JP2005097527A - Surface treating agent, surface treating method and product treated thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treating agent and a method for treating the surface with the agent that can easily fill in flaws on a surface, particularly a coated surface or the like even without applying coatings to the surface again, when the flaws have occurred on the surface, and can protect the surface for a long time. <P>SOLUTION: The surface treating agent comprises an organopolysiloxane (a) containing an Si-C bond and a hydrolyzable silyl group and an organopolysiloxane (b) that does not contain an alkoxysilyl group, wherein the amount of component (a) is 13-99.9 wt.% and the amount of component (b) is 0.1-87 wt.% based on the total amount of components (a) and (b). The surface treating method is carried out by applying the agent to the surface of a material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a surface treatment agent, and in particular, conceals scratches such as scratches and polishing scratches on a painted surface of an automobile or the like, and gives gloss to the painted surface, thereby protecting the appearance of the painted surface for a long period of time. The present invention relates to a surface treatment agent, a surface treatment method, and a treated article.

  In order to protect or polish a painted surface of an automobile or the like, a wax is widely applied. In general, wax coating is known to have an effect of improving the gloss of the painted surface immediately after coating, but it is difficult to maintain the initial gloss for a long time after coating, and the wax coating is performed periodically. There is a need. However, there has been a problem that repeated coating of the wax may cause fine scratches on the painted surface.

  On the other hand, the painted surface formed on automobiles has many opportunities to cause scratches and fine cracks due to external factors such as friction, rain, mud, dust, etc. during car washing in addition to the above wax application work. There is a need for a simple processing method that conceals the defect site and makes it inconspicuous.

  For example, Patent Document 1 discloses a specific organopolysiloxane composition as a deteriorated coating film for automobiles and a small wound repairing and polishing agent. According to the composition, it is disclosed that a deteriorated coating film can be repaired and a highly durable coating film having excellent gloss can be formed. However, since the composition contains a large amount of volatile components, the volatile components in the polish were volatilized after application, and there was a tendency that a significant volume reduction occurred in the coating over time. For this reason, when the polishing agent is applied to, for example, a concave portion of a scratch generated on a painted surface, many of the concave portions of the scratch are exposed again, and there are cases where repair and concealment of the scratch are insufficient. In addition, the film after application tends to become dirty over time, and the attached dirt may be difficult to wipe off.

JP-A-10-36771

  The object of the present invention is to provide a surface on which a film can be formed so that the film after coating can be sufficiently concealed without shrinking the volume, the film after coating is less likely to become dirty with time, and the attached dirt component can be easily removed. It is to propose a treatment agent.

As a result of intensive investigations to solve the above problems, the present inventors have found that organopolysiloxanes containing Si—C bonds and hydrolyzable silyl groups and organopolysiloxanes containing no alkoxy groups at a specific blending ratio. The present invention has been reached by the specific surface treatment agent contained. That is, the present invention
1. An organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group and an organopolysiloxane (b) containing no alkoxy group are contained, and the total weight of the component (a) and the component (b) A surface treating agent characterized in that the amount of component (a) is 13 to 99.9% by weight and the amount of component (b) is in the range of 0.1 to 87% by weight;
2. An organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group and an organopolysiloxane (b) containing no alkoxy group are contained, and the total weight of the component (a) and the component (b) A surface treatment agent, wherein the amount of component (a) is in the range of 50 to 99.9% by weight and the amount of component (b) is in the range of 0.1 to 50% by weight;
3. The surface treatment agent according to item 1 or 2, wherein the amount of the organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group is 20% by weight or more in the treatment agent,
4). 4. The surface according to any one of items 1 to 3, wherein the refractive index of the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group is in the range of 1.39 to 1.55. Processing agent,
5). The surface treating agent according to any one of 1 to 4, wherein the organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group has a benzene ring structure,
6). The organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group contains an organopolysiloxane skeleton having a three-dimensional structure and a linear organopolysiloxane skeleton in the molecule (a1). 6) The surface treatment agent according to any one of 1 to 5, which contains
7). 7. The organopolysiloxane (b) containing no alkoxy group is a linear polysiloxane and / or a cyclic polysiloxane having a molecular weight in the range of 200 to 1,000. Surface treatment agent,
8). The surface treatment agent according to any one of 1 to 7, further comprising an organosilicate compound (c),
9. 1 to 8 further comprising at least one compound (d) selected from the group consisting of polytetrafluoroethylene, a compound containing a perfluoroalkyl group, and an alkoxysilane containing a hydrocarbon group having 6 or more carbon atoms. The surface treating agent according to any one of the items,
10. The surface treatment agent according to any one of 1 to 9, which contains an organometallic compound in an amount of 0.1 to 10% by weight based on the surface treatment agent.
11. 11. The surface treatment agent according to any one of items 1 to 10, wherein the kinematic viscosity is in the range of 1 to 300 mm ² / s.
12 A surface treatment method comprising applying the surface treatment agent according to any one of items 1 to 11 to a surface to be coated,
13. The surface treatment method according to item 12, wherein the surface to be coated is a painted surface on which a coating film is formed,
14 The surface treatment method according to item 12, wherein the surface to be coated is a painted surface on which a clear coating film is formed,
15. An article treated by the method of any one of paragraphs 12-12 to 14,
About.

  Since the surface treatment agent of the present invention has good application workability and the volumetric shrinkage of the film after application is small, it is reapplied even when applied to a coated surface where scratches are generated. The film formed from the surface treatment agent of the present invention has the property that dirt does not adhere easily and can be easily removed even if dirt adheres. It can be made to. Moreover, the surface can be modified to be hydrophilic by applying the surface treating agent according to claim 8 containing an organosilicate compound. On the other hand, it contains at least one compound selected from the group consisting of polytetrafluoroethylene, a compound containing a perfluoroalkyl group, and an alkylalkoxysilane containing a hydrocarbon group having 6 or more carbon atoms. By applying the described surface treating agent, the surface can be modified to be water repellent or slippery. Thus, according to the surface treating agent of the present invention, for example, scratches can be concealed on the painted surface and the aesthetic appearance can be maintained for a long time.

  The surface treatment agent of the present invention contains an organopolysiloxane (a) containing an Si—C bond and a hydrolyzable silyl group and an organopolysiloxane (b) containing no alkoxy group, and the component (a) and the component ( The amount of component (a) is 13 to 99.9% by weight, preferably 16 to 99.9% by weight, more preferably 30 to 99.9% by weight, based on the total weight of b). The amount is 0.1 to 87% by weight, preferably 0.1 to 84% by weight, more preferably 0.1 to 70% by weight.

  In the present invention, the surface treatment agent contains an organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group and an organopolysiloxane (b) containing no alkoxy group, and the component (a) and The amount of component (a) is 50 to 99.9% by weight, preferably 60 to 90% by weight, and the amount of component (b) is 0.1 to 50% by weight, preferably based on the total weight of component (b). Is particularly preferably in the range of 10 to 40% by weight.

  If the amount of the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group is less than 13% by weight, the flaw filling property tends to be insufficient, whereas if it exceeds 99.9% by weight, the coating operation is performed. Tend to decrease.

  Next, each component contained in the surface treating agent of the present invention will be described.

Organopolysiloxane containing Si-C bond and hydrolyzable silyl group (a)
As the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group, conventionally known ones can be used without limitation. For example, an organopolysiloxane containing a Si—C bond in the molecule can be used. Examples include a method of hydrolyzing and condensing halosilane and alkoxylating with alcohol; a method of hydrolyzing and condensing organoalkoxysilane containing Si—C bond in the molecule.

  Specifically, as these methods, various conditions can be adopted using an organosilane compound containing at least one selected from organosilane compounds containing Si—C bonds represented by the following formulas (1) to (3) as raw materials. It hydrolyzes and condenses.

In the above formulas (1) to (3), R ¹ is the same or different and is a substituted or unsubstituted hydrocarbon group or a polymerizable unsaturated group, and X is the same or different and is a hydroxyl group, an alkoxy group, Represents a halogen atom.

Specific examples of R ¹ are the same or different, and are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, i -Pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, i-heptyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group, n-octadecyl group, etc. Alkyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl group such as benzyl group, phenethyl group and phenylpropyl group; 3-chloropropyl group; Halogenated alkyl group such as 3,3,3-trifluoropropyl group; vinyl group, allyl group, i-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl A cycloalkenyl group such as 2-cyclohexylenyl group, 3-cyclohexylenyl group, 2-vinylcyclohexyl group, 3-vinylcyclohexyl group, 4-vinylcyclohexyl group, 2-vinylphenyl group, 3-vinylphenyl group, 4- Polymerizable unsaturated groups such as vinylphenyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 3-allyloxypropyl group, 3- (meth) acryloyloxypropyl group; aminoethyl group, Examples thereof include aminoalkyl groups such as 3-aminopropyl group; glycidoxyalkyl groups such as 3-glycidoxypropyl group.

  On the other hand, X may be the same or different and may be methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, tert-butoxy group, n-pentyloxy group, i- Examples thereof include alkoxy groups such as a pentyloxy group, n-hexyloxy group, i-hexyloxy group and phenoxy group; halogens such as chlorine, bromine and fluorine;

  Specific examples of the organosilane compounds represented by the above formulas (1) to (3) include monoalkoxysilanes such as trimethylmethoxysilane; dialkoxysilanes such as dimethyldimethoxysilane and diphenyldimethoxysilane; methyltrimethoxysilane, methyl And trialkoxysilanes such as triethoxysilane and phenyltrimethoxysilane; organohalosilanes such as dimethyldichlorosilane and trimethylchlorosilane; and the like.

  In the present invention, the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group is generally composed mainly of an organosilane compound represented by the formula (1) and / or the formula (2). An organopolysiloxane having a three-dimensional structure is preferable. Moreover, in order to adjust the hardness, flexibility, bending resistance, etc. of the coating, an organosilane compound represented by the formula (3) and / or the formula (4) can be appropriately mixed as a raw material.

  Specific examples of the organosilane compound represented by the above formula (4) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraphenoxysilane; tetrahalosilanes such as tetrachlorosilane, and the like. Can be mentioned.

  Moreover, the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group is produced by using a bifunctional organosilane compound represented by the formula (2) as a main component. An organopolysiloxane having a linear structure may be used.

  In the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group, the alkoxy group bonded to the silicon atom as the hydrolyzable silyl group, that is, the alkoxysilyl group is caused by moisture or moisture in the air. It is known that it is hydrolyzed to become silanol, and the condensation reaction between silanols proceeds at room temperature. In the present invention, the weight average molecular weight is 200 as the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group from the drying property of the coating film at normal temperature and the strength and coating workability of the coating film to be formed. Organopolysiloxanes having a three-dimensional structure in the range of ~ 30,000, preferably 300 to 25,000 are desirable. In addition, in this specification, a weight average molecular weight is the value which converted the molecular weight measured by the gel permeation chromatography on the basis of the weight average molecular weight of polystyrene.

  Moreover, in order for the coating film by the surface treating agent of the present invention to exert stain resistance or stain removability with respect to hydrophilic or hydrophobic stain components, it contains a Si—C bond and a hydrolyzable silyl group. It is desirable that the organopolysiloxane (a) to be substituted has a methyl group as a substituent, and that the methyl group concentration of the organopolysiloxane (a) is 20 mol% or more, preferably 40 mol% or more. .

  In this specification, the methyl group concentration of the organopolysiloxane (a) can be calculated based on the following formula.

Methyl group concentration (mol%) of organopolysiloxane (a) = (n2 / n1) × 100
n1: Total number of moles of substituent R ¹ in the organosilane compounds of the above formulas (1), (2), (3) and (4), n2: Number of moles of methyl group in substituent R ^{1 In} the present invention, The organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group is used for the purpose of making the scar after concealment unnoticeable when the surface treatment agent of the present invention is applied to a scratch or the like. It is desirable that the rate is in the range of 1.39 to 1.55, preferably 1.45 to 1.55. In this specification, the refractive index is measured with an Abbe refractometer in accordance with JIS K0062.

  For the purpose of making the scars after concealment unnoticeable, the organopolysiloxane (a) containing the Si—C bond and hydrolyzable silyl group preferably contains a benzene ring structure.

  Further, in the present invention, the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group is improved in coating spreadability and flaw filling properties, and the effect of easily removing attached dirt is improved. It is desirable to contain an organopolysiloxane (a1) that contains both an organopolysiloxane skeleton having a structure and a linear organopolysiloxane skeleton in the molecule.

  Examples of the linear organopolysiloxane skeleton include a structure represented by the following formula (5).

In the formula (5), j represents an integer of ² to 1,000, R ² is the same or different and represents a substituted or unsubstituted hydrocarbon group, and the hydrocarbon group is a saturated group, May be the same or different, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n- Pentyl group, i-pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, i-heptyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group, n- Alkyl groups such as octadecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group, phenethyl group and phenylpropyl group; 3 Halogenated alkyl groups such as chloropropyl group and 3,3,3-trifluoropropyl group, aminoalkyl groups such as aminoethyl group and 3-aminopropyl group; glycidoxyalkyl groups such as 3-glycidoxypropyl group In particular, a methyl group is preferable.

  Examples of a method for producing an organopolysiloxane (a1) that contains both an organopolysiloxane skeleton having a three-dimensional structure and a linear organopolysiloxane skeleton in the molecule include (1) an alkoxy group in the molecule and polymerization. A method of reacting an organopolysiloxane having a three-dimensional structure containing a polymerizable unsaturated group with a linear organopolysiloxane containing Si-H groups at both ends, or (2) an alkoxy group in the molecule And a method of reacting an organopolysiloxane having a three-dimensional structure containing a Si—H group with a linear organopolysiloxane containing a polymerizable unsaturated group at both ends.

  Examples of the polymerizable unsaturated group include a vinyl group, an allyl group, an i-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group and the like; a 2-cyclohexylenyl group, a 3-cyclohexylenyl group, Cycloalkenyl groups such as 2-vinylcyclohexyl group, 3-vinylcyclohexyl group, 4-vinylcyclohexyl group; vinylphenyl groups such as 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group; 2-allylphenyl Group, 3-allylphenyl group, allylphenyl group such as 4-allylphenyl group; 3-allyloxypropyl group, 3- (meth) acryloyloxypropyl group, among others, vinyl due to reactivity with Si-H group A group is desirable.

  In the reactions (1) and (2) above, simple metals such as Ni, Rh, Pd, and Pt and compounds thereof in the presence of an organic solvent such as hexane, pentane, toluene, xylene, etc., if necessary, in accordance with conventional methods The hydrosilylation reaction can be performed using the complex as a catalyst.

  In the reactions (1) and (2) above, in order to minimize the amount of unreacted linear organopolysiloxane and obtain the desired compound without gelation, The functional group (polymerizable unsaturated group or Si-H group) of the organopolysiloxane having a three-dimensional structure is excessive with respect to the functional group (Si-H group or polymerizable unsaturated group) of siloxane. It is desirable to make it.

  The amount of the organopolysiloxane (a1) is 1 to 60% by weight, preferably 3 to 50% by weight, based on the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group. It is desirable from the viewpoints of soil removability and curability (touch drying property).

  In the present invention, the organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group includes “SR2406”, “SR2410”, “SR2420”, “SR2416”, “SR2402”, “AY42-161”. (Toray Dow Corning Silicone Co., Ltd.), FZ-3704, FZ-3511 (Nihon Unicar Co., Ltd.), KC-89S, KR-500, X-40- 9225 "," X-40-9246 "," X-40-9250 "," KR-217 "," KR-9218 "," KR-213 "," KR-510 "," X-40-9227 " , “X-40-9247”, “X-41-1053”, “X-41-1056”, “X-41-1805”, “X-41-1810”, “X-40-265” 1 "," X-40-2308 "," X-40-9238 "," X-40-2239 "," X-40-2327 "," KR-400 "," X-40-175 "," Commercial products such as “X-40-9740” (manufactured by Shin-Etsu Chemical Co., Ltd.) are applicable.

Organopolysiloxane containing no alkoxy group (b)
In the present invention, the organopolysiloxane (b) containing no alkoxy group does not substantially hydrolyze itself, and is blended to improve the spreadability and make the formed film uniform. is there. The organopolysiloxane (b) containing no alkoxy group preferably has a molecular weight in the range of 200 to 1,000, preferably 300 to 700, from the viewpoint of spreadability. (6) Or the linear polysiloxane and / or cyclic polysiloxane which are represented by the following Formula (8) can be mentioned.

  As said linear polysiloxane compound, the compound represented by the following Formula (6) can be mentioned.

R ³ is the same or different and represents a substituted or unsubstituted hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl. Group, n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; phenyl group and other aryl groups; benzyl group and phenylpropyl group An aralkyl group such as an aminoalkyl group such as an aminoethyl group and a 3-aminopropyl group; a glycidoxyalkyl group such as a 3-glycidoxypropyl group and the like. Groups, in particular methyl groups, are preferred. Y represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms or a polyoxyalkylene group represented by the following formula (7). When Y is an alkyl group, for example, an n-hexyl group, i -Hexyl group, n-heptyl group, i-heptyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group and the like, among which an alkyl group having 6 to 9 carbon atoms is preferable. . k1 represents an integer of 1 to 8, and k2 represents an integer of 1 to 8. In the compound represented by the above formula (6), it is preferable that k1 and k2 are both 1 because the spreadability of the surface treatment agent of the present invention is excellent.
_{^{-O- (CHR 4 -CH 2 -O)}} k3 -R 41 (7)
k3 represents an integer of 1 to 20, preferably 2 to 20, and R ⁴ represents a methyl group or a hydrogen atom. R ⁴¹ represents hydrogen or a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, particularly preferably hydrogen or a methyl group.

  In the linear organopolysiloxane compound represented by the above formula (6), by introducing a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms or a polyoxyalkylene group as Y, hydrophilicity / hydrophobicity of the compound It is possible to control the degree of compatibility, and is useful for improving the compatibility with organopolysiloxane (a) containing Si—C bond and hydrolyzable silyl group and various components described later, and the adhesion of the treated film. it can.

  Examples of the cyclic polysiloxane compound that can be used as the organopolysiloxane (b) include compounds represented by the following formula (8).

R ⁵ is the same or different and represents a substituted or unsubstituted hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl. Group, n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; phenyl group and other aryl groups; benzyl group and phenylpropyl group An aralkyl group such as an aminoalkyl group such as an aminoethyl group and a 3-aminopropyl group; a glycidoxyalkyl group such as a 3-glycidoxypropyl group and the like. Groups, in particular methyl groups, are preferred. l represents an integer of 3 to 10. Specific examples of suitable cyclic polysiloxane compounds include methylcyclopolysiloxanes such as decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, and dodecamethylcyclohexasiloxane.

  The above exemplified compounds may be used singly or in combination.

Organosilicate compound (c)
The surface treating agent of the present invention preferably further contains an organosilicate compound (c). Thereby, there is an advantage that the surface of the coating film formed by the surface treatment agent is modified to become hydrophilic with time by rain water or the like, and is less likely to become dirty. Examples of the organosilicate compound (c) that can be used for such a purpose include linear compounds represented by the following formula (9).

Wherein, ^{R 6} are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 1 to 100. Examples of the hydrocarbon group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, i-pentyl group, Alkyl groups such as n-hexyl group, i-hexyl group and n-octyl group, and aryl groups such as phenyl group are preferred. In particular, R ⁶ is preferably an alkyl group having 1 to 4 carbon atoms. As the organosilicate compound (c), those having an average degree of condensation of 2 to 15 are suitable, and the weight fraction of the silica remaining as silica when the organosilicate compound (c) is baked at 900 ° C. Preference is given to organosilicate compounds which have been condensed to a range of 20 to 60% by weight. Further, the organosilicate compound (c) in the present invention may contain a branched or cyclic structure condensate in addition to the linear condensate represented by the above formula (9). The organosilicate compound (c) is desirably contained in an amount of 20% by weight or less, preferably 1 to 15% by weight, based on the treating agent.

One or more compounds (d) selected from the group consisting of polytetrafluoroethylene, a compound containing a perfluoroalkyl group, and an alkoxysilane containing a hydrocarbon group having 6 or more carbon atoms
The surface treating agent of the present invention is one or more compounds selected from the group consisting of polytetrafluoroethylene, a compound containing a perfluoroalkyl group, and an alkoxysilane containing a hydrocarbon group having 6 or more carbon atoms (d ) Is desirable. By compounding the compound (d), there is an advantage that the coating film formed by the surface treatment agent is modified to have water repellency or water slidability, and the dirt component is difficult to adhere. Here, the water-repellent film means a film that easily repels water droplets, and the water-slidable film means a film that easily drops water droplets and the like.

  Examples of the polytetrafluoroethylene include those having an average particle diameter of 10 μm or less. By having such a shape, it is possible to improve the flaw filling properties on the painted surface and the like. The particulate polytetrafluoroethylene may be blended as it is in a particle state (powder), but may be blended in advance as a dispersion dispersed by mixing with a dispersion medium, a dispersant and / or a dispersion resin. The average particle size is a value of 50% average particle size by laser diffraction method.

  Examples of the compound containing a perfluoroalkyl group include alkoxysilane compounds containing a perfluoroalkyl group represented by the following formula (10).

R ⁷ is the same or different and represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, m1 represents an integer of 0 to 12, m2 represents an integer of 0 to 4, and a is 1 to 3, preferably an integer of 3.

  Perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyltrimethylammonium salt, perfluoroalkylbetaine, perfluoroalkylamine oxide, perfluoroalkylethylene oxide addition to compounds containing perfluoroalkyl groups Fluorosurfactants such as products are also included.

Examples of the alkoxysilane containing a hydrocarbon group having 6 or more carbon atoms include a compound represented by the following formula (11).
R ⁸ _(4-b) Si (OR ⁹ ) _b (11)
R ⁸ is the same or different and represents a hydrocarbon group having 6 or more carbon atoms, and R ⁹ is the same or different and represents an aryl group or an alkyl group having 1 to 4 carbon atoms. b represents an integer of 1 to 3, preferably 3. R ⁸ is the same or different and represents a substituted or unsubstituted hydrocarbon group. For example, the same or different, R ⁸ represents an n-hexyl group, i-hexyl group, n-heptyl group, i-heptyl group, n-octyl group. Group, i-octyl group, n-nonyl group, n-decyl group, n-octadecyl group and other alkyl groups; cyclohexyl group and other cycloalkyl groups; phenyl group, tolyl group, xylyl group, naphthyl group and other aryl groups; Examples thereof include aralkyl groups such as benzyl group, phenethyl group, and phenylpropyl group. R ⁹ may be the same or different and is an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-propyl group, an n-butyl group, an i-butyl group or a t-butyl group; an aryl such as a phenyl group Group; etc., and a methyl group is particularly preferable.

  The above compound (d) can be used alone or in a suitable manner, and can be used in an amount of 1 to 30% by weight, preferably 2 to 25% by weight, based on the surface treatment agent of the present invention. .

  In the surface treating agent of the present invention, it is desirable to include an organometallic compound in order to improve the curability of the resulting formed film. Examples of the organometallic compound include diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, diacetyltin dioctoate, tin octylate, dibutyltin diacetate, and dibutyltin dioctoate; aluminum trimethoxy Organic aluminum compounds such as aluminum tris (acetylacetonate), aluminum tri-n-butoxide, aluminum tris (acetoacetate ethyl), aluminum diisopropoxy (acetoacetate ethyl), aluminum acetylacetonate; titanium tetra (monoethyl) Ethoxide), titanium tetra (monoethyl ethoxide), titanium tetra (monobutyl ethoxide), titanium tetrakis (acetylacetate) ), Organic titanium compounds such as tetranormal butyl titanate; zirconium tetra (monomethyl ethoxide), zirconium tetra (monoethyl ethoxide), zirconium tetra (monobutyl ethoxide), zirconium normal propylate, zirconium normal butyrate, Organic zirconium compounds such as zirconium tetrakis (acetylacetonate); organic zinc compounds such as zinc naphthenate; organic cobalt compounds such as cobalt octylate and cobalt naphthenate; trimethyl borate, triethyl borate, tripropyl borate, boric acid Boric acid compounds such as boric acid esters such as tributyl, triphenyl borate, tri (4-chlorophenyl) borate, trihexafluoroisopropyl borate, and the like. In combination it can be used for more than species. Among these, an organic titanium compound or an organoaluminum compound is preferable from the viewpoint of curability and ease of use. The organometallic compound is contained in an amount of 0.1 to 10% by weight, preferably 0.5 to 7% by weight, based on the surface treatment agent of the present invention.

  The surface treatment agent of the present invention preferably contains a dehydrating agent from the viewpoint of storage stability. As the dehydrating agent, a dehydrating agent known per se can be used. Specifically, aluminum isopropylate, aluminum sec-butyrate, tetraisopropyl titanate, tetranormal butyl titanate, zirconium normal butyrate, ethyl silicate, Metal alkoxides such as vinyltrimethoxysilane; Organic alkoxy compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, orthopropyl ortho orthoacetate, and dimethoxypropane; “Additive TI” (trade name, Sumitomo Bayer Urethane Monofunctional isocyanates such as those manufactured by Kogyo Co., Ltd., and these can be used alone or in combination of two or more. The mixing ratio of the dehydrating agent is generally 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the surface treatment agent of the present invention.

  The surface treating agent of the present invention can contain an organic solvent for the purpose of adjusting the coating workability and the curing speed. Examples of such organic solvents include aliphatic organic solvents such as n-hexane, n-octane, i-octane, n-nonane, cyclohexane, methylcyclohexane, mineral spirits, etc .; “Swazol 100” (product of Maruzen Petrochemical Co., Ltd.) Petroleum organic solvents such as petroleum ether, petroleum benzene and petroleum naphtha; aromatic organic solvents such as toluene and xylene; ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester organic solvents such as butyl acetate and the like These can be used alone or in combination of two or more. In general, the organic solvent can be contained in an amount of 50% by weight or less, preferably 40% by weight or less based on the surface treatment agent of the present invention.

  The surface treating agent of the present invention can include a colorant having the same hue as the surface to be coated, a colorant such as a bright pigment and a dye, and the hue can be adjusted according to the surface to be coated.

  The surface treatment agent of the present invention may further include a modifying resin such as an acrylic resin, a urethane resin, an epoxy resin, an amino resin, a polyester resin, an acrylic silicon resin, a fluororesin; a silicone oil; an oxidation having photocatalytic activity. Titanium; Needle-like single crystal inorganic powder such as zinc whisker; Silane coupling agent; Titanium coupling agent; Colloidal silica, resin particles, surface conditioner, viscosity modifier, UV absorber, light stabilizer, antioxidant , Additives such as surfactants, film-forming aids, thickeners; crosslinking agents such as isocyanate compounds and melamine resins;

Surface treatment agent of the present invention, from the viewpoint of coating stretch resistance and scratch filling properties, kinematic viscosity of 1 to 300 mm ² / s, it is desirable that preferably in the range 3~250mm ² / a. In this specification, the kinematic viscosity is obtained by measuring the outflow time of the sample using a Canon-Fenske viscometer holder in accordance with the JIS K 2283 kinematic viscosity test method at a temperature of 25 ° C. It is a calculated value.

  The surface treatment agent of the present invention is desirably contained in a sealable container such as an extruded tube, a metal can, or a bottle so as not to be affected by moisture or moisture in the air.

  Next, a method for applying the surface treatment agent will be described.

  The surface treatment method of the present invention is a surface treatment method characterized by applying a surface treatment agent obtained as described above to a surface to be coated.

  Examples of the application method include a method of spreading the surface treatment agent with a spreading material such as sponge or cloth, a conventionally known method such as spray coating, brush coating, dip coating, roll coating, and the like as necessary. The excess can be wiped off with a wiping material.

  The material of the coating material is not limited as long as it is a material that does not damage the surface to be coated and is not affected by the surface treatment agent, and examples thereof include polyester, polypropylene, acrylic, cotton, silk, hemp, wool, polyurethane, and nylon. The shape can be appropriately selected, and examples thereof include sponge, cloth, flannel, felt, and fleece. Moreover, as a wiping material, the same material and shape as those listed in the description of the spreading material can be appropriately selected and used.

  Examples of the coated surface to which the surface treatment method of the present invention is applied include various substrate surfaces and coated surfaces on which a coating film is formed. Examples of the substrate include iron, zinc, and iron / zinc. Metals such as alloys; inorganic base materials such as wood, concrete, gypsum board, slate, siding material, porcelain tile wall surface, lightweight cellular concrete, mortar, brick, stone, glass, etc .; plastics; leather; On the other hand, the coating surface on which the coating film is formed on the substrate is not particularly limited, but a top coating film formed by painting a solid color paint, a top coating formed by painting a metallic paint. Examples thereof include a coating film, a top coating film formed by applying a light interference coating, and a top coating film formed by applying a clear coating. Moreover, the multilayer coating film formed by apply | coating 2 or more types of top-coat paints chosen from the said top-coat paint may be sufficient. Moreover, as said top coat film, it is desirable to form a cured coating film, and undercoat and / or intermediate coat film formed by applying undercoat paint or intermediate coat paint to the lower layer of these top coat films is provided. May be.

  Specific examples of the surface to be coated include passenger cars, trucks, buses, motorcycles, trains, and other vehicles, airplanes, buildings, and home appliances.

  The painted surface to which the surface treatment method of the present invention is applied may be a newly painted surface or an existing painted surface. On the other hand, on the existing painted surface, it is possible to exert a scratch filling effect especially on the painted surface on which a coating film in which scratches are generated is formed. Examples of the depth of the scratch include 0.1 to 5 μm, and further about 0.5 to 3 μm. In particular, when the coated surface is a painted surface with a clear coating film (including a multilayer coating surface in which the uppermost layer is a painted surface with a clear coating film formed), it is generated on the clear painted surface. This makes it possible to make the scratches inconspicuous and exert its effect.

  Further, according to the surface treatment method of the present invention, after the surface treatment agent obtained as described above is applied to the surface to be coated, the dirt component adhering to the treatment film can be easily removed.

  Examples of the dirt component include sand, earth, bird droppings, oil, scale, pollen, oil smoke, carbon, and acid rain.

  As a method of removing the dirt component, a method of wiping the treatment film with the surface treatment agent of the present invention by impregnating the above-described coating spreading material with the cleaning liquid, and a method of directly applying the cleaning liquid to the processing film And a method of wiping after directly applying the cleaning liquid to the treatment film. The cleaning liquid can be appropriately selected according to the type of the soil component such as water, a surfactant aqueous solution, or an organic solvent.

  Further, in the surface treatment method of the present invention, the appearance such as the gloss of the painted surface can be restored and protected for a long time only by applying the surface treatment agent. For example, a conventionally known wax such as a water-sliding wax containing a hydroxyl group-containing siloxane polymer and a polyisocyanate compound, a polishing agent, or the like may be applied.

  Next, an Example is given and this invention is demonstrated more concretely.

Examples will be described.
“Part” and “%” indicate “part by weight” and “% by weight”, respectively.

Production of organopolysiloxane containing Si-C bond and hydrolyzable silyl group Production Example 1
To a three-necked flask, 80 parts of methyltrimethoxysilane and 20 parts of dimethyldimethoxysilane were added, and 10 parts of 0.05N aqueous hydrochloric acid was added dropwise with stirring, followed by hydrolysis and condensation at 68 ° C. for 1 hour. This was heated to 120 ° C. to remove by-product methanol and filtered to obtain organopolysiloxane A containing a hydrolyzable silyl group. The kinematic viscosity was 200 mm ² / s, and the refractive index was 1.41.

Production Example 2
To a three-necked flask, 80 parts of methyltrimethoxysilane and 20 parts of dimethyldimethoxysilane were added, and 10 parts of 0.05N aqueous hydrochloric acid was added dropwise with stirring, followed by hydrolysis and condensation at 68 ° C. for 2 hours. This was heated to 120 ° C. to remove by-product methanol and filtered to obtain organopolysiloxane B containing a hydrolyzable silyl group. The kinematic viscosity was 500 mm ² / s, and the refractive index was 1.41.

Production Example 3
To a three-necked flask, 50 parts of methyltrimethoxysilane, 20 parts of dimethyldimethoxysilane and 30 parts of phenyltrimethoxysilane were added, and 10 parts of 0.05N hydrochloric acid was added dropwise with stirring, followed by hydrolysis and condensation at 68 ° C. for 1 hour. This was heated to 120 ° C. to remove by-product methanol and filtered to obtain organopolysiloxane C containing a hydrolyzable silyl group. The kinematic viscosity was 250 mm ² / s, and the refractive index was 1.50.

Production Example 4
Hydrolyze a mixture consisting of 108.8 parts of methyltrimethoxysilane, 18.0 parts of dimethyldimethoxysilane, 12.2 parts of diphenyldimethoxysilane and 12.0 parts of water in a three-necked flask, and distill off the by-produced methanol under reduced pressure. Thus, organopolysiloxane D containing a hydrolyzable silyl group was obtained. The kinematic viscosity was 200 mm ² / s, and the refractive index was 1.48.

Production Example 5
To a three-necked flask, 85 parts of methyltrimethoxysilane and 15 parts of vinylmethyldimethoxysilane were added, and 15 parts of 0.05N aqueous hydrochloric acid was added dropwise with stirring, followed by hydrolysis and condensation at 68 ° C. for 2 hours. This was heated to 120 ° C. to remove byproduct methanol and filtered to obtain polyorganosiloxane E.
In another three-necked flask, 250 parts of polyorganosiloxane E, 125 parts of dimethylsiloxane oil with both ends Si—H group as a component having a linear dimethylsiloxane skeleton (note), “CAT-PL-50T” (product) (Name, Shin-Etsu Chemical Co., Ltd., Pt catalyst) 1.5 parts is added, hydrosilylation reaction is performed at 80 ° C. for 8 hours, this is subjected to reduced pressure treatment at 120 ° C. and 10 mmHg for 2 hours, filtered, and three-dimensional structure An organopolysiloxane F containing both an organopolysiloxane skeleton having a straight chain and a linear dimethylpolysiloxane skeleton in the molecule and a hydrolyzable silyl group was obtained. The kinematic viscosity was 250 mm ² / s, and the refractive index was 1.41.
(Note) Dimethylsiloxane oil: H- [Me ₂ SiO] ₁₉ -Me ₂ Si-H as a main component.

Production Example 6
100 parts of methyltrimethoxysilane was added to a three-necked flask, and 10 parts of 0.05N aqueous hydrochloric acid was added dropwise with stirring, followed by hydrolysis and condensation at 68 ° C. for 2 hours. This was heated to 120 ° C. to remove by-product methanol and filtered to obtain organopolysiloxane G containing a hydrolyzable silyl group. The kinematic viscosity was 50 mm ² / s, and the refractive index was 1.41.

Production of surface treating agents Examples 1-21 and Comparative Examples 1-5
Each component was blended according to the blending composition shown in Table 1 to obtain each surface treatment agent, which was then housed in a can equipped with a hermetic lid.

(Note 1) Heptamethyloctyltrisiloxane: a compound in which R ³ is a methyl group, Y is an octyl group, and k1 and k2 are both 1 (Note 2) “Ethyl silicate 40”: trade name, Colcoat Tetraethoxysilane condensate, average condensation degree 6 and tetraethoxysilane condensed to a state containing 40% by weight as SiO ₂ (Note 3) “Ethyl silicate 48”: trade name, manufactured by Colcoat An ethoxysilane condensate, a product obtained by condensing tetraethoxysilane to a state containing 48% by weight as SiO ₂ (Note 4) “Fluon PTFE Lubricant L173J”: trade name, manufactured by Asahi Glass Co., Ltd., polytetrafluoroethylene powder. Average particle size 7μm
(* Note) heptadecafluorodecyltrimethoxysilane: In formula (10), m1 is 7, m @ 2 is 2, a is 3, the compound ^{R 7} is a methyl group.

Comparative Examples 6-9
Each surface treating agent was manufactured by blending each component described in Table 2 below.

(Note 5) “X-40-175”: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., organopolysiloxane containing Si—C bond and hydrolyzable silyl group (Note 6) “SR2406”: trade name, Toray Dow Corning Silicone, organopolysiloxane containing Si—C bond and hydrolyzable silyl group (Note 7) “KF994”: trade name, Shin-Etsu Chemical Co., Ltd., cyclic dimethylpolysiloxane (Note 8) “KF414” : Trade name, Shin-Etsu Chemical Co., Ltd., alkyl-modified silicone oil (Note 9) “KF96L-5”: Trade name, Shin-Etsu Chemical Co., Ltd., dimethyl silicone oil (Note 10) “KF96L-1.5”: Trade name , Shin-Etsu Chemical Co., Ltd., dimethyl silicone oil (Note 11) “SH230”: Toray Dow Corning Silicone Co., Ltd., alkylaralkyl-modified silicone Oil.

The following commercial products were further used as treatment agents for comparative examples.
Comparative Example 10: Carnauba Wax Comparative Example 11: Comparison of commercially available waxes having an organopolysiloxane content of less than 10% by weight containing a Si-C bond and a hydrolyzable silyl group, manufactured by SOFT99 Co., Ltd. Example 12: “Kizukuri R” trade name, manufactured by SOFT99, commercially available wax containing Si—C bond and hydrolyzable silyl group and containing less than 10% by weight of organopolysiloxane, composition: acrylic resin, urethane resin, Petroleum solvent.

Application of surface treatment agent to automobile body <br/> Automobile outer plate on which a multi-layer coating film is formed, with the top layer being a clear coating film with fine scratches (depth of about 1 [mu] m) due to car washing or waxing Further, each surface treatment agent was spread using a cloth and then wiped with another clean cloth until there was no unevenness.

Performance evaluation The performance evaluation of each surface treatment agent described in Examples 1-21 and Comparative Examples 1-12 and each test specimen coated with the surface treatment agent was performed. The results are shown in Table 3.

(* 1) Scratch concealing property Each test specimen whose surface was treated by the above-mentioned method was visually observed under outdoor sunlight, and it was evaluated according to the following criteria whether scratches before application of each surface treatment agent were concealed.
◎: Scratches are not visible at all, ○: Scratches are hardly visible, △: Scratches are slightly visible, X: Scratches are hardly concealed (* 2) Coating workability Coating workability with each surface treatment agent is as follows Evaluated by criteria.
○: Easily finishes without unevenness, △: It is not easy to finish without unevenness, and it takes a lot of time to finish, X: Unevenness remains even after much time (* 3) Easiness to remove dirt Each of the obtained test specimens was exposed outdoors for 3 months, and then the ease of removing the dirt of each test specimen after the exposure was evaluated according to the following criteria.
◎: Dirt can be removed simply by washing the exposed specimen with water. ○: After exposing the specimen after washing with water, the dirt can be wiped clean with a cloth. △: After exposing the specimen with water, cloth Even if wiped with, the stain remains slightly, X: The exposed specimen is washed with water and wiped with a cloth.

The surface treatment agent of the present invention is very useful for applications such as repairing, polishing and maintaining the appearance of scratches and the like generated on coatings or substrates provided on automobiles, railway vehicles, airplanes, structures, leather, fibers, etc. Useful for.

Claims (15)

An organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group and an organopolysiloxane (b) containing no alkoxy group are contained, and the total weight of the component (a) and the component (b) A surface treating agent, wherein the amount of component (a) is in the range of 13 to 99.9% by weight and the amount of component (b) is in the range of 0.1 to 87% by weight. An organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group and an organopolysiloxane (b) containing no alkoxy group are contained, and the total weight of the component (a) and the component (b) A surface treating agent, wherein the amount of component (a) is in the range of 50 to 99.9% by weight and the amount of component (b) is in the range of 0.1 to 50% by weight. The surface treatment agent according to claim 1 or 2, wherein the amount of the organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group is 20% by weight or more in the treatment agent. The surface according to any one of claims 1 to 3, wherein the refractive index of the organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group is in the range of 1.39 to 1.55. Processing agent. The surface treating agent according to any one of claims 1 to 4, wherein the organopolysiloxane (a) containing a Si-C bond and a hydrolyzable silyl group has a benzene ring structure. The organopolysiloxane (a) containing a Si—C bond and a hydrolyzable silyl group contains an organopolysiloxane skeleton having a three-dimensional structure and a linear organopolysiloxane skeleton in the molecule (a1). The surface treating agent according to any one of claims 1 to 5, which comprises The organopolysiloxane (b) containing no alkoxy group is a linear polysiloxane and / or a cyclic polysiloxane having a molecular weight in the range of 200 to 1,000. Surface treatment agent. The surface treatment agent according to any one of claims 1 to 7, further comprising an organosilicate compound (c). The compound further comprises at least one compound (d) selected from the group consisting of polytetrafluoroethylene, a compound containing a perfluoroalkyl group, and an alkoxysilane containing a hydrocarbon group having 6 or more carbon atoms. The surface treating agent according to any one of 8. The surface treatment agent according to any one of claims 1 to 9, comprising an organometallic compound in an amount of 0.1 to 10% by weight based on the surface treatment agent. The surface treating agent according to claim 1, wherein the kinematic viscosity is in the range of 1 to 300 mm ² / s. A surface treatment method comprising applying the surface treatment agent according to any one of claims 1 to 11 to a surface to be coated. The surface treatment method according to claim 12, wherein the surface to be coated is a painted surface on which a coating film is formed. The surface treatment method according to claim 12, wherein the surface to be coated is a painted surface on which a clear coating film is formed. 15. An article treated by the method of any one of claims 12-14.