, but polydimethylsiloxane and polymethylphenylsiloxane are preferable, and polydimethylsiloxane is particularly preferable because the obtained properties are good.

The coating composition of the present invention contains, as a main component, a silicone mixture of the components (1) and (2), and this mixture is present in an amount of 10 to 80% by weight of the component (1). Component (2) comprises 90 to 20% by weight of the composition. Preferably, the properties of the coating composition obtained are good, so that 50 to 70% by weight of component (1) and 50 to 30% by weight of component (2)
It is blended in a composition by weight. The coating composition of the present invention is obtained by mixing and stirring the components (1) and (2), and if necessary, by using an organic solvent or by mixing and stirring in a heated state. The coating composition of the present invention may contain various organic solvents, condensation reaction catalysts, various fillers, etc. in addition to the components (1) and (2). As an organic solvent, 1,1,2-trichloro-1,2,2-
CFC-based solvents such as trifluoroethane, methylene chloride, chlorine-containing hydrocarbons such as chloroform, hexane,
Examples thereof include hydrocarbons such as toluene, alcohols such as methanol and ethanol, and volatile siloxanes such as hexamethyldisiloxane and octamethylcyclotetrasiloxane. Among these, from the viewpoint of improving the stability of the coating agent composition, it is preferable to contain 1 to 20% by weight, particularly 2 to 10% by weight of alcohol, particularly ethanol. Examples of various fillers include inorganic fine powders such as silica, talc, titanium oxide, and zinc carbonate; polyethylene fine powders; fluororesin fine powders; polymethylsilsesquioxane fine powders; and organic fine powders such as silicone rubber fine powders; And those obtained by surface-treating these with silicone, silane, titanium compound and the like. When using an organic solvent, in the coating composition, component (1)
And the total amount of component (2) is 5 to 80% by weight, preferably
4040% by weight, and the storage may be performed in the form of this composition.
The coating composition was further diluted with the organic solvent exemplified above, and the total amount of the components (1) and (2) was 1 to
It is preferable to prepare and use a coating agent so as to be 5% by weight. The application of the coating agent to the base material can be performed by a common application method such as dipping, brushing, spraying, and the like, and the solvent is volatilized and cured by leaving at room temperature or by heating, so that good lubricity is obtained. Is formed.

[0014]

The coating composition of the present invention is characterized by imparting good lubricity to various substrates and maintaining its properties for a long period of time. Further, the treatment can be carried out by heating at room temperature or at a relatively low temperature, and it can be applied to various kinds of substrates without fear of deterioration of the substrate due to heating. Further, there is an advantage that corrosion resistance and water repellency can be imparted simultaneously with imparting slipperiness.
The coating composition of the present invention can be applied to various substrates such as metals, rubbers, plastics, glasses, ceramics, and woods, and particularly, iron, aluminum, stainless steel, duralumin, titanium alloy, copper, and brass. Suitable for products made of various metals or wood products.
Such metal products include scalpels, razors, rail fittings, fasteners, knives, combs, pins, videotapes,
Guide rollers and guide pins such as cassette tapes, and sliding doors and the like for wood products.

[0015]

The present invention will be described below with reference to examples. In addition, the part in an Example represents a weight part, and% represents weight%. The viscosity indicates a value at 25 ° C. Preparation Example 1 To 20 parts of polydimethylsiloxane containing silanol groups at both ends having an average degree of polymerization of 6000, 78 parts of toluene was added, and the mixture was stirred at 50 ° C. for 3 hours, and then γ- [N- (β-aminoethyl) amino] propylmethyldimethoxy 2 parts of silane was added and reacted at 80 ° C. for 12 hours to obtain an amino group-containing polyorganosiloxane (A
-1) was obtained. The siloxane obtained by the reaction was represented by the following average formula. The silicone content in the obtained reaction solution was about 20%.

[0016]

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Preparation Example 2 To 20 parts of polydimethylsiloxane containing silanol groups at both ends having an average degree of polymerization of 3000, 78 parts of toluene was added, and the mixture was stirred at 50 ° C. for 3 hours, and 3 parts of γ-aminopropyltrimethoxysilane was added. The mixture was reacted at 12 ° C. for 12 hours, and the volatile components such as the solvent and unreacted silane were distilled off to obtain amino group-containing polyorganosiloxane (A-2). The obtained siloxane was represented by the following average formula.

[0018]

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Further, in the examples, compounds represented by the following average formula were used.

[0020]

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Example 1 50 parts of amino group-containing polyorganosiloxane A-1, B
-1, 5 parts of polydiorganosiloxane C-1,
30 parts of toluene and 5 parts of ethanol were added and mixed and stirred to prepare a coating composition of the present invention. Further, 400 parts of methylene chloride was added for dilution to obtain a colorless and transparent coating agent. Next, this coating agent was applied to a polished, degreased and cleaned stainless steel plate having a width of 3 cm, and allowed to stand at room temperature for 12 hours to evaporate the solvent to form a slippery film. A 400 g polypropylene plate was placed on this stainless plate and pulled with a horizontal force on the stainless plate. The force required to move the polypropylene plate [slip force (initial)] was as shown in Table 1. Also, place a 2kg polypropylene plate on a stainless steel plate and move it horizontally as well,
After 100 reciprocations, the force (sliding force (durability)) required to move the polypropylene plate was measured in the same manner as described above. Examples 2 to 7 In the same manner as in Example 1 with the compositions shown in Table 1, coating agents were prepared, and stainless steel plates were surface-treated. Next, the slipperiness was measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Examples 1 and 2 A coating agent was prepared with a composition not containing the component (2) of the present invention as shown in Table 2, and a stainless steel plate was surface-treated. Next, the slipperiness was measured in the same manner as in Example 1. Table 2 shows the results. Comparative Example 3 Slipperiness was measured on an untreated stainless plate in the same manner as in Example 1. Table 2 shows the results.

[0023]

[Table 1]

[0024]

[Table 2]

Embodiments 8 to 10 A fastener in which the meshing portion is made of aluminum is used.
After immersion in the coating agents of Nos. 3 to 5 for 5 minutes, the film was left at room temperature for 12 hours to form a slippery film. Table 3 shows the force required to open and close these fasteners [opening and closing force (initial)].
Weighed 50-80 g. Furthermore, these fasteners were immersed in perchlorethylene (80 ° C.) for dry cleaning for 10 minutes, taken out, and after evaporating the perchlorethylene at room temperature, the force required to open and close these fasteners [ Opening / closing force (durability)] was 60 to 90 g as shown in Table 3. Comparative Examples 4 and 5 For comparison, the force required to open and close the fastener treated with the coating agent of Comparative Example 2 was measured.
As shown in the figure, the weight was 70 to 100 g, and the weight after immersion in perchlorethylene was 80 to 120 g. The force required to open and close the untreated fastener was measured and found to be 150-200 g as shown in Table 3.

Examples 11 to 13 A fastener made of aluminum having a meshing portion was opened and closed 500 times to release the aluminum oxide layer on the surface. Similarly, a slippery film was formed. Replace these fasteners with 5
After immersing in a 10% aqueous sodium chloride solution (30 ° C) for 10 days, the force required to open and close the fastener (opening and closing force) was measured.
As shown in Table 4, the weight was 50 to 80 g. The fabric portion of the fastener was kept dry by repelling water with a silicone film. Comparative Examples 6 and 7 For comparison, the force required to open and close the fastener was measured in the same manner as in Example 11 except that the coating agent of Comparative Example 2 was used. g. The fabric portion of the fastener was kept dry by repelling water with a silicone film. When the fastener from which the aluminum oxide layer on the surface was removed was subjected to a similar experiment without any treatment, the aluminum was corroded and blisters occurred, and as shown in Table 4, a force of 150 to 560 g was required for opening and closing. . Further, the fabric portion of the fastener was wet and absorbed water.

[0027]

[Table 3]

[0028]

[Table 4]

Claims (5)

(57) [Claims] (1) The general formula: (In the formula, R ¹ is -OH, -OR ³ (where R ³ is a group selected from the group consisting of) and monovalent hydrocarbon radical represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ² Is a monovalent hydrocarbon group, A is a group selected from the group consisting of a monovalent hydrocarbon group and an amino group-containing group, m is an integer of 1 to 10,000, and n is 0 to 10,000.
And an amino group-containing polyorganosiloxane containing at least one amino group in one molecule in an amount of 10 to 80% by weight. A coating composition comprising a silicone mixture consisting of 20 to 90% by weight of a polydiorganosiloxane having organosilyl groups. 2. An amino group-containing polyorganosiloxane of the component (1) is different from an amino group-containing alkoxysilane in polymerization degree.
The coating composition according to claim 1, which is a reaction product of 1,000 to 8,000 with a polydiorganosiloxane having silanol groups at both molecular chain terminals. 3. An amino group-containing polyorganosiloxane of the component (1) is different from the amino group-containing alkoxysilane in polymerization degree.
A mixture of a reaction product of 1,000 to 8,000 polydiorganosiloxane having silanol groups at both molecular chain terminals and an amino group-containing polyorganosiloxane containing an amino group in the side chain and having a degree of polymerization of 10 to 800. Claim 1
The coating composition according to any one of the preceding claims. 4. The polydiorganosiloxane of component (2)
The coating composition according to claim 1, which is a polydimethylsiloxane. 5. The polydiorganosiloxane of component (2)
The coating composition according to claim 1, which is polymethylphenylsiloxane.