Coating composition, surface treatment agent containing the composition, and article surface-treated with the surface treatment agent

Abstract

The coating composition can form a cured film having excellent lipophilicity and abrasion resistance, and the coating composition contains the following (A) and (B) as essential components: (A) a (hydrolyzable) organosiloxane compound containing a lipophilic group and / or a partial (hydrolyzed) condensate thereof, which contains a (-C(=O)OR 1 )、(‑O‑C(=O)R 1 )、(‑C(=O)NR 1 2) (‑C(=O)SR 1 ) and (‑P(=O)(OR 1 )2)(R 1 (A) is a polyol ester composed of a condensate of a 2-6-valent alcohol and a fatty acid having 3 to 22 carbon atoms, and the mass ratio of the components (A) to (B) is 0.1<(A) / (B)<10.

Description

Technical Field

[0001] The present invention relates to a coating composition having excellent lipophilicity and abrasion resistance, a surface treating agent containing the composition, and an article surface-treated with the surface treating agent. Background Art

[0002] In recent years, the use of touch panels in displays, especially in mobile phones, has been accelerating. Since they are operated by touching with fingers, fingerprints and other dirt adhere to the display, which makes it unsightly. Therefore, in order to improve the appearance and visibility, the demand for technology to make it difficult for fingerprints to adhere to the display surface and to make fingerprints less noticeable is increasing year by year, and it is hoped that materials that can meet these requirements will be developed.

[0003] Generally, silane coupling agents are known as surface modifiers for substrates such as glass and cloth, and are widely used as coating agents for the surfaces of various substrates. Silane coupling agents have an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule, and the hydrolyzable silyl group undergoes a self-condensation reaction using moisture in the air to form a film. The film is chemically and physically bonded to the surface of glass, metal, etc. through the hydrolyzable silyl group to form a durable and firm film.

[0004] Therefore, a large number of compositions have been disclosed that can form a film having water-repellent, oil-repellent, antifouling properties, etc. on the surface of a substrate by using a fluoropolyether group-containing polymer in which a hydrolyzable silyl group is introduced into a fluoropolyether group-containing compound (Patent Documents 1 to 6: Japanese Unexamined Patent Application Publication No. 2008-534696, Japanese Unexamined Patent Application Publication No. 2008-537557, Japanese Unexamined Patent Application Publication No. 2012-072272, Japanese Unexamined Patent Application Publication No. 2012-157856, Japanese Unexamined Patent Application Publication No. 2013-136833, Japanese Unexamined Patent Application Publication No. 2015-199906).

[0005] However, the coating layer made of conventional fluoropolyether-containing polymers has high water and oil repellency and excellent dirt removability, but has the problem that fingerprints are easily visible because the sebum contained in fingerprints is repelled from the surface to form tiny oil droplets and scatter light.

[0006] There is also disclosed a composition which can form a lipophilic film on the surface of a substrate by using a silane compound having a hydrolyzable silyl group introduced into a lipophilic compound (Patent Document 7: Japanese Patent Application Laid-Open No. 2001-353808).

[0007] The composition containing the silane compound in which a hydrolyzable silyl group is introduced into the lipophilic compound can form a cured film having excellent lipophilicity. Therefore, when fingerprints or the like are attached, sebum does not scatter light, and the fingerprints are less noticeable.

[0008] However, conventional coating compositions capable of forming cured films having excellent lipophilicity are consumed due to wear and tear accompanying actual use, and their lipophilicity decreases. Therefore, they do not have performance that satisfies practical needs.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application No. 2008-534696

[0012] Patent Document 2: Japanese Patent Application No. 2008-537557

[0013] Patent Document 3: Japanese Patent Application Publication No. 2012-072272

[0014] Patent Document 4: Japanese Patent Application Publication No. 2012-157856

[0015] Patent Document 5: Japanese Patent Application Publication No. 2013-136833

[0016] Patent Document 6: Japanese Patent Application Publication No. 2015-199906

[0017] Patent Document 7: Japanese Patent Application Publication No. 2001-353808 Summary of the invention

[0018] Problems to be solved by the invention

[0019] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a coating composition capable of forming a cured film having excellent lipophilicity and abrasion resistance, a surface treating agent containing the composition, and an article surface-treated with the surface treating agent.

[0020] Means for solving problems

[0021] The present inventors have conducted intensive studies to achieve the above-mentioned purpose and have found that a coating composition containing the following components (A) and (B) as essential components, wherein the mass ratio of the components (A) to (B) is within the range of 0.1<(A) / (B)<10, can form a cured film having excellent lipophilicity and abrasion resistance, thereby solving the problems of the above-mentioned prior art and completing the present invention.

[0022] (A) a (hydrolyzable) organosiloxane compound containing a lipophilic group and / or a partial (hydrolyzed) condensate thereof, which contains a compound selected from the group consisting of (—C(═O)OR 1 ) represented by the formula (-OC(=O)R 1 ) represented by the formula (-C(=O)NR 1 2) A group represented by the formula (-C(=O)SR 1 ) and a group represented by the formula (-P(=O)(OR 1 )2)(wherein R 1 are independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. The lipophilic group and the silanol group or the hydrolyzable silyl group in the group represented by

[0023] (B) A polyol ester composed of a condensate of a di- to hexavalent alcohol and a fatty acid having 3 to 22 carbon atoms.

[0024] Therefore, the present invention provides the following coating agent composition, a surface treatment agent comprising the composition, and an article surface-treated with the surface treatment agent.

[0025] 1. A coating composition comprising the following (A) and (B) as essential components:

[0026] (A) a (hydrolyzable) organosiloxane compound containing a lipophilic group and / or a partial (hydrolyzed) condensate thereof, which contains a compound selected from the group consisting of (—C(═O)OR 1 ) represented by the formula (-OC(=O)R 1 ) represented by the formula (-C(=O)NR 1 2) A group represented by the formula (-C(=O)SR 1 ) and a group represented by the formula (-P(=O)(OR 1 )2)(wherein R 1 are independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. The lipophilic group and the silanol group or the hydrolyzable silyl group in the group represented by

[0027] (B) a polyol ester composed of a condensate of a 2- to 6-valent alcohol and a fatty acid having 3 to 22 carbon atoms,

[0028] The mass ratio of the component (A) to the component (B) is within the range of 0.1<(A) / (B)<10.

[0029] 2. The coating composition according to 1, wherein the component (A) is a (hydrolyzable) organosiloxane compound containing a lipophilic group and represented by the following general formula (1) and / or a partial (hydrolyzed) condensate thereof:

[0030] [Chemistry 1]

[0031]

[0032] [wherein A is -C(=O)OR 1 、-OC(=O)R 1 、-C(=O)NR 1 2. -C(=O)SR 1 OR-P(=O)(OR 1 )2(R 1 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. ), Y is independently a divalent organic group, W is independently an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group, or a hydrolyzable group, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, and q is an integer of 1 to 3.]

[0033] 3. The coating composition according to 2, wherein in the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the general formula (1) of the component (A), Y is independently a divalent group selected from -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR-, -OC(=O)NR- (R is an alkyl group having 1 to 4 carbon atoms or a phenyl group), a silylene group, a silylene group, and a linear, branched or cyclic divalent organo(poly)siloxane residue having 2 to 10 silicon atoms, and an alkylene group having 2 to 30 carbon atoms which may contain an arylene group having 6 to 20 carbon atoms.

[0034] 4. The coating composition according to 2 or 3, wherein in the (hydrolyzable) organosiloxane compound containing a lipophilic group represented by the general formula (1) of the component (A), W is independently selected from an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom, an oxime group, an isocyanate group, and a cyanate group.

[0035] 5. The coating composition according to any one of 1 to 4, wherein the component (A) is a (hydrolyzable) organosiloxane compound containing a lipophilic group and / or a partial (hydrolyzed) condensate thereof represented by the following general formula (2):

[0036] [Chemistry 2]

[0037]

[0038] (Where R 2is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, Q is a single bond, or a divalent group selected from a silylene group, a silylene group, and a linear, branched, or cyclic divalent organic (poly)siloxane residue having 2 to 10 silicon atoms, m is independently an integer of 1 to 20, and X is independently a hydroxyl group or a hydrolyzable group.

[0039] 6. The coating composition according to any one of 1 to 5, wherein the component (B) is a polyol ester composed of a condensate of a polyol selected from neopentyl glycol, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol and dipentaerythritol and a fatty acid having 3 to 22 carbon atoms.

[0040] 7. A surface treatment agent comprising the coating agent composition according to any one of 1 to 6.

[0041] 8. The surface treatment agent according to 7, further comprising a solvent.

[0042] 9. The surface treatment agent according to 7 or 8, further comprising a hydrolysis condensation catalyst.

[0043] 10. The surface treatment agent according to any one of 7 to 9, which provides a cured film having an oleic acid contact angle of 30° or less at 25° C. and a relative humidity of 40%.

[0044] 11. An article having a cured film of the surface treatment agent according to any one of 7 to 10 on its surface.

[0045] Effects of the Invention

[0046] The coating composition of the present invention contains a specific organic siloxane compound containing a lipophilic group and a silyl group (silanol group) or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof and a specific polyol ester in a specific ratio. When a fingerprint is attached, the cured film coated on the surface of the substrate using a surface treatment agent containing the composition can wet and spread the sebum contained in the fingerprint on the substrate. In addition, the coating composition contains a polyol ester with excellent lubricity, thereby reducing friction and providing a cured film with excellent wear resistance. Thus, the article having a cured film surface-treated with a surface treatment agent containing the coating composition has excellent lipophilicity and wear resistance. DETAILED DESCRIPTION

[0047] The coating composition of the present invention is characterized in that it contains: a specific lipophilic group-containing (hydrolyzable) organosiloxane compound containing a lipophilic group and a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof (hereinafter referred to as component (A)), and a specific polyol ester (hereinafter referred to as component (B)) as essential components, and the mass ratio of component (A) to component (B) is in the range of 0.1<(A) / (B)<10.

[0048] The present inventors have found that when a (hydrolyzable) organosiloxane compound containing a lipophilic group and / or a partial (hydrolyzed) condensate thereof as component (A) that exhibits adhesion to a substrate and a polyol ester as component (B) that exhibits surface lubricity are mixed in a specific ratio, the coating composition can form a cured film having excellent lipophilicity and abrasion resistance.

[0049] The first essential component (A) in the coating composition of the present invention is a component selected from the group consisting of (-C(=O)OR 1 ) represented by the formula (-OC(=O)R 1 ) represented by the formula (-C(=O)NR 1 2) A group represented by the formula (-C(=O)SR 1 ) and a group represented by the formula (-P(=O)(OR 1 The (hydrolyzable) organosiloxane compound containing a lipophilic group and a silanol group or a hydrolyzable silyl group in the group represented by )2) may be a partial (hydrolyzed) condensate thereof or a mixture of one or more thereof.

[0050] Among them, R 1 The alkyl group is independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. The alkyl group may be a linear, branched, or cyclic alkyl group, or a combination thereof. A linear alkyl group having 1 to 8 carbon atoms is preferred, and a linear alkyl group having 2 to 4 carbon atoms is more preferred.

[0051] As R 1 Specific examples include hydrogen atoms, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isopropyl, isobutyl, tert-butyl, neopentyl, tert-hexyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylmethyl, norbornyl, decahydronaphthyl, adamantyl, adamantylmethyl and other alkyl groups, phenyl, tolyl, naphthyl and other aryl groups, benzyl, phenylethyl, phenylpropyl and other aralkyl groups. 1 , preferably methyl, ethyl, butyl, octyl.

[0052] The lipophilic group-containing (hydrolyzable) organosiloxane compound of the component (A) is preferably represented by the following general formula (1).

[0053] [Chemistry 3]

[0054]

[0055] [wherein A is -C(=O)OR 1 、-OC(=O)R 1 、-C(=O)NR 1 2. -C(=O)SR 1 OR-P(=O)(OR 1 )2(R 1 independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms), Y independently a divalent organic group, W independently a alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group, or a hydrolyzable group, R independently a alkyl group having 1 to 4 carbon atoms or a phenyl group, X independently a hydroxyl group or a hydrolyzable group, n independently a integer of 1 to 3, and q independently a integer of 1 to 3.]

[0056] In the above formula (1), A is -C(=O)OR 1 、-OC(=O)R 1 The ester, carboxylic acid or aldehyde, -C(=O)NR 1 2, unsubstituted or substituted amide, -C(=O)SR 1 The thioester or thioacid shown, and -P(=O)(OR 1 ) Any of the phosphonate or phosphonic acid represented by 2 is the lipophilic terminal group in the present invention.

[0057] It should be noted that R 1 With the above R 1 The same groups can be exemplified, and preferably a methyl group, an ethyl group, a butyl group, and an octyl group.

[0058] As A, for example, the following groups can be exemplified.

[0059] [Chemistry 4]

[0060]

[0061] c4H9OOC- (C2H5)2NOC- (CH3O)2OP-

[0062] 8H 17 OOC-C8H 17 SOC- (C2H5O)2OP-

[0063] [Chemistry 5]

[0064]

[0065] In the above formula (1), W is an alkyl group having 1 to 4 carbon atoms which may be different from each other, a phenyl group, a hydroxyl group or a hydrolyzable group. Examples of such W include alkyl groups such as methyl, ethyl, propyl, and butyl groups, phenyl groups, hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups, alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy groups, acyloxy groups having 1 to 10 carbon atoms such as acetoxy groups, alkenyloxy groups having 2 to 10 carbon atoms such as isopropenyloxy groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, oxime groups, isocyanate groups, and cyanate groups. Among them, methyl, methoxy, ethoxy, isopropenyloxy, and chlorine atoms are preferred.

[0066] In the above formula (1), X may be different from each other and may be a hydroxyl group or a hydrolyzable group. Examples of such X include hydroxyl groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups and other alkoxy groups having 1 to 10 carbon atoms, methoxymethoxy groups, methoxyethoxy groups and other alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, acetoxy groups and other acyloxy groups, isopropenyloxy groups and other alkenyloxy groups having 2 to 10 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms and other halogen atoms, oxime groups, isocyanate groups, cyanate groups and the like. Among them, methoxy groups, ethoxy groups, isopropenyloxy groups and chlorine atoms are preferred.

[0067] In the above formula (1), R is independently an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or phenyl, and methyl is preferred.

[0068] In the above formula (1), Y is independently a divalent organic group, preferably a divalent group selected from -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR-, -OC(=O)NR- (R is the same as above), a silylene group, a silylene group, and a linear, branched or cyclic divalent organic (poly)siloxane residue having 2 to 10 silicon atoms, and an alkylene group having 2 to 30 carbon atoms, particularly 2 to 20 carbon atoms, which may include an arylene group having 6 to 20 carbon atoms, and more preferably a divalent group represented by the following formula (3).

[0069] [Chemistry 6]

[0070] -R 3 -Z-(R 3 ) a - (3)

[0071] In the above formula (3), R 3The independently divalent hydrocarbon group specifically includes alkylene groups having 1 to 30 carbon atoms such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene, decamethylene, and alkylene groups having 7 to 30 carbon atoms including arylene groups having 6 to 20 carbon atoms such as phenylene, and preferably alkylene groups having 2 to 20 carbon atoms.

[0072] In the above formula (3), Z is a single bond, or a divalent group selected from -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR-, -OC(=O)NR-, a silylene group, a silylene group, and a linear, branched or cyclic divalent organic (poly)siloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, and R is the same as above.

[0073] Among them, the following groups can be exemplified as the silanylene group and the silanylene group.

[0074] [Chemistry 7]

[0075]

[0076] (Where R 4 is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, or an aryl group having 6 to 10 carbon atoms, such as phenyl, 4 Can be the same or different. 5 It is an alkylene group having 1 to 12 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene, or an arylene group having 6 to 12 carbon atoms, such as phenylene.

[0077] Examples of the linear, branched or cyclic divalent organo(poly)siloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms include the following groups.

[0078] [Chemistry 8]

[0079]

[0080] (Where R 4 Same as above. g is an integer of 1 to 9, preferably 1 to 4, and h is an integer of 1 to 8, preferably 1 to 3.)

[0081] In the above formula (3), a is 0 or 1. When a is 1, R 3 The total number of carbon atoms of the alkylene group is preferably 2 to 30. When a is 0, Z is preferably a single bond.

[0082] Specific examples of Y include the following groups.

[0083] [Chemical Formula 9]

[0084] -CH2CH2-

[0085] -CH2CH2CH2-

[0086] -CH2CH2CH2CH2-

[0087] -CH2CH2CH2CH2CH2-

[0088] -CH2CH2CH2CH2CH2CH2-

[0089] -CH2CH2CH2CH2CH2CH2CH2-

[0090] -CH2CH2CH2CH2CH2CH2CH2CH2-

[0091] -CH2CH2CH2CH2CH2CH2CH2CH2CH2-

[0092] -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-

[0093] -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-

[0094]

[0095] [Chemical Formula 10]

[0096] -CH2CH2-O-CH2CH2-

[0097] -(CH2) 10 -O-CH2CH2-

[0098]

[0099] -CH2CH2-S-CH2CH2-

[0100]

[0101] [Chemical Formula 11]

[0102]

[0103] [Chemical Formula 12]

[0104]

[0105] [Chemical Formula 13]

[0106]

[0107] In the above formula (1), n ​​is an integer of 1 to 3, and q is an integer of 1 to 3. Preferably, n is 2 or 3, and q is 2 or 3. More preferably, n is 3, and q is 3.

[0108] Examples of the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1) include compounds represented by the following formulas.

[0109] [Chemistry 14]

[0110]

[0111] [Chemistry 15]

[0112]

[0113] [Chemistry 16]

[0114]

[0115] [Chemistry 17]

[0116]

[0117] [Chemistry 18]

[0118]

[0119] [Chemistry 19]

[0120]

[0121] [Chemistry 20]

[0122]

[0123] [Chemistry 21]

[0124]

[0125] [Chemistry 22]

[0126]

[0127] [Chemistry 23]

[0128]

[0129] The lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1) is more preferably represented by the following general formula (2).

[0130] [Chemistry 24]

[0131]

[0132] (Where R 2 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, Q is a single bond, or a divalent group selected from a silylene group, a silylene group, and a linear, branched or cyclic divalent organic (poly)siloxane residue having 2 to 10 silicon atoms, m is independently an integer of 1 to 20, preferably an integer of 2 to 10, and X is the same as above.)

[0133] In the above formula (2), R 2 It is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and is preferably a linear alkyl group having 1 to 8 carbon atoms.

[0134] As R 2 Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isopropyl, isobutyl, tert-butyl, neopentyl, texyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylmethyl, norbornyl, decahydronaphthyl, adamantyl, and adamantylmethyl; aryl groups such as phenyl, tolyl, and naphthyl; and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl. 2 , preferably methyl, ethyl, butyl, octyl.

[0135] In the above formula (2), Q is a single bond or a divalent group selected from silanylene groups, silanylene groups, and linear, branched or cyclic divalent organo(poly)siloxane residues having 2 to 10, preferably 2 to 5 silicon atoms.

[0136] Among them, as for the silanylene group, silanylene group, and a linear, branched or cyclic divalent organo(poly)siloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, there can be exemplified the same groups as exemplified as the silanylene group, silanylene group, or a linear, branched or cyclic divalent organo(poly)siloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms in Z of the above-mentioned formula (3).

[0137] m is independently an integer of 1 to 20, preferably 2 to 10. When Q is a single bond, the total of two m's present on both sides of Q is preferably an integer of 2 to 20, particularly preferably 2 to 10.

[0138] Examples of the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (2) include compounds represented by the following formulas.

[0139] [Chemistry 25]

[0140]

[0141] [Chemistry 26]

[0142]

[0143] [Chemistry 27]

[0144]

[0145] [Chemistry 28]

[0146]

[0147] [Chemistry 29]

[0148]

[0149] Examples of methods for producing the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1), particularly the lipophilic group-containing hydrolyzable organosiloxane compound wherein R is a methyl group, include the following methods.

[0150] A siloxane compound (organohydrogensiloxane compound) having A in the above formula (1) and a plurality of SiH groups (hydrogen atoms bonded to silicon atoms) at the molecular chain ends is heated and stirred at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C., and a hydrosilylation reaction catalyst, such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, is added. Then, a silane compound having a hydrolyzable silyl group and an olefin moiety (such as an alkenyl group) at the molecular chain ends is dropped, and the mixture is aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 10 minutes to 12 hours, preferably 1 to 6 hours, more preferably about 3 hours. In addition, the reaction may be diluted with an organic solvent.

[0151] Among them, examples of the siloxane compound (organohydrogensiloxane compound) having A in the above formula (1) and a plurality of SiH groups at the molecular chain ends thereof include siloxane compounds represented by the following general formula (4).

[0152] [Chemistry 30]

[0153]

[0154] (Wherein, A, Y, W, and q are the same as above.)

[0155] Specific examples of the siloxane compound represented by the formula (4) include organohydrogensiloxane compounds represented by the following general formulae (a) to (h).

[0156] [Chemistry 31]

[0157]

[0158] [Chemistry 32]

[0159]

[0160] [Chemistry 33]

[0161]

[0162] [Chemistry 34]

[0163]

[0164] [Chemistry 35]

[0165]

[0166] [Chemistry 36]

[0167]

[0168] [Chemistry 37]

[0169]

[0170] [Chemistry 38]

[0171]

[0172] (Where R 2 , W, m, q are the same as above. m' is an integer of 2 to 20, preferably 2 to 10, and Q' is a divalent group selected from silylene, silylene, and a linear, branched or cyclic divalent organic (poly)siloxane residue having 2 to 10 silicon atoms.

[0173] Specific examples of the organohydrogensiloxane compound represented by the formula (a) include the following compounds.

[0174] [Chemistry 39]

[0175]

[0176] [Chemistry 40]

[0177]

[0178] [Chemistry 41]

[0179]

[0180] Specific examples of the organohydrogensiloxane compound represented by the formula (b) include the following compounds.

[0181] [Chemistry 42]

[0182]

[0183] [Chemistry 43]

[0184]

[0185] [Chemistry 44]

[0186]

[0187] Specific examples of the organohydrogensiloxane compound represented by the formula (c) include the following compounds.

[0188] [Chemistry 45]

[0189]

[0190] [Chemistry 46]

[0191]

[0192] Specific examples of the organohydrogensiloxane compound represented by the formula (d) include the following compounds.

[0193] [Chemistry 47]

[0194]

[0195] [Chemistry 48]

[0196]

[0197] [Chemistry 49]

[0198]

[0199] Specific examples of the organohydrogensiloxane compound represented by the formula (e) include the following compounds.

[0200] [Chemistry 50]

[0201]

[0202] [Chemistry 51]

[0203]

[0204] Specific examples of the organohydrogensiloxane compound represented by the formula (f) include the following compounds.

[0205] [Chemistry 52]

[0206]

[0207] [Chemistry 53]

[0208]

[0209] [Chemistry 54]

[0210]

[0211] Specific examples of the organohydrogensiloxane compound represented by the formula (g) include the following compounds.

[0212] [Chemistry 55]

[0213]

[0214] [Chemistry 56]

[0215]

[0216] Specific examples of the organohydrogensiloxane compound represented by the formula (h) include the following compounds.

[0217] [Chemistry 57]

[0218]

[0219] [Chemistry 58]

[0220]

[0221] [Chemistry 59]

[0222]

[0223] As a method for preparing the organohydrogensiloxane compound represented by the above formula (4), especially the formulas (a) to (h), a silane or siloxane compound having A in the above formula (1) and a hydrolyzable silyl group at the molecular chain end is stirred at a temperature of -20 to 40°C, preferably -10 to 20°C, and more preferably 0 to 10°C, and a tetramethyldisiloxane (1,3-dihydro-1,1,3,3-tetramethyldisiloxane) or other tetraorganodisiloxane (1,3-dihydro-1,1,3,3-tetraorganodisiloxane) and a co-hydrolysis reaction catalyst such as hydrochloric acid or sulfuric acid are added dropwise, and the mixture is aged at a temperature of -20 to 40°C, preferably -10 to 20°C, and more preferably 0 to 10°C for 10 minutes to 12 hours, preferably 1 to 6 hours. In addition, an organic solvent may be used for dilution during the reaction.

[0224] Among them, examples of the silane or siloxane compound having A in the above formula (1) and a hydrolyzable silyl group at the molecular chain end include silane or siloxane compounds represented by the following general formula (5).

[0225] [Chemistry 60]

[0226]

[0227] (Wherein, A, Y, W, and q are the same as above.)

[0228] Specific examples of the silane or siloxane compound represented by formula (5) include the following compounds.

[0229] [Chemistry 61]

[0230] C2H5-OOC-(CH2)4-Si(OCH3)3

[0231] C2H5-OOC-(CH2) 10 -Si(OCH3)3

[0232] C2H5-OOC-(CH2) 13 -Si(OCH3)3

[0233] [Chemistry 62]

[0234] CH3-OOC-(CH2) 10 -Si(OCH3)3

[0235] C4H9-OOC-(CH2) 10 -Si(OCH3)3

[0236]

[0237] [Chemistry 63]

[0238]

[0239] [Chemistry 64]

[0240]

[0241] [Chemistry 65]

[0242]

[0243] [Chemistry 66]

[0244] (C2H5)2-NOC-(CH2)4-Si(OCH3)3

[0245] (C2H5)2-NOC-(CH2) 10 -Si(OCH3)3

[0246] (C4H9)2-NOC-(CH2) 10 -Si(OCH3)3

[0247] [Chemistry 67]

[0248]

[0249] [Chemistry 68]

[0250]

[0251] [Chemistry 69]

[0252]

[0253] [Chemistry 70]

[0254] CH3-SOC-(CH2) 10 -Si(OCH3)3

[0255] C2H5-SOC-(CH2)4-Si(OCH3)3

[0256] C2H5-SOC-(CH2) 10 -Si(OCH3)3

[0257] C4H9-SOC-(CH2) 10 -Si(OCH3)3

[0258]

[0259] [Chemistry 71]

[0260]

[0261] [Chemistry 72]

[0262]

[0263] [Chemistry 73]

[0264]

[0265] [Chemistry 74]

[0266] (CH3O)2OP-(CH2)4-Si(OCH3)3

[0267] (CH3O)2OP-(CH2) 10 -Si(OCH3)3

[0268] (C2H5O)2OP-(CH2) 10 -Si(OCH3)3

[0269] [Chemistry 75]

[0270]

[0271] [Chemistry 76]

[0272]

[0273] [Chemistry 77]

[0274]

[0275] [Chemistry 78]

[0276]

[0277] [Chemistry 79]

[0278]

[0279] [Chemistry 80]

[0280]

[0281] [Chemistry 81]

[0282]

[0283] As a method for preparing a silane or siloxane compound represented by formula (5) having A in the above formula (1) and a hydrolyzable silyl group at the molecular chain end, in particular, a silane or siloxane compound in which Y in formula (5) is an alkylene group containing a divalent group selected from a silylene group, a silylene group, and a linear, branched or cyclic divalent organic (poly)siloxane residue having 2 to 10 silicon atoms, a compound having two SiH groups at the molecular chain end, for example, 1,4-bis(dimethylsilyl)benzene, is heated and stirred at a temperature of 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C., and a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex is added. Next, a compound having A in the above formula (1) and an olefin part (e.g., alkenyl) at the molecular chain end is slowly dripped over a period of time, and aged at a temperature of 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 10 minutes to 12 hours, preferably 1 to 6 hours, thereby obtaining a silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain end. In addition, the reaction may be diluted with an organic solvent.

[0284] Next, the silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain terminal is heated and stirred at a temperature of 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C., and a hydrosilylation reaction catalyst, such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, is added. Next, a silane compound having a hydrolyzable silyl group and an olefin moiety (such as an alkenyl group) at the molecular chain terminal is dropped, and the mixture is aged at a temperature of 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 10 minutes to 12 hours, preferably 1 to 6 hours, more preferably 3 to 6 hours. In addition, the reaction may be diluted with an organic solvent.

[0285] Among them, specific examples of the compound having two SiH groups at the molecular chain terminals include the following compounds.

[0286] [Chemistry 82]

[0287]

[0288] In addition, specific examples of the compound having A in the above formula (1) and an olefin site at the molecular chain end include the following compounds.

[0289] [Chemistry 83]

[0290] C2H5OOC-(CH2)2-CH=CH2

[0291] C2H5OOC-(CH2)8-CH=CH2

[0292] C2H5OOC-(CH2) 11 -CH=CH2

[0293] H3COOC-(CH2)8-CH=CH2

[0294] C4H9OOC-(CH2)8-CH=CH2

[0295] 8H 17 OOC-(CH2)8-CH=CH2

[0296]

[0297] [Chemistry 84]

[0298] (C2H5)2NOC-(CH2)2-CH=CH2

[0299] (C2H s )2NOC-(CH2)8-CH=CH2

[0300] (C4H9)2NOC-(CH2)2-CH=CH2

[0301] (C4H9)2NOC-(CH2)8-CH=CH2

[0302] C2H5SOC-(CH2)2-CH=CH2

[0303] C2H s SOC-(CH2)8-CH=CH2

[0304] C4H g SOC-(CH2)2-CH=CH2

[0305] C4H9SOC-(CH2)8-CH=CH2

[0306]

[0307] (CH3O)2OP-(CH2)2-CH=CH2

[0308] (CH3O)2OP-(CH2)8-CH=CH2

[0309] (C2H5O)2OP-(CH2)2-CH=CH2

[0310] (C2H5O)2OP-(CH2)8-CH=CH2

[0311] The amount of the compound having A in the above formula (1) and an olefin moiety at the molecular chain ends is 0.05 to 0.5 equivalents, more preferably 0.1 to 0.4 equivalents, and even more preferably 0.2 equivalents, relative to 1 equivalent of the compound having two SiH groups at the molecular chain ends.

[0312] In the preparation of the silane or siloxane compound represented by the above formula (5), examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0313] The amount of the hydrosilylation reaction catalyst used in the reaction of the compound having two SiH groups at the molecular chain ends and the compound having A in the above formula (1) and an olefin portion at the molecular chain ends is 0.1 to 100 ppm, more preferably 0.2 to 50 ppm, in terms of transition metal conversion (mass), relative to the total mass of the compound having two SiH groups at the molecular chain ends and the compound having A in the above formula (1) and an olefin portion at the molecular chain ends.

[0314] In the preparation of the silane or siloxane compound represented by the above formula (5), an organic solvent can be used. As the organic solvent used, ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, etc.) and hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.) can be exemplified. Among these, toluene is particularly preferred.

[0315] The amount of the organic solvent used in the reaction of the compound having two SiH groups at the ends of the molecular chain and the compound having A in the above formula (1) and an olefin portion at the ends of the molecular chain, respectively, can be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, relative to 100 parts by mass of the compound having A in the above formula (1) and an olefin portion at the ends of the molecular chain, respectively.

[0316] Next, the reaction is terminated and the organic solvent is distilled off to obtain a silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain terminal.

[0317] In the preparation of the silane or siloxane compound represented by the above formula (5), specific examples of the silane compound having a hydrolyzable silyl group and an olefin moiety (eg, alkenyl group) at the molecular chain end include the following compounds.

[0318] [Chemistry 85]

[0319] CH2=CH-Si(OCH3)3

[0320] CH2=CH-CH2-Si(OCH3)3

[0321] CH2=CH-(CH2)4-Si(OCH3)3

[0322] CH2=CH-(CH2)6-Si(OCH3)3

[0323]

[0324] The amount of the silane compound having a hydrolyzable silyl group and an olefin moiety at the molecular chain terminal can be 1 to 5 equivalents, more preferably 1.1 to 2.5 equivalents, based on 1 equivalent of the silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain terminal obtained above.

[0325] In the preparation of the silane or siloxane compound represented by the above formula (5), as the hydrosilylation reaction catalyst used in the reaction of the silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain terminal obtained above and the silane compound having a hydrolyzable silyl group and an olefin moiety at the molecular chain terminal, the same catalyst as mentioned above can be exemplified, and the amount of the hydrosilylation reaction catalyst used is 0.1 to 100 ppm, more preferably 0.2 to 50 ppm, relative to the total mass of the silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain terminal and the silane compound having a hydrolyzable silyl group and an olefin moiety at the molecular chain terminal, calculated as transition metal (mass).

[0326] In the preparation of the silane or siloxane compound represented by the above formula (5), when an organic solvent is used in the reaction of the silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain end obtained above and the silane compound having a hydrolyzable silyl group and an olefin moiety at the molecular chain end, as the organic solvent, the same organic solvents as mentioned above can be exemplified, and the amount of the organic solvent used can be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, relative to 100 parts by mass of the silane or siloxane compound having A in the above formula (1) and a terminal SiH group at the molecular chain end obtained above.

[0327] Next, by stopping the reaction and distilling off the organic solvent and unreacted components, a silane or siloxane compound represented by the above formula (5) can be obtained, particularly a silane or siloxane compound in which Y in the formula (5) is an alkylene group containing a divalent group selected from a silylene group, a silylene group, and a linear, branched or cyclic divalent organic (poly)siloxane residue having 2 to 10 silicon atoms.

[0328] In addition, as a method for preparing a silane or siloxane compound represented by formula (5) having A in the above formula (1) and a hydrolyzable silyl group at the end of the molecular chain, in particular, a silane or siloxane compound in which Y in formula (5) is an alkylene group, the above-mentioned compound having A in the above formula (1) and an olefin portion (e.g., alkenyl) at the end of the molecular chain is heated and stirred at a temperature of 40 to 120° C., preferably 60 to 100° C., and more preferably about 80° C., and a hydrosilylation reaction catalyst, such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, is added. Next, a silane compound having a hydrolyzable silyl group and a SiH group at the molecular chain end is slowly added dropwise over a period of time, and aged at a temperature of 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 10 minutes to 12 hours, preferably 1 to 6 hours, more preferably 1 to 3 hours, thereby obtaining a silane or siloxane compound having A in the above formula (1) and a hydrolyzable silyl group, particularly a silane or siloxane compound in which Y in the formula (5) is an alkylene group. In addition, the reaction may be diluted with an organic solvent.

[0329] Among them, specific examples of the silane compound having a hydrolyzable silyl group and a SiH group at the molecular chain terminal include the following compounds.

[0330] [Chemistry 86]

[0331] H-Si(OCH3)3

[0332]

[0333]

[0334] The amount of the compound having A in the above formula (1) and an olefin moiety (e.g., alkenyl) at the molecular chain end is 0.2 to 1 equivalent, more preferably 0.4 to 1 equivalent, per 1 equivalent of the silane compound having a hydrolyzable silyl group and a SiH group at the molecular chain end.

[0335] In the preparation of a silane or siloxane compound in which Y in the above formula (5) is an alkylene group, the same compounds as mentioned above can be exemplified as hydrosilylation reaction catalysts, and the amount of the hydrosilylation reaction catalyst used is 0.1 to 100 ppm, more preferably 0.2 to 50 ppm, in terms of transition metal conversion (mass), relative to the total mass of the compound having A in the above formula (1) and an olefin portion at the molecular chain end and the silane compound having a hydrolyzable silyl group and a SiH group at the molecular chain end.

[0336] In the preparation of a silane or siloxane compound in which Y in the above formula (5) is an alkylene group, when an organic solvent is used, the same organic solvent as mentioned above can be exemplified as the organic solvent, and the amount of the organic solvent used can be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, relative to 100 parts by mass of the compound having A in the above formula (1) and an olefin portion at the end of the molecular chain.

[0337] In the preparation of the organohydrogensiloxane compounds represented by the above formula (4), especially formulas (a) to (h), the amount of the silane or siloxane compound represented by formula (5) having A in the above formula (1) and a hydrolyzable silyl group at the end of the molecular chain can be 0.2 to 0.6 equivalents, more preferably 0.3 to 0.5 equivalents, and even more preferably 0.4 to 0.5 equivalents, relative to 1 equivalent of tetraorganodisiloxane.

[0338] In the preparation of the organohydrogensiloxane compounds represented by the above formula (4), especially formulas (a) to (h), examples of the co-hydrolysis reaction catalyst include organotin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organotitanium compounds (tetra-n-butyl titanate, etc.), organic acids (acetic acid, methanesulfonic acid, etc.), and inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.). Among these, hydrochloric acid and sulfuric acid are preferred.

[0339] The amount of the co-hydrolysis catalyst used is 1 to 5 equivalents, more preferably 2 to 4 equivalents, and even more preferably 2 to 3 equivalents, per 1 equivalent of the silane or siloxane compound having A in the above formula (1) and a hydrolyzable silyl group at the molecular chain end.

[0340] An organic solvent may be used in the preparation of the organohydrogensiloxane compound represented by the above formula (4), especially formulas (a) to (h). Examples of the organic solvent used include ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, etc.), hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.), and fluorine solvents (perfluorohexane, 1,4-bis(trifluoromethyl)benzene, etc.). Among these, toluene and 1,4-bis(trifluoromethyl)benzene are particularly preferred.

[0341] The organic solvent can be used in an amount of 10 to 300 parts by mass, preferably 50 to 150 parts by mass, based on 100 parts by mass of the silane or siloxane compound having A in the formula (1) and a hydrolyzable silyl group at a molecular chain end.

[0342] Next, the reaction is stopped and the organic solvent is distilled off to obtain the organohydrogensiloxane compound represented by the above formula (4), particularly formulas (a) to (h).

[0343] In the preparation of the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by formula (1), specific examples of the silane compound having a hydrolyzable silyl group and an olefin moiety (eg, alkenyl group) at the molecular chain ends include the following compounds.

[0344] [Chemistry 87]

[0345] CH2=CH-Si(OCH3)3

[0346] CH2=CH-CH2-Si(OCH3)3

[0347] CH2=CH-(CH2)4-Si(OCH3)3

[0348] CH2=CH-(CH2)6-Si(OCH3)3

[0349]

[0350] The amount of the silane compound having a hydrolyzable silyl group and an olefin moiety at the ends of the molecular chain can be 3 to 5 equivalents, more preferably 3.5 to 4.5 equivalents, and even more preferably 4.0 to 4.3 equivalents, relative to 1 equivalent of the organohydrogensiloxane compound having A in the above formula (1) and a plurality of SiH groups at the ends of the molecular chain.

[0351] In the preparation of the (hydrolyzable) organosiloxane compound containing a lipophilic group represented by the above formula (1), examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0352] The amount of the hydrosilylation reaction catalyst used is 0.1 to 100 ppm, more preferably 0.2 to 50 ppm, in terms of transition metal conversion (mass) relative to the total mass of the organohydrogensiloxane compound having A in the above formula (1) and a plurality of SiH groups at the molecular chain ends and the silane compound having a hydrolyzable silyl group and an olefin moiety at the molecular chain ends.

[0353] An organic solvent may be used in the preparation of the (hydrolyzable) organosiloxane compound containing a lipophilic group represented by the above formula (1). Examples of the organic solvent include ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, etc.) and hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.). Among these, toluene is particularly preferred.

[0354] The organic solvent can be used in an amount of 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, based on 100 parts by mass of the organohydrogensiloxane compound having A in the formula (1) and a plurality of SiH groups at molecular chain ends.

[0355] Next, the reaction is terminated and the organic solvent and unreacted components are distilled off to obtain the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1).

[0356] For example, as the organohydrogensiloxane compound having A in the above formula (1) and a plurality of SiH groups at the molecular chain ends, a compound represented by the following formula is used:

[0357] [Chemistry 88]

[0358]

[0359] As the silane compound having a hydrolyzable silyl group and an olefin moiety at the molecular chain end, a compound represented by the following formula is used:

[0360] [Chemistry 89]

[0361] CH2=CH-(CH2)6-Si(OCH3)3

[0362] In the case of , a siloxane compound represented by the following formula is obtained.

[0363] [Chemistry 90]

[0364]

[0365] The (hydrolyzable) organosiloxane compound containing a lipophilic group represented by the general formula (1) obtained by the above reaction can be purified and isolated by concentration, column purification, distillation, extraction or the like. Alternatively, the reaction solution can be used as a mixture containing the (hydrolyzable) organosiloxane compound containing a lipophilic group represented by the general formula (1) as it is, or can be further diluted with an organic solvent or the like.

[0366] The component (A) may include a partial (hydrolyzed) condensate obtained by condensing hydroxyl groups of the lipophilic group-containing (hydrolyzable) organosiloxane compound represented by the above formula (1) or hydroxyl groups of the terminal hydrolyzable groups of the siloxane compound partially hydrolyzed in advance by a known method.

[0367] The polyol ester as the component (B) which is the second essential component in the coating composition of the present invention is composed of a condensate of a di- to hexavalent alcohol and a saturated or unsaturated fatty acid having 3 to 22 carbon atoms, and may be one kind or a mixture of two or more kinds.

[0368] Preferred examples of the divalent to hexavalent alcohol include polyols such as neopentyl glycol, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, and dipentaerythritol. Polyol esters composed of condensates of such polyols and fatty acids having 3 to 22 carbon atoms are excellent in terms of availability and lubricity.

[0369] Preferred examples of the saturated fatty acid or unsaturated fatty acid having 3 to 22 carbon atoms, preferably 6 to 18 carbon atoms, include propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, etc. Polyol esters composed of condensates of such saturated fatty acids or unsaturated fatty acids having 3 to 22 carbon atoms and polyols are excellent in terms of availability and lubricity.

[0370] Specific preferred examples of the component (B) include neopentyl glycol di(2-ethylhexanoate), neopentyl glycol di(oleate), neopentyl glycol di(stearate), trimethylolethane tri(2-ethylhexanoate), trimethylolethane tri(oleate), trimethylolethane tri(stearate), trimethylolpropane tri(2-ethylhexanoate), trimethylolpropane tri(oleate), trimethylolpropane tri(stearate), glycerol tri(2-ethylhexanoate), glycerol tri(oleate), glycerol tri(stearate), pentaerythritol tetra(2-ethylhexanoate), pentaerythritol tetra(oleate), pentaerythritol tetra(stearate), dipentaerythritol hexa(2-ethylhexanoate), dipentaerythritol hexa(oleate), and dipentaerythritol hexa(stearate).

[0371] The component (B) may be a single compound or a mixture of a plurality of compounds meeting the above definition. In the case of a mixture, the total content of the compounds corresponding to the component (B) may be calculated as the content of the component (B). The compound corresponding to the component (B) may be synthesized by a known method as required, and various products may be sold from reagent manufacturers, etc., or may be used directly.

[0372] The coating composition of the present invention contains the above-mentioned component (A) and the above-mentioned component (B) in a predetermined ratio, that is, the mass ratio of the component (A) to the component (B) is within the range of 0.1<(A) / (B)<10, preferably 0.5<(A) / (B)<10, and more preferably 1≦(A) / (B)≦9. If the amount of the component (A) that ensures adhesion to the substrate is too small, the wear resistance is reduced, and if the amount of the component (B) that ensures lubricity is too small, a sufficient effect of improving the wear resistance cannot be obtained.

[0373] The present invention also provides a surface treating agent comprising the above coating agent composition.

[0374] The surface treatment agent may contain an appropriate solvent. Examples of such solvents include alcohol solvents (propylene glycol monomethyl ether, butanol, isopropyl alcohol, etc.), ether solvents (dibutyl ether, ethyl ether, tetrahydrofuran, etc.), hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, alcohol solvents and ether solvents are preferred in terms of solubility, wettability, etc., and propylene glycol monomethyl ether and dibutyl ether are particularly preferred.

[0375] The above-mentioned solvent may be mixed with two or more thereof, and it is preferred that the above-mentioned components (A) and (B) are uniformly dissolved. The optimal concentration of the total mass of the components (A) and (B) dissolved in the solvent varies depending on the treatment method, and any amount that can be easily weighed will suffice. In the case of direct coating, it is preferably 0.01 to 10 parts by mass (0.01 to 10% by mass), and particularly preferably 0.05 to 5 parts by mass (0.05 to 5% by mass), in 100 parts by mass of the mixture of the solvent and the components (A) and (B) (surface treatment agent). In the case of vapor deposition treatment, it is preferably 0.01 to 10 parts by mass (0.01 to 10% by mass), and particularly preferably 0.05 to 5 parts by mass (0.05 to 5% by mass), in 100 parts by mass of the mixture of the solvent and the components (A) and (B). In the case of wet treatment, the amount of the solvent and the mixture of components (A) and (B) (surface treatment agent) is preferably 0.01 to 10 parts by mass (0.01 to 10 parts by mass), and particularly preferably 0.05 to 1 part by mass (0.05 to 1 part by mass).

[0376] The surface treatment agent may be added with a hydrolysis condensation catalyst, such as an organic tin compound (dimethoxydibutyltin, dibutyltin dilaurate, etc.), an organic titanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, etc.). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, etc. are particularly preferred.

[0377] The amount of the hydrolysis condensation catalyst added is preferably 0.1 to 150 parts by mass, particularly preferably 25 to 125 parts by mass, and further preferably 50 to 110 parts by mass based on 100 parts by mass of the mixture of components (A) and (B) (surface treatment agent).

[0378] The surface treatment agent of the present invention can be applied to the substrate by known methods such as brush coating, dipping, spraying, and evaporation treatment. The heating method during the evaporation treatment can be either a resistance heating method or an electron beam heating method, and is not particularly limited. In addition, the curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferably 25 to 200°C, especially 25 to 150°C for 15 minutes to 36 hours, especially 30 minutes to 24 hours. It can be cured under humidification. In addition, in the case of application by evaporation treatment, the range of 20 to 200°C is preferred. It can be cured under humidification. The film thickness of the cured film is appropriately selected according to the type of substrate, usually 0.1 to 100 nm, especially 1 to 20 nm. In addition, for example, in spraying, it is diluted in an organic solvent to which water has been added in advance, hydrolyzed, that is, Si-OH is generated, and then sprayed, and the curing after coating is fast.

[0379] The surface treatment agent of the present invention can form a cured film having a contact angle of preferably 30° or less, more preferably 25° or less, to oleic acid at 25°C and a relative humidity of 40%, as measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.). Therefore, when sebum adheres, the contact angle is small, visibility is reduced, and fingerprints are not noticeable.

[0380] The surface treatment agent of the present invention can form a cured film having excellent wear resistance, which does not cause visually observable damage to the substrate when abraded with steel wool.

[0381] The substrate to be processed with the surface treatment agent of the present invention is not particularly limited, and can be a substrate of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc. The surface treatment agent of the present invention can give water and oil repellency to the above-mentioned substrate. Especially, it can be suitable as the surface treatment agent of SiO2 processed glass and film.

[0382] Articles treated with the surface treatment agent of the present invention include car navigation, mobile phones, smart phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical devices such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films and other optical articles. The cured film formed by the surface treatment agent of the present invention is difficult to be seen even if fingerprints and sebum adhere to the above-mentioned articles, and can be used as an oleophilic layer of touch panel displays, anti-reflection films, etc.

[0383] Example

[0384] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

[0385] [Synthesis example 1]

[0386] 10.0 g (4.71 × 10 -2 mol) was heated to 80°C. Then, 1.0×10 -2 g (calculated as Pt single substance, containing 0.3×10 -7 mol), 8.6 g (7.06 × 10 -2 mol), heated and stirred at 80°C for 1 hour. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (A):

[0387] [Chemistry 91]

[0388] C2H5-OOC-(CH2) 10 -Si(OCH3)3 (A)

[0389] The expressed compound was 12.1 g.

[0390] 1 H-NMR

[0391] δ0.8(-(CH2)7C H2 -Si(OCH3)3)2H

[0392] δ1.2-1.4(-(C H2 )7-,-OCH2C H3 )17H

[0393] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0394] δ2.3(-OOC-C H2 -)2H

[0395] δ3.5(-Si(OC H3 )3)9H

[0396] δ4.1(-OC H2 CH3)2H

[0397] 4.5 g (3.4 × 10 -2 mol), 3.6 g of 12N hydrochloric acid aqueous solution, and 2.5 g of 1,4-bis(trifluoromethyl)benzene were cooled to 0°C. Then, the above-obtained

[0398] [Chemistry 92]

[0399] C2H5-OOC-(CH2) 10 -Si(OCH3)3 (A)

[0400] The compound represented by 5.0g (1.5×10 -2 mol), and aged at 0°C for 6 hours. Then, the lower layer was recovered by liquid separation operation, and the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (B):

[0401] [Chemistry 93]

[0402]

[0403] The product weight was 5.8 g.

[0404] 1 H-NMR

[0405] δ0.1-0.2(-Si-C H3 )18H

[0406] δ0.5(-(CH2)7C H2 -Si(O-Si(CH3)2-)3)2H

[0407] δ1.2-1.5(-(C H2 )7-,-OCH2C H3 )17H

[0408] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0409] δ2.3(-OOC-C H2 -)2H

[0410] δ4.1(-OC H2 CH3)2H

[0411] δ4.7(-Si-H)3H

[0412] The above-obtained compound represented by the following formula (B) is placed in a reaction container.

[0413] [Chemistry 94]

[0414]

[0415] The compound represented by 5.0g (1.1×10 -2 mol) was heated to 80°C. Then, 5.0×10-3 g (calculated as Pt single substance, containing 1.5×10 -8 mol), then 7.3 g (4.5 × 10 -2 mol), and heated and stirred at 80°C for 3 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (C):

[0416] [Chemistry 95]

[0417]

[0418] The amount of the product (hydrolyzable organosiloxane compound 1 containing a lipophilic group) was 8.8 g.

[0419] 1 H-NMR

[0420] δ0.1-0.2(-Si-C H3 )18H

[0421] δ0.5(-(CH2)7C H2 -Si(O-Si(CH3)2-)3)2H

[0422] δ0.6-0.8(-SiCH2CH2C H2 -Si(OCH3)3, -SiC H2 CH2CH2-Si(OCH3)3)12H

[0423] δ1.2-1.4(-(C H2 )7-,-OCH2C H3 )17H

[0424] δ1.5(-SiCH2C H2 CH2-Si(OCH3)3)6H

[0425] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0426] δ2.3(-OOC-C H2 -)2H

[0427] δ3.5(-SiCH2CH2CH2-Si(OC H3 )3)27H

[0428] δ4.1(-OC H2 CH3)2H

[0429] [Synthesis example 2]

[0430] 10.0 g (4.34 × 10 -2 mol) was heated to 80°C. Then, 1.0×10 -2 g (calculated as Pt single substance, containing 0.3×10 -7 mol), 1.9 g (8.95 × 10 -3 mol), heated and stirred at 80°C for 1 hour. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (D):

[0431] [Chemistry 96]

[0432]

[0433] The product represented was 4.1 g.

[0434] 1 H-NMR

[0435] δ0.2-0.4(-Si-C H3 )12H

[0436] δ0.7(-C H2 -Si-)6H

[0437] δ1.2-1.5(-(C H2 )7-,-(C H2 )6-,-OCH2C H3 )29H

[0438] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0439] δ2.3(-OOC-C H2 -)2H

[0440] δ4.1(-OC H2 CH3)2H

[0441] δ4.4(-Si-H)1H

[0442] The above-obtained compound represented by the following formula (D) is placed in a reaction container.

[0443] [Chemistry 97]

[0444]

[0445] The compound represented by 4.0 g (9.03 × 10 -3mol) was heated to 80°C. Then, 1.0×10 -2 g (calculated as Pt single substance, containing 0.3×10 -7 mol), 2.9 g (1.26 × 10 -2 mol), heated and stirred at 80°C for 3 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (E):

[0446] [Chemistry 98]

[0447]

[0448] The represented compound was 5.0 g.

[0449] 1 H-NMR

[0450] δ0.2(-Si-C H3 )12H

[0451] δ0.6(-C H2 -Si-)10H

[0452] δ0.7(-C H2 -Si(OCH3)3)2H

[0453] δ1.2-1.4(-(C H2 )7-,-(C H2 )6-,-OCH2C H3 )41H

[0454] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0455] δ2.3(-OOC-C H2 -)2H

[0456] δ3.5(-SiCH2(CH2)6CH2-Si(OC H3 )3)9H

[0457] δ4.1(-OC H2 CH3)2H

[0458] 1.8 g (1.36 × 10 -2 mol), 1.5 g of 12N hydrochloric acid aqueous solution, and 5.0 g of 1,4-bis(trifluoromethyl)benzene were cooled to 0°C. Then, the above-obtained

[0459] [Chemistry 99]

[0460]

[0461] The compound represented by 4.0g (5.92×10 -3 mol), and aged at 0°C for 6 hours. Then, the lower layer was recovered by liquid separation operation, and the solvent and unreacted products were removed by reduced pressure distillation to obtain the following formula (F):

[0462] [Chemical 100]

[0463]

[0464] The product represented was 3.3 g.

[0465] 1 H-NMR

[0466] δ0.1-0.2(-Si-C H3 )30H

[0467] δ0.5(-(CH2)7C H2 -Si(O-Si(CH3)2-)3)2H

[0468] δ0.7-0.8(-Si-C H2 -)8H

[0469] δ1.2-1.5(-(C H2 )7-,-OCH2C H3 , -Si-CH2(C H2 )6CH2-Si-)41H

[0470] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0471] δ2.3(-OOC-C H2 -)2H

[0472] δ4.1(-OC H2 CH3)2H

[0473] δ4.7(-Si-H)3H

[0474] The above-obtained compound of the following formula (F) is placed in a reaction container.

[0475] [Chemistry 101]

[0476]

[0477] The compound represented by 2.0 g (2.48 × 10 -3mol) was heated to 80°C. Then, 5.0×10 -3 g (calculated as Pt single substance, containing 1.5×10 -8 mol), 2.4 g (1.04 × 10 -2 mol), heated and stirred at 80°C for 3 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (G):

[0478] [Chemistry 102]

[0479]

[0480] The product (hydrolyzable organosiloxane compound 2 containing a lipophilic group) was 3.8 g.

[0481] 1 H-NMR

[0482] δ0.1-0.2(-Si-C H3 )30H

[0483] δ0.5(-(CH2)7C H2 -Si(O-Si(CH3)2-)3)2H

[0484] δ0.6-0.8(-Si-C H2 -, -C H2 -Si(OCH3)3)20H

[0485] δ1.2-1.4(-(C H2 )6-,-(C H2 )7-,-OCH2C H3 )77H

[0486] δ1.5(-SiCH2(C H2 )6CH2-Si(OCH3)3)36H

[0487] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0488] δ2.3(-OOC-C H2 -)2H

[0489] δ3.5(-SiCH2CH2CH2-Si(OC H3 )3)27H

[0490] δ4.1(-OC H2 CH3)2H

[0491] [Synthesis example 3]

[0492] 31.6 g (2.35 × 10 -1 mol) was heated to 80°C. Then, 1.0×10 -2 g (calculated as Pt single substance, containing 0.3×10 -7 mol), 10.0 g (4.71 × 10 -2 mol), heated and stirred at 80°C for 1 hour. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (H):

[0493] [Chemistry 103]

[0494]

[0495] The product represented was 16.4 g.

[0496] 1 H-NMR

[0497] δ0.2-0.4(-Si-C H3 )12H

[0498] δ0.7(-(CH2)7C H2 -Si-)2H

[0499] δ1.2-1.5(-(C H2 )7-,-OCH2C H3 )17H

[0500] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0501] δ2.3(-OOC-C H2 -)2H

[0502] δ4.1(-OC H2 CH3)2H

[0503] δ4.4(-Si-H)1H

[0504] The above-obtained compound represented by the following formula (H) is placed in a reaction container.

[0505] [Chemistry 104]

[0506]

[0507] The compound represented by 10.0 g (2.88 × 10 -2mol) was heated to 80°C. Then, 1.0×10 -2 g (calculated as Pt single substance, containing 0.3×10 -7 mol), 9.4 g (4.04 × 10 -2 mol), heated and stirred at 80°C for 3 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (I):

[0508] [Chemistry 105]

[0509]

[0510] The expressed compound was 15.1 g.

[0511] 1 H-NMR

[0512] δ0.2-0.3(-Si-C H3 )12H

[0513] δ0.7(-(CH2)7C H2 -Si-, -SiC H2 (CH2)6CH2-Si(OCH3)3)4H

[0514] δ0.8(-SiCH2(CH2)6C H2 -Si(OCH3)3)2H

[0515] δ1.2-1.4(-(C H2 )7-,-SiCH2(C H2 )6CH2-Si(OCH3)3,-OCH2C H3 )29H

[0516] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0517] δ2.3(-OOC-C H2 -)2H

[0518] δ3.5(-SiCH2(CH2)6CH2-Si(OC H3 )3)9H

[0519] δ4.1(-OC H2 CH3)2H

[0520] 5.1 g (3.8 × 10 -2mol), 4.1 g of 12N hydrochloric acid aqueous solution, and 5.0 g of 1,4-bis(trifluoromethyl)benzene were cooled to 0°C. Then, the above-obtained

[0521] [Chemistry 106]

[0522]

[0523] The compound represented by 10.0 g (1.7 × 10 -2 mol), and aged at 0°C for 6 hours. Then, the lower layer was recovered by liquid separation operation, and the solvent and unreacted products were removed by reduced pressure distillation to obtain the following formula (J):

[0524] [Chemistry 107]

[0525]

[0526] The product weight was 8.6 g.

[0527] 1 H-NMR

[0528] δ0.1-0.2(-Si-C H3 )30H

[0529] δ0.5-0.6(-O-Si(CH3)2-C H2 -)6H

[0530] δ1.2-1.5(-(C H2 )7-,-OCH2C H3 , -Si-CH2(C H2 )6CH2-Si-)29H

[0531] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0532] δ2.3(-OOC-C H2 -)2H

[0533] δ4.1(-OC H2 CH3)2H

[0534] δ4.7(-Si-H)3H

[0535] The above-obtained compound represented by the following formula (J) is placed in a reaction container.

[0536] [Chemistry 108]

[0537]

[0538] The compound represented by 5.0g (7.0×10 -3 mol) was heated to 80°C. Then, 5.0×10 -3 g (calculated as Pt single substance, containing 1.5×10 -8 mol), 6.5 g (2.8 × 10 -2 mol), and heated and stirred at 80°C for 3 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (K):

[0539] [Chemistry 109]

[0540]

[0541] The amount of the product (hydrolyzable organosiloxane compound 3 containing a lipophilic group) was 7.6 g.

[0542] 1 H-NMR

[0543] δ0.1-0.2(-Si-C H3 )30H

[0544] δ0.5-0.7(-O-Si(CH3)2-C H2 -,-SiCH2(C H2 )6C H2 -Si(OCH3)3, -SiC H2 (CH2)6CH2-Si(OCH3)3)18H

[0545] δ1.2-1.4(-(C H2 )7-,-OCH2C H3 )17H

[0546] δ1.5(-SiCH2(C H2 )6CH2-Si(OCH3)3)36H

[0547] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0548] δ2.3(-OOC-C H2 -)2H

[0549] δ3.5(-SiCH2CH2CH2-Si(OC H3 )3)27H

[0550] δ4.1(-OC H2 CH3)2H

[0551] [Synthesis Example 4]

[0552] 45.7 g (2.35 × 10 -1 mol) was heated to 80°C. Then, 1.0×10 chloroplatinic acid / vinylsiloxane complex toluene solution was added. -2 g (calculated as Pt single substance, containing 0.3×10 -7 mol), then 10.0 g (4.71 × 10 -2 mol), heated and stirred at 80°C for 1 hour. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (L):

[0553] [Chemistry 110]

[0554]

[0555] The product represented was 18.0 g.

[0556] 1 H-NMR

[0557] δ0.2-0.4(-Si-C H3 )12H

[0558] δ0.7(-(CH2)7C H2 -Si-)2H

[0559] δ1.2-1.5(-(C H2 )7-,-OCH2C H3 )17H

[0560] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0561] δ2.3(-OOC-C H2 -)2H

[0562] δ4.1(-OC H2 CH3)2H

[0563] δ4.4(-Si-H)1H

[0564] δ7.5(-Si-C6 H4 -Si-)4H

[0565] The above-obtained compound of the following formula (L) is placed in a reaction container.

[0566] [Chemistry 111]

[0567]

[0568] The compound represented by 10.0 g (2.46 × 10 -2 mol) was heated to 80°C. Then, 1.0×10 chloroplatinic acid / vinylsiloxane complex toluene solution was added. -2 g (calculated as Pt single substance, containing 0.3×10 -7 mol), 9.10 g (3.94 × 10 -2 mol), heated and stirred at 80°C for 4 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (M):

[0569] [Chemistry 112]

[0570]

[0571] The expressed compound was 14.0 g.

[0572] 1 H-NMR

[0573] δ0.2(-Si-C H3 )12H

[0574] δ0.6(-SiC H2 (CH2)6CH2-Si(OCH3)3)2H

[0575] δ0.7(-(CH2)7C H2 -Si-, -SiCH2(CH2)6C H2 -Si(OCH3)3)4H

[0576] δ1.2-1.4(-(C H2 )7-,-(C H2 )6-,-OCH2C H3 )29H

[0577] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0578] δ2.3(-OOC-C H2 -)2H

[0579] δ3.5(-SiCH2(CH2)6CH2-Si(OC H3 )3)9H

[0580] δ4.1(-OC H2 CH3)2H

[0581] δ7.5(-Si-C6H4 -Si-)4H

[0582] 3.3 g (2.5 × 10 -2 mol), 2.6 g of 12N hydrochloric acid aqueous solution, and 3.5 g of 1,4-bis(trifluoromethyl)benzene were cooled to 0°C. Then, the above-obtained

[0583] [Chemistry 113]

[0584]

[0585] The compound represented by 7.0 g (1.1 × 10 -2 mol), and aged at 0°C for 6 hours. Then, by liquid separation operation, the lower layer was recovered, and the solvent and unreacted products were removed by reduced pressure distillation to obtain the following formula (N):

[0586] [Chemistry 114]

[0587]

[0588] The product weight was 5.6 g.

[0589] 1 H-NMR

[0590] δ0.1-0.2(-Si-C H3 )30H

[0591] δ0.5(-(CH2)7C H2 -Si(O-Si(CH3)2-)3)2H

[0592] δ0.7-0.8(-C6H4-Si-C H2 -)4H

[0593] δ1.2-1.5(-(C H2 )7-,-OCH2C H3 , -Si-CH2(C H2 )6CH2-Si-)29Hδ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0594] δ2.3(-OOC-C H2 -)2H

[0595] δ4.1(-OC H2 CH3)2H

[0596] δ4.7(-Si-H)3H

[0597] δ7.5(-Si-C6 H4 -Si-)4H

[0598] The above-obtained compound represented by the following formula (N) is placed in a reaction container.

[0599] [Chemistry 115]

[0600]

[0601] The compound represented was 1.8 g (2.3 × 10 -3 mol) was heated to 80°C. Then, 2.0×10 -3 g (calculated as Pt single substance, containing 6.0×10 -9 mol), 2.3 g (9.8 × 10 -3 mol), and heated and stirred at 80°C for 3 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (O):

[0602] [Chemistry 116]

[0603]

[0604] The obtained product (hydrolyzable organosiloxane compound 4 containing a lipophilic group) was 2.7 g.

[0605] 1 H-NMR

[0606] δ0.1-0.2(-Si-C H3 )30H

[0607] δ0.5(-(CH2)7C H2 -Si(O-Si(CH3)2-)3)2H

[0608] δ0.6-0.8(-C6H4-Si-C H2 -,-SiCH2(C H2 )6C H2 -Si(OCH3)3, -SiC H2 (CH2)6CH2-Si(OCH3)3)16H

[0609] δ1.2-1.4(-(C H2 )7-,-OCH2C H3 )17H

[0610] δ1.5(-SiCH2(C H2 )6CH2-Si(OCH3)3)36H

[0611] δ1.6(-OOC-CH2C H2 (CH2)7CH2-Si-)2H

[0612] δ2.3(-OOC-C H2 -)2H

[0613] δ3.5(-SiCH2(CH2)6CH2-Si(OC H3 )3)27H

[0614] δ4.1(-OC H2 CH3)2H

[0615] δ7.5(-Si-C6 H4 -Si-)4H

[0616] [Synthesis example 5]

[0617] 40.6 g (2.09 × 10 -1 mol) was heated to 80°C. Then, 1.0×10 chloroplatinic acid / vinylsiloxane complex toluene solution was added. -2 g (calculated as Pt single substance, containing 0.3×10 -7 mol), and then the following formula (P) was added dropwise over 3 hours.

[0618] [Chemistry 117]

[0619]

[0620] The compound represented by 10.0 g (4.18 × 10 -2 mol), heated and stirred at 80°C for 6 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (Q):

[0621] [Chemistry 118]

[0622]

[0623] The product represented was 17.1 g.

[0624] 1 H-NMR

[0625] δ0.2-0.4(-Si-C H3 )12H

[0626] δ0.7(-(CH2)7C H2 -Si-)2H

[0627] δ1.0-1.2(-N(CH2CH3 )2)6H

[0628] δ1.2-1.5(-(C H2 )7-)14H

[0629] δ1.6(-NOC-CH2C H2 (CH2)7CH2-Si-)2H

[0630] δ2.3(-NOC-C H2 -)2H

[0631] δ3.2-3.4(-N(C H2 CH3)2)4H

[0632] δ4.4(-Si-H)1H

[0633] δ7.5(-Si-C6 H4 -Si-)4H

[0634] The above-obtained compound represented by the following formula (Q) is placed in a reaction container.

[0635] [Chemistry 119]

[0636]

[0637] The compound represented by 10.0 g (2.31 × 10 -2 mol) was heated to 80°C. Then, 1.0×10 chloroplatinic acid / vinylsiloxane complex toluene solution was added. -2 g (calculated as Pt single substance, containing 0.3×10 -7 mol), 7.5 g (3.23 × 10 -2 mol), heated and stirred at 80°C for 6 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (R):

[0638] [Chemistry 120]

[0639]

[0640] The expressed compound was 12.6 g.

[0641] 1 H-NMR

[0642] δ0.2-0.3(-Si-C H3 )12H

[0643] δ0.7(-(CH2)7C H2 -Si-, -SiC H2(CH2)6CH2-Si(OCH3)3)4H

[0644] δ0.8(-SiCH2(CH2)6C H2 -Si(OCH3)3)2H

[0645] δ1.0-1.2(-N(CH2C H3 )2)6H

[0646] δ1.2-1.4(-(C H2 )7-)14H

[0647] δ1.5(-SiC H2 (CH2)6CH2-Si(OCH3)3)2H

[0648] δ1.6(-NOC-CH2C H2 (CH2)7CH2-Si-)2H

[0649] δ2.3(-NOC-C H2 -)2H

[0650] δ3.2-3.4(-N(C H2 CH3)2)4H

[0651] δ3.5(-SiCH2(CH2)6CH2-Si(OC H3 )3)9H

[0652] δ7.5(-Si-C6 H4 -Si-)4H

[0653] 4.5 g (3.4 × 10 -2 mol), 3.6 g of 12N hydrochloric acid aqueous solution, and 5.0 g of 1,4-bis(trifluoromethyl)benzene were cooled to 0°C. Then, the above-obtained

[0654] [Chemistry 121]

[0655]

[0656] The compound represented by 10.0 g (1.5 × 10 -2 mol), and aged at 0°C for 6 hours. Then, the lower layer was recovered by liquid separation operation, and the solvent and unreacted products were removed by reduced pressure distillation to obtain the following formula (S):

[0657] [Chemistry 122]

[0658]

[0659] The product weight was 8.6 g.

[0660] 1 H-NMR

[0661] δ0.1-0.2(-Si-C H3 )30H

[0662] δ0.5(-(CH2)7C H2 -Si(O-Si(CH3)2-)3)2H

[0663] δ0.7-0.8(-C6H4-Si-C H2 -)4H

[0664] δ1.0-1.2(-N(CH2C H3 )2)6H

[0665] δ1.2-1.5(-(C H2 )7-,-Si-CH2(C H2 )6CH2-Si-)26H

[0666] δ1.6(-NOC-CH2C H2 (CH2)7CH2-Si-)2H

[0667] δ2.3(-NOC-C H2 -)2H

[0668] δ3.2-3.4(-N(C H2 CH3)2)4H

[0669] δ4.7(-Si-H)3H

[0670] δ7.5(-Si-C6 H4 -Si-)4H

[0671] The above-obtained compound represented by the following formula (S) is placed in a reaction container.

[0672] [Chemistry 123]

[0673]

[0674] The compound represented by 5.0 g (6.3 × 10 -3 mol) was heated to 80°C. Then, 5.0×10 -3 g (calculated as Pt single substance, containing 1.5×10 -8 mol), 5.9 g (2.5 × 10 -2mol), heated and stirred at 80°C for 3 hours. Then, the solvent and unreacted products were removed under reduced pressure to obtain the following formula (T):

[0675] [Chemistry 124]

[0676]

[0677] The amount of the product (hydrolyzable organosiloxane compound 5 containing a lipophilic group) was 8.1 g.

[0678] 1 H-NMR

[0679] δ0.1-0.2(-Si-C H3 )30H

[0680] δ0.5(-(CH2)7C H2 -Si(O-Si(CH3)2-)3)2H

[0681] δ0.6-0.8(-C6H4-Si-C H2 -,-SiCH2(CH2)6C H2 -Si(OCH3)3, -SiC H2 (CH2)6CH2-Si(OCH3)3)16H

[0682] δ1.0-1.2(-N(CH2C H3 )2)6H

[0683] δ1.2-1.4(-(C H2 )7-,-Si-CH2(C H2 )6CH2-Si-)26H

[0684] δ1.5(-SiCH2(CH2)6C H2 -Si(OCH3)3)6H

[0685] δ1.6(-NOC-CH2C H2 (CH2)7CH2-Si-)2H

[0686] δ2.3(-NOC-C H2 -)2H

[0687] δ3.2-3.4(-N(C H2 CH3)2)4H

[0688] δ3.5(-SiCH2(CH2)6CH2-Si(OC H3 )3)27H

[0689] δ7.5(-Si-C6H4 -Si-)4H

[0690] [Examples 1 to 14, Comparative Examples 1 to 3]

[0691] The (hydrolyzable) organosiloxane compounds (Compound 1) to (Compound 5) containing lipophilic groups obtained above and the following polyol esters (B-1) to (B-6) were mixed in the ratios shown in Tables 1 to 3, dissolved in propylene glycol monomethyl ether to prepare a 0.2 mass % solution, and a surface treatment agent was prepared. Then, it was sprayed on Gorilla Glass manufactured by Corning Incorporated and cured at 40°C and 80% RH for 12 hours to prepare a cured film with a thickness of about 5 nm.

[0692] (B-1) Neopentyl glycol dioleate

[0693] (B-2) Tri(2-ethylhexanoate) trimethylolpropane

[0694] (B-3) Tri(oleic acid) trimethylolpropane ester

[0695] (B-4) trioleylglycerol

[0696] (B-5) Tristearate

[0697] (B-6) Pentaerythritol Tetra(2-ethylhexanoate)

[0698] [Evaluation of fingerprint visibility]

[0699] Sebum was attached to the glass having the cured film formed thereon with a load of 1 kg, and the visibility was evaluated visually according to the following 4 levels. It should be noted that "almost no fingerprints can be seen" means that the fingerprints are not visible at first glance, and the fingerprints can only be seen when the eyes are focused, and "faintly visible fingerprints" means that the fingerprints are faintly visible at first glance. The results are shown in Tables 1 to 3.

[0700] 4: Almost no fingerprints can be seen~no fingerprints can be seen

[0701] 3: Fingerprints can be vaguely seen

[0702] 2: Fingerprints are light but clearly visible

[0703] 1: Fingerprints can be clearly seen

[0704] [Evaluation of lipophilicity]

[0705] The contact angle of the cured film on the glass formed with the cured film was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) for oleic acid (oleic acid contact angle) (droplet: 2 μl, temperature: 25°C, humidity (RH): 40%, measurement time: 40 seconds). The results are shown in Tables 1 to 3.

[0706] [Evaluation of wear resistance]

[0707] The glass formed with the cured film produced above was abraded 50 times under the following conditions using a friction tester (manufactured by Shinto Scientific Co., Ltd.), and the process of visually confirming the presence or absence of surface damage was repeated until damage could be confirmed, as an evaluation of wear resistance. The more times damage can be confirmed, the higher the wear resistance, and the fewer times damage can be confirmed, the lower the wear resistance. The test environment conditions were 25°C and 40% humidity. The number of wear times when damage was visually confirmed (the number of times steel wool was durable) is shown in Tables 1 to 3.

[0708] Steel wool abrasion resistance

[0709] Steel wool: BONSTAR#0000 (manufactured by Japan Steel Wool Co., Ltd.)

[0710] Contact area: 10mmφ

[0711] Moving distance (one way): 40mm

[0712] Moving speed: 3200mm / min

[0713] Load: 1.5kg / cm

[0714] [Table 1]

[0715]

[0716] [Table 2]

[0717]

[0718] [Table 3]

[0719]

[0720] The examples showed excellent low fingerprint visibility, lipophilicity, and wear resistance. On the other hand, Comparative Example 1 having only a (hydrolyzable) organosiloxane compound containing a lipophilic group (component (A)) showed extremely low wear resistance. In addition, Comparative Example 2 having only a polyol ester (component (B)) showed low wear resistance. In addition, Comparative Example 3, in which the amount of polyol ester (component (B)) blended was less than the amount specified in the present invention, did not sufficiently improve the wear resistance.

Claims

1. A coating composition comprising the following components (A) and (B) as essential components: (A) an organosiloxane compound containing a lipophilic group and / or a partial condensate thereof, which contains a compound selected from the group consisting of: (-C(=O)OR 1 ) represented by the formula (-OC(=O)R 1 ) represented by the formula (-C(=O)NR 1 2) A group represented by the formula (-C(=O)SR 1 ) and a group represented by the formula (-P(=O)(OR 1 ) 2) The lipophilic group and the silanol group or the hydrolyzable silyl group in the group represented by, wherein R 1 are independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, (B) a polyol ester composed of a condensate of a 2- to 6-valent alcohol and a fatty acid having 3 to 22 carbon atoms, The mass ratio of the component (A) to the component (B) is in the range of 0.1<(A) / (B)<10.

2. The coating composition according to claim 1, wherein The component (A) is an organosiloxane compound containing a lipophilic group and / or a partial condensate thereof represented by the following general formula (1): [Chemistry 1] In the formula, A is -C(=O)OR 1 、-OC(=O)R 1 、-C(=O)NR 1 2. -C(=O)SR 1 OR-P(=O)(OR 1 )2, R 1 independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, Y independently is a divalent organic group, W independently is an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group, or a hydrolyzable group, R independently is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X independently is a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, and q is an integer of 1 to 3.

3. The coating composition according to claim 2, wherein In the lipophilic group-containing organosiloxane compound represented by the general formula (1) of the component (A), Y is independently a divalent group selected from -O-, -S-, -NR-, -C(=O)-, -C(=O)O-, -C(=O)NR-, -OC(=O)NR-, a silylene group, a silylene group, and a linear, branched or cyclic divalent organosiloxane residue having 2 to 10 silicon atoms, and an alkylene group having 2 to 30 carbon atoms which may contain an arylene group having 6 to 20 carbon atoms, and R is an alkyl group having 1 to 4 carbon atoms or a phenyl group.

4. The coating composition according to claim 2 or 3, wherein In the lipophilic group-containing organosiloxane compound represented by the general formula (1) of the component (A), W is independently selected from an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom, an oxime group, an isocyanate group, and a cyanate group.

5. The coating composition according to claim 1, wherein The component (A) is an organosiloxane compound containing a lipophilic group and / or a partial condensate thereof represented by the following general formula (2): [Chemistry 2] In the formula, R 2 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, Q is a single bond, or a divalent group selected from a silylene group, a silylene group, and a linear, branched or cyclic divalent organosiloxane residue having 2 to 10 silicon atoms, m is independently an integer of 1 to 20, and X is independently a hydroxyl group or a hydrolyzable group.

6. The coating composition according to any one of claims 1 to 3 and 5, wherein The component (B) is a polyol ester comprising a condensate of a polyol selected from the group consisting of neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol and a fatty acid having 3 to 22 carbon atoms.

7. The coating composition according to claim 4, wherein The component (B) is a polyol ester comprising a condensate of a polyol selected from the group consisting of neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol and a fatty acid having 3 to 22 carbon atoms.

8. A surface treating agent comprising the coating agent composition according to any one of claims 1 to 7. 9 . The surface treating agent according to claim 8 , further comprising a solvent.

10. The surface treatment agent according to claim 8 or 9, further comprising a hydrolysis condensation catalyst. 11 . The surface treatment agent according to claim 8 or 9 , which provides a cured film having an oleic acid contact angle of 30° or less at 25° C. and a relative humidity of 40%. 12 . The surface treatment agent according to claim 10 , which provides a cured film having an oleic acid contact angle of 30° or less at 25° C. and a relative humidity of 40%.

13. An article having a cured film of the surface treatment agent according to any one of claims 8 to 12 on its surface.

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