JP2005298572A - Stainproof coating agent and coated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stainproof coating agent which exhibits excellent surface-protecting functions, forms a durable stainproof water-repellent film and is highly safe, and a coated article comprising a substrate having a cured film of the coating agent formed thereon. <P>SOLUTION: The stainproof coating agent comprises an organosilicon compound represented by general compositional formula (I) (wherein R is the same or different and are each a 1-6C alkyl group or a phenyl group; X is a hydroxy group, a halogen atom, a 1-6C alkoxy, acyloxy or alkenoxy group or an -NCO group; Y is -O-, a 2-10C alkylene group, an arylene group or a group composed of a combination thereof; a is an integer of 1-100; m, p and q are numbers satisfying 0.01≤m<1, 0≤p<1, 0.5≤q<3 and 0.51≤m+q+p<4). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  In the present invention, a linear diorganosiloxane chain is fixed in the molecule at one end, and an oligomeric or polymeric organosilicon compound having a hydrolyzable silyl group or silanol group in the same molecule is an essential component. And an antifouling coating agent capable of forming an antifouling film having excellent durability and a coated article on which a cured film of the coating agent is formed.

  Various attempts have been made in the past to form a coating film excellent in water repellency and oil repellency on the surface of a substrate to impart antifouling properties such as antifouling properties, contaminant removal properties, and fingerprint adhesion prevention properties.

  There are many studies using fluorinated alkyl-substituted silanes or fluorinated polyether-substituted silanes. For example, fluorinated alkyl-substituted alkoxysilanes or silazanes thereof (Patent Document 1: JP-A-10-7438), perfluoropolyether group-substituted silanes (Patent Document 2: JP-A 2000-143991), fluorinated alkyl-substituted Acid hydrolyzate of alkoxysilane and tetraalkoxysilane (Patent Document 3: JP 2000-351938 A) Hydrolysis condensate of two types of fluorine-containing silane and non-fluorine-containing silane (Patent Document 4: JP 2002-53804 gazette) and the like. These systems are preferable because they provide excellent water repellency and oil repellency and high durability, but are economically disadvantageous in that the raw material silane compound is expensive, and these silane compounds containing fluorine atoms or their When the cured product (coating film) is incinerated at the time of disposal, harmful HF is generated, which may cause a concern in terms of safety.

  Silicone-based surface treatment agents have also been studied from the viewpoints of economy and safety, but simple silicone resin-based coating agents have excellent scratch resistance but lack water and oil repellency. ing. Therefore, a system containing a diorganosiloxane chain has been studied. For example, a specific compound having a hydrolyzable silyl group having extremely high hydrolyzability such as Si-Cl or Si-NCO group and / or part thereof via a spacer to a silane compound having three linear silicones Hydrolyzate (Patent Document 5: JP 2000-129247 A), a system in which dimethyl silicone containing hydrolyzable silyl groups at both ends is dispersed in a silica matrix (Patent Document 6: JP 2003-206160 A) Publication), a system in which a layer containing a fluorine-containing silane compound is provided on a substrate, and a layer containing a linear silicone compound having a hydrolyzable silyl group is laminated thereon (Patent Document 7: JP 2001-205747 A). Issue gazette).

  In the first system, the base material is limited with the aim of fixing to the glass surface with a monomolecular layer, and the hydrophobic group is bulky, so that fixing does not occur sufficiently, and it is a good solvent for silicones such as toluene When the surface dirt is to be removed, the film is easily dropped, which is inferior in durability. In the second system, the dimethyl silicone component having hydrolyzable silyl groups at both ends lacks compatibility with the silica matrix, so that phase separation (floating at the top) results in repelling during film formation. Since it is not fixed, there is a drawback that it is easily removed by washing with a solvent such as toluene. In the third system, the silicone compound is treated on the fluorine-containing silane layer without hydrolysis, which is also inferior in adhesiveness and insufficient in durability, and further treated with fluorine-containing silane. As a result, there may be concerns about safety.

Japanese Patent Laid-Open No. 10-7438 JP 2000-143991 A JP 2000-351938 A JP 2002-53804 A JP 2000-129247 A JP 2003-206160 A JP 2001-205747 A

  The present invention has been made in view of the above circumstances, and is capable of forming a durable antifouling and water-repellent coating film with excellent surface protection function, and also has a highly safe antifouling coating agent and substrate. It aims at providing the coated article in which the hardened film of the agent was formed.

  As a result of intensive investigations to achieve the above-mentioned object, the inventors of the present invention have a silyl group having a single-end-capped diorganopolysiloxane group that has not been known so far and can be condensation-cured in the same molecule. When the antifouling coating agent containing the following organosilicon compound (I) containing is treated on the surface of the substrate, the above-mentioned conventional problems have been solved, and durability that does not fall off even when washed with a solvent such as toluene It has been found that a protective film excellent in water repellency and antifouling properties can be formed, and the present invention has been made.

（式中、Ｒは炭素数１〜６のアルキル基又はフェニル基を示し、各Ｒは同一であっても異なっていてもよい。Ｘは水酸基、ハロゲン原子、炭素数１〜６のアルコキシ基、アシルオキシ基又はアルケノキシ基、又は−ＮＣＯ基を示し、Ｙは−Ｏ−、又は炭素数２〜１０のアルキレン基、アリーレン基又はこれらが結合した基を示す。ａは１〜１００の整数、ｍ、ｐ、ｑは、０．０１≦ｍ＜１、０≦ｐ＜１、０．５≦ｑ＜３、０．５１≦ｍ＋ｐ＋ｑ＜４を満足する数である。） That is, the present invention
An antifouling coating agent comprising an organosilicon compound represented by the following general composition formula (I).

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and each R may be the same or different. X represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, An acyloxy group, an alkenoxy group, or an —NCO group, Y represents —O—, an alkylene group having 2 to 10 carbon atoms, an arylene group, or a group to which these are bonded, a represents an integer of 1 to 100, m, p and q are numbers satisfying 0.01 ≦ m <1, 0 ≦ p <1, 0.5 ≦ q <3, and 0.51 ≦ m + p + q <4.)

In this case, the organosilicon compound (I) includes (a) an organosilicon compound represented by the following general formula (II) and / or a (partial) hydrolyzate thereof, and (b) represented by the following general formula (III). Organosilicon compound and / or its (partial) hydrolyzate, using component (a) and component (b) in a molar ratio (a) / (b) = 1/99 to 99/1. , Preferably obtained by (partial) cohydrolysis / condensation of these components,
(I) hydrolyzing the organosilicon compound represented by the general formula (II);
(Ii) An organosilicon compound represented by the above general formula (III) and / or a (partial) hydrolyzate thereof is added thereto.
(Iii) The mixture is preferably prepared through a process of (partially) cohydrolyzing and condensing.

（式中、Ｒ、ａは上記と同様の意味を示し、Ｚはハロゲン原子、炭素数１〜６のアルコキシ基、アシルオキシ基又はアルケノキシ基、又は−ＮＣＯ基を示し、ｂは０，１又は２である。またｎは０，１又は２である。）

(In the formula, R and a have the same meanings as described above, Z represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group, an alkenoxy group, or an —NCO group, and b represents 0, 1 or 2) And n is 0, 1 or 2.)

  The antifouling coating agent may contain a silicone resin condensation catalyst and / or an organic solvent.

  In addition, the present invention is directly or via other layers (in particular, a resin layer containing a metal oxide or a Si-X group (X is as described above)) on a substrate such as plastic, metal, glass, or ceramic. Thus, a coated article in which a cured film of the antifouling coating agent is formed as an antifouling protective film is provided. In this case, the coated article can be a transparent article for an optical component.

  The antifouling coating agent of the present invention is excellent in that the organosilicon compound (I) contains a large amount of condensation-curing groups at the molecular terminals, so that the substrate surface can be firmly coated and protected. Gives the surface protection function.

  In addition, since one end-capped diorganopolysiloxane group is contained in the same molecule, a portion having a hydrolyzable group or SiOH group is fixed on the substrate side during coating, and the diorganosiloxane is oriented outward. Since it is easy, the cured film exhibits good water repellency and antifouling property (contamination removal property). And since it has adhered firmly, a film is maintained also by the wiping operation using solvents, such as toluene, and the performance is excellent in durability.

  The third feature is that it does not contain a fluorine atom. Fluorine-containing compounds exhibit excellent water repellency and oil repellency, but toxic hydrogen fluoride is generated when burned, which may cause problems when discarded. There is no generation and it is safe.

  Therefore, the antifouling coating agent of the present invention is a protective film / plate for automobiles, train plastics and ceramics window glass, various displays such as computers, televisions, plasma displays, mobile phones, digital cameras, and liquid crystal display devices. It can be suitably used to form a durable antifouling property (contamination prevention, contamination removal, fingerprint adhesion prevention) protective coating on the surface of optical parts such as various instrument covers.

  The antifouling coating agent of the present invention is excellent in surface protection function, can form a durable antifouling film, and has high safety.

  The antifouling coating agent of the present invention contains an organosilicon compound represented by the following general composition formula (I).

（式中、Ｒは炭素数１〜６のアルキル基又はフェニル基を示し、各Ｒは同一であっても異なっていてもよい。Ｘは水酸基、ハロゲン原子、炭素数１〜６のアルコキシ基、アシルオキシ基又はアルケノキシ基、又は−ＮＣＯ基を示し、Ｙは−Ｏ−、又は炭素数２〜１０のアルキレン基、アリーレン基又はこれらが結合した基を示す。ａは１〜１００の整数、ｍ、ｐ、ｑは、０．０１≦ｍ＜１、０≦ｐ＜１、０．５≦ｑ＜３、０．５１≦ｍ＋ｐ＋ｑ＜４を満足する数である。）

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and each R may be the same or different. X represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, An acyloxy group, an alkenoxy group, or an —NCO group, Y represents —O—, an alkylene group having 2 to 10 carbon atoms, an arylene group, or a group to which these are bonded, a represents an integer of 1 to 100, m, p and q are numbers satisfying 0.01 ≦ m <1, 0 ≦ p <1, 0.5 ≦ q <3, and 0.51 ≦ m + p + q <4.)

  Here, specific examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and a phenyl group. Use of a methyl group is preferable because good antifouling properties can be obtained and it is economically advantageous.

  Specific examples of X include halogen atoms such as OH group, Cl, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, alkoxy group such as methoxyethoxy group, alkenoxy group such as isopropenoxy group, acetoxy group, etc. And an acyloxy group, -NCO group (isocyanate group) and the like.

  Y represents a spacer group for bonding the one-end blocked diorganopolysiloxane group to the oligomeric organosilicon compound having a hydrolyzable group.

Specific examples of Y include etheric oxygen (in this case, meaning a siloxane bond), — (CH ₂ ) ₂ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ —, — (CH ₂ ) _{10 -, - (CH 2) 2} -C 6 H 4 - (CH 2) 2 -, - (CH 2) 2 -C 6 H 10 - , and the like. Etheric oxygen or — (CH ₂ ) ₂ — is preferable from the economical advantage, and particularly when light resistance is required, etheric oxygen in which all basic skeletons are formed by siloxane bonds is preferable.

  M representing the degree of substitution of the one-end blocked diorganopolysiloxane group preferably satisfies the range of 0.01 ≦ m <1. If m is less than 0.01, sufficient antifouling property cannot be obtained, and if it is 1 or more, the curability deteriorates. Particularly preferably, 0.02 ≦ m ≦ 0.7 is satisfied.

  p represents the degree of substitution of the substituent R, and preferably satisfies the range of 0 ≦ p <1. When it is 1 or more, the cross-linking density of the cured film is lowered, so that the strength of the film is lowered and the durability is inferior. Particularly preferably, 0 ≦ p ≦ 0.7 is satisfied.

  q represents the degree of substitution of the OH group or hydrolyzable group, and preferably satisfies the range of 0.5 ≦ q <3. If it is less than 0.5, the crosslinking density of the cured film is lowered, so that the strength of the film is lowered and the durability is inferior. When it is 3 or more, it means a monomer of an organosilicon compound, and the one-end-capped diorganopolysiloxane group is not well oriented on the treated surface and good antifouling property cannot be obtained, which is not preferable. Particularly preferably, 1 ≦ q ≦ 2.5 is satisfied.

  Further, m + p + q is 0.51 ≦ m + p + q <4, preferably 0.6 ≦ m + p + q ≦ 3, and particularly preferably 0.8 ≦ m + p + q ≦ 2.5.

  A representing the degree of polymerization of the diorganosiloxy unit should satisfy the range of a = 1 to 100. If a is less than 1, the diorganosiloxane chain length is short and sufficient antifouling property cannot be obtained, which is not preferable. If a exceeds 100, the orientation on the surface does not proceed well during processing, so that a satisfactory antifouling property cannot be obtained, and the surface fixing is not sufficient, and the durability is insufficient, which is not preferable. More preferably, the range of a = 1 to 50 should be satisfied.

  Any material can be used as long as these conditions are satisfied. In this case, the number average molecular weight (Mw) is preferably 500 to 50,000, particularly 1,000 to 20,000.

  The organosilicon compound (I) is represented by (a) an organosilicon compound represented by the following general formula (II) and / or a (partial) hydrolyzate thereof, and (b) represented by the following general formula (III). Using organosilicon compound and / or its (partial) hydrolyzate, component (a) and component (b) in molar ratio (a) / (b) = 1/99 to 99/1 It can be obtained by (partially) cohydrolyzing and condensing the components.

（式中、Ｒ、ａは上記と同様の意味を示し、Ｚはハロゲン原子、炭素数１〜６のアルコキシ基、アシルオキシ基又はアルケノキシ基、又は−ＮＣＯ基を示し、ｂは０，１又は２である。またｎは０，１又は２である。）

(In the formula, R and a have the same meanings as described above, Z represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group, an alkenoxy group, or an —NCO group, and b represents 0, 1 or 2) And n is 0, 1 or 2.)

  In the present invention, the (partial) hydrolyzate means a partial hydrolyzate, a complete hydrolyzate, or a mixture thereof.

  Here, Z represents a hydrolyzable group, specifically, a halogen atom such as Cl, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, or a methoxyethoxy group, an isopropenoxy group, or the like And an acyloxy group such as an alkenoxy group and an acetoxy group, an -NCO group (isocyanate group), and the like. A methoxy group or an ethoxy group silane compound is preferable because it is easy to handle and can easily control the reaction during hydrolysis.

  Specific examples of the organosilicon compound represented by the general formula (II) include the following.

The organosilicon compound represented by the general formula (II) can be synthesized by a conventionally known method as shown below.
(A) R ₃ Si— (O—R ₂ Si—) _a-1 —R ₂ Si—Y′—a compound having an unsaturated double bond at the terminal represented by —CH═CH ₂ (provided that Y ′ is A method in which a hydrosilylation reaction is performed on a residue obtained by removing Y from —CH═CH ₂ ) and H—SiR _b Z _{3-b in} the presence of a hydrosilylation catalyst.
(B) a compound having a Si—H group at a terminal represented by R ₃ Si— (O—R ₂ Si—) _a-1 —R ₂ Si—H;
A method in which CH ₂ ═CH—Y′—SiR _b Z _3-b is subjected to a hydrosilylation reaction in the presence of a hydrosilylation catalyst.
(C) a compound having a SiOH group at the terminal represented by R ₃ Si— (O—R ₂ Si—) _a-1 —R ₂ Si—OH and an excess of SiR _b Z _4-b , Thereafter, excess silane monomer is removed under reduced pressure.

Specific examples of the organosilicon compound represented by the general formula (III) include SiCl ₄ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC _4). H ₉ ) ₄ , Si (OCOCH ₃ ) ₄ , Si (NCO) ₄ , (C ₄ H ₉ O) ₂ Si (OCOCH ₃ ) ₂ , CH ₃ SiCl ₃ , CH ₃ Si (OCH ₃ ) ₃ , CH ₃ Si (OC ₂ H ₅ ) ₃ , CH ₃ Si (OC ₃ H ₇ ) ₃ , CH ₃ Si (OC ₄ H ₉ ) ₃ , CH ₃ Si (OCOCH ₃ ) ₃ , CH ₃ Si (OC (CH ₃ ) = CH ₂ ) ₃ , CH ₃ Si (NCO) ₃ , C ₆ H ₅ Si (OCH ₃ ) ₃ , C ₆ H ₁₁ Si (OCH ₃ ) ₃ , C ₆ H ₁₃ Si (OCH ₃ ) ₃ , (CH ₃ ) _{2 SiCl 2, (CH 3) 2} Si (OCH 3) 2, (CH 3) 2 Si (OC 2 H 5) 2, (CH 3) 2 Si (OC 3 _{7) 2, (CH 3)} 2 Si (OC 4 H 9) 2, (CH 3) 2 Si (OCOCH 3) 2, (CH 3) 2 Si (NCO) 2, (C 6 H 5) 2 Si ( OCH ₃ ) _{2 and the} like.

  The compounding ratio of the organosilicon compound of the above general formula (II) and / or its (partial) hydrolyzate (a) and the organosilicon compound of the above general formula (III) and / or its (partial) hydrolyzate (b) Is preferably used in a molar ratio in the range of (a) / (b) = 1/99 to 99/1. If it is less than 1/99, the proportion of the component (a) that exhibits antifouling properties is too low, and sufficient antifouling properties cannot be obtained, which is not preferable. On the other hand, if it exceeds 99/1, a sufficient cross-linking density is not achieved, and the durability becomes insufficient. More preferably, (a) / (b) = 2/98 to 70/30, particularly preferably (a) / (b) = 3/97 to 50/50.

  In addition to the organosilicon compound, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxy) is used for the purpose of improving the adhesion to the substrate within a range that does not affect the required properties. (Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane A compound such as silane coupling agents such as silane coupling agents can be used in combination (partially) with co-hydrolysis.

  When using these compounds, the usage-amount is 0.1-50 mass parts with respect to 100 mass parts of compounds (I).

Organosilicon compound (II) and / or its (partial) hydrolyzate and one or more types selected from organosilicon compound (III) and / or its (partial) hydrolyzate are (partial) cohydrolyzed As the condensation method, conventionally known methods as shown below can be adopted.
(A) Two kinds of raw materials are mixed and co- (partially) hydrolyzed. (Partial) condensation is carried out if necessary.
(B) The organosilicon compound (II) is hydrolyzed, and the organosilicon compound (III) and / or its (partial) hydrolyzate is added thereto to co- (partially) hydrolyze. (Partial) condensation is carried out if necessary.
(C) A hydrolyzed organosilicon compound (II) and a hydrolyzed organosilicon compound (III) are mixed. (Partial) condensation is carried out if necessary.

Any of the above methods may be applied. Since the hydrolysis rate of the organosilicon compound (II) is slightly slow, it is particularly preferable to employ the method (ii) in which the organosilicon compound (II) is hydrolyzed in advance, since two components are uniformly incorporated. That is, the preferred method is
(I) hydrolyzing the organosilicon compound represented by the general formula (II);
(Ii) An organosilicon compound represented by the above general formula (III) and / or a (partial) hydrolyzate thereof is added thereto.
(Iii) It is a method that undergoes a step of (partially) cohydrolyzing and condensing this mixture.

  In performing the hydrolysis / condensation, a solvent may be used. Specific examples thereof include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol mono Glycol ethers such as ethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetyl acetone, esters such as ethyl acetate, butyl acetate and ethyl acetoacetate, xylene and toluene Etc. can be shown.

  Further, when performing hydrolysis / condensation, various conventionally known catalysts for hydrolysis / condensation can be used. Specifically, the following can be exemplified. Namely, acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, maleic acid and methanesulfonic acid, amine compounds such as NaOH, ammonia, triethylamine, dibutylamine, hexylamine, octylamine and dibutylamine, and salts of amine compounds , Bases such as quaternary ammonium salts such as benzyltriethylammonium chloride and tetramethylammonium hydroxide, fluorides such as potassium fluoride and sodium fluoride, solid acidic catalysts or solid basic catalysts (eg ion exchange resins) Catalysts), metal salts of organic carboxylic acids such as iron-2-ethylhexoate, titanium naphthate, zinc stearate, dibutyltin diacetate, tetrabutoxytitanium, tetra-i-propoxytitanium, dibutoxy- (bis- 2,4-pentanedionate) titanium Organic titanium esters such as di-i-propoxy (bis-2,4-pentanedionate) titanium, tetrabutoxyzirconium, tetra-i-propoxyzirconium, dibutoxy- (bis-2,4-pentanedionate) zirconium, di Organic metal compounds such as organozirconium esters such as i-propoxy (bis-2,4-pentanedionate) zirconium, alkoxyaluminum compounds such as aluminum triisopropoxide, aluminum chelate compounds such as aluminum acetylacetonate complex, γ -Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, etc. Ami Alkyl-substituted alkoxysilanes are exemplified may be used singly or in combination. Further, these catalysts may be used in the present antifouling coating agent when coating for the purpose of obtaining a dense and strong cured film.

  In this case, when performing hydrolysis / condensation of the components (a) and (b), the addition amount of the hydrolysis / condensation catalyst is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the raw material.

  The conditions for the hydrolysis / condensation may be the reaction in the temperature range from room temperature (25 ° C.) to 100 ° C. for about 1 minute to 10 days. Even in the system in which the two types of hydrolyzate (c) are mixed, the condensation progresses and becomes uniform while maintaining at room temperature for a long time. Even if it is uniform.

  The antifouling coating agent of the present invention may contain a condensation catalyst for silicone resin and an organic solvent in addition to the organosilicon compound of the above formula (I). In this case, in the antifouling coating agent of the present invention, The content of the organosilicon compound of the formula (I) is 0.01 to 10% by mass, particularly 0.1 to 5% by mass. Further, as the condensation catalyst for silicone resin, those mentioned in the above hydrolysis / condensation catalyst can be used, and the content thereof is 0.001 to 1% by mass, especially 0 in the antifouling coating agent. 0.002 to 0.1% by mass. As the organic solvent, the same organic solvents as mentioned in the hydrolysis / condensation can be used, and the content thereof is 90 to 99.99% by mass, particularly 92 to 99% by mass in the coating agent.

  In addition to the antifouling coating agent of the present invention, organic and inorganic ultraviolet absorbers, leveling agents, and buffering agents for controlling the pH in the system to pH 2-7 where silanol groups are likely to exist stably, for example, Optional components such as acetic acid-sodium acetate and disodium hydrogen phosphate-citric acid may be contained.

  The cured film formed on the substrate surface by the antifouling coating agent of the present invention functions as long as it has a thickness of a monomolecular layer or more. Usually, the film thickness is 0.1 nm to 100 nm, preferably 0.5 to 30 nm. The method for coating the surface of the composition with the composition is not particularly limited, such as dipping, spin coating, flow coating, roll coating, spray coating, screen printing, etc. Therefore, it is preferable to carry out the film thickness to a predetermined thickness by a dipping method, a spray method and a roll coating method. When used, it can be used by diluting with a solvent which can be used in the above-mentioned reaction. The concentration can be applied up to 0.1 to 10% by mass.

  The coating film is preferably cured at room temperature to 300 ° C. for 4 minutes to 1 week.

  As the transparent substrate on which the antifouling coating agent of the present invention is applied, glass, various ceramics, metals, and various plastics are suitable. Specific examples of plastics are all applicable as long as they have excellent optical properties, but polycarbonate resins, polyalkylene terephthalate resins such as PET, cellulose resins such as diacetyl cellulose, acetate butyrate cellulose, and triacetyl cellulose. , Acrylic resins, polystyrene resins, polyimide resins, polyester resins, polyethersulfone resins, liquid crystalline resins such as polyarylate, polyurethane resins, polysulfone resins, polyetherketone resins, polyolefin resins such as trimethylpentene, polyvinylnorbornene, Although high refractive index resin containing sulfur and these composite resin can be illustrated, it is not limited to this. Particularly preferred are polycarbonate resins, polyalkylene terephthalate resins such as PET, and triacetyl cellulose resins. The transparent substrate may be a molded part, a plate, or a film.

Even if the base material surface on which the antifouling coating agent of the present invention is applied is used, a metal oxide layer or a resin layer containing Si-X groups (X is as described above) is laminated in advance. Good. When applied to a plastic substrate, it is suitable because excellent adhesion can be obtained. As the metal _{oxide, SiO 2, TiO 2, ZrO} 2, InO 2, Al 2 O 3, ZnO, CeO 2, SnO 2, HfO 2, Sb 2 O 5 is preferred. These metal oxides may be laminated on the surface of the substrate by vapor deposition such as CVD, coating by sputtering, sol-gel method, or the like. In addition, as a resin containing Si-X group, various organic resins such as acrylic resin modified with silicone resin, polyester resin, epoxy resin, alkyd resin, and hydrolyzable silane compound having unsaturated double bond are copolymerized. An acrylic resin, an organosilicon oligomer containing a Si-X group, a silicone resin, or the like can be used. In addition, the thickness of the metal oxide layer and the resin layer containing a Si—X group is 0.01 μm to 10 μm, particularly preferably 0.1 to 5 μm.
The transparent substrate coated with the antifouling coating agent of the present invention can be suitably used particularly for optical parts.

  Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example,% is mass%, a part is mass part, and the average molecular weight in this specification shows the number average molecular weight of polystyrene conversion by gel permeation chromatography (henceforth GPC).

[Preparation Example 1]
Into a 3 liter flask equipped with a stirrer, a condenser and a thermometer, 175 g (0.20 mol) of the following organosilicon compound (i), 700 g of t-butanol, and 8 g of a solid acid catalyst were charged and stirred at 25 ° C. . Here, 36 g (2.0 mol) of ion-exchanged water was dropped in 10 minutes. Immediately after the dropping, the solution was cloudy, but gradually generated heat. After 1 hour, hydrolysis was completed and the system became transparent. To this, 832 g (4.0 mol) of tetraethoxysilane was added. After stirring for 1 hour at room temperature, 288 g (16.0 mol) of ion-exchanged water was added dropwise over 30 minutes. Heat was gradually generated, and the internal temperature increased to a maximum of 55 ° C. After completion of dropping, the mixture was stirred at room temperature for 24 hours. Thereafter, the solid acid catalyst of the catalyst was removed by filtration to prepare a coating liquid (1).
When this product was analyzed by GPC, it had a number average molecular weight of 9,730 and a single peak. ^{29 From the} results of Si-NMR analysis, the ratio of each structural unit is M / D / Q-1 / Q-2 / Q-3 / Q-4≈4 / 36/7/18/21/14 Thus, a resin solution in which each parameter in the general formula (I) is represented by m = 0.07, a = 9, p = 0, q = 0.78 (provided that R = CH ₃ , Y = O, X = OH, OCH 3).

[Preparation Example 2]
A coating liquid (2) was prepared in the same manner as in Preparation Example 1, except that 488.4 g (0.20 mol) of the following organosilicon compound (ii) was used instead of the organosilicon compound (i).
When this product was analyzed by GPC, it had a number average molecular weight of 12,900 and a single peak. A resin solution in which each parameter in the general formula (I) is represented by m = 0.06, a = 30, p = 0, q = 0.80 (provided that R = CH ₃ , Y = _{CH 2 CH 2, X = OH} , OCH 3, OC 2 H 5).

[Preparation Example 3]
Instead of the organosilicon compound (i), 67.6 g (0.20 mol) of the following organosilicon compound (iii) and 20.8 g (0.10 mol) of tetraethoxysilane instead of tetraethoxysilane (4.0 mol) ) And 13.6 g (0.1 mol) of methyltrimethoxysilane were used to prepare a coating solution (3) in the same manner as in Preparation Example 1.
When this product was analyzed by GPC, it had a number average molecular weight of 3,450 and a single peak. A resin solution in which each parameter in the general formula (I) is represented by m = 0.50, a = 1, p = 0.25, q = 0.76 (provided that R = CH ₃ , _{Y = CH 2 CH 2, X} = OH, OCH 3, OC 2 H 5).

[Preparation Example 4]
A 2 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 175 g (0.20 mol) of organosilicon compound (i) and 700 g of t-butanol, and stirred and mixed at 25 ° C. To this, 36 g (2.0 mol) of 0.1N hydrochloric acid was added dropwise over 10 minutes. Immediately after the dropping, the solution was cloudy, but gradually generated heat. After 1 hour, hydrolysis was completed and the system became transparent. This is designated coating solution (4) -A.
A 1 liter flask equipped with another stirrer, condenser and thermometer was charged with 832 g (4.0 mol) of tetraethoxysilane. To this, 288 g (16.0 mol) of 0.25N aqueous acetic acid was added dropwise over 30 minutes. Heat was gradually generated, and the internal temperature increased to a maximum of 55 ° C. After completion of dropping, the mixture was stirred at room temperature for 24 hours to prepare a coating liquid (4) -B.
The two were sufficiently mixed and then stored at room temperature for 1 week to prepare a coating solution (4).
When this product was analyzed by GPC, it had a number average molecular weight of 8,120 and a single peak. A resin solution in which each parameter in the general formula (I) is represented by m = 0.07, a = 9, p = 0, q = 0.78 (provided that R = CH ₃ , Y = _{O, X = OH, OCH 3} , OC 2 H 5).

[Preparation Example 5]
A 2 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 338 g (0.20 mol) of the following organosilicon compound (iv), 700 g of t-butanol, and 8 g of a solid acid catalyst, and stirred and mixed at 25 ° C. . Here, 10.8 g (0.6 mol) of ion-exchanged water was dropped in 5 minutes. Immediately after the dropping, the solution was cloudy, but gradually generated heat. After 1 hour, hydrolysis was completed and the system became transparent. To this, 166.4 g (0.8 mol) of tetraethoxysilane was added. After stirring for 1 hour at room temperature, 4.2 g (0.23 mol) of ion-exchanged water was added. After completion of dropping, the mixture was stirred with heating at 60 ° C. for 6 hours. Thereafter, the solid acid catalyst of the catalyst was removed by filtration to prepare a coating liquid (5).

When this product was analyzed by GPC, the number average molecular weight was 2,750, the molecular terminal was an alkoxy group, and each parameter in the general formula (I) was m = 0.20, a = 20, p = 0, A resin solution represented by q = 1.43 was obtained (provided that R = CH ₃ , Y═O, X═OH, OCH ₃ , OC ₂ H ₅ ).

[Comparative Preparation Example 1]
Into a 3 liter flask equipped with a stirrer, a condenser and a thermometer, 175 g (0.20 mol) of the organosilicon compound (i), 700 g of t-butanol, and 8 g of a solid acid catalyst were charged and stirred at 25 ° C. . Here, 36 g (2.0 mol) of ion-exchanged water was dropped in 10 minutes. Immediately after the addition, the solution was cloudy, but gradually generated heat. After 1 hour, hydrolysis was completed, but the system remained slightly opaque. Furthermore, it stirred at room temperature for 24 hours. Thereafter, the solid acid catalyst of the catalyst was removed by filtration to prepare a coating liquid (6).
When this product was analyzed by GPC, it had a number average molecular weight of 1,290 and a single peak. A resin solution in which each parameter in the general formula (I) is represented by m = 1.00, a = 9, p = 0, q = 2.1 (provided that R = CH ₃ , Y = _{O, X = OH, OCH 3} ).

[Comparative Preparation Example 2]
A 0.5 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 97.0 g of butyl acetate and 3.00 g (0.0030 mol) of the following 3-branched organosilicon compound (v) at 25 ° C. for 24 hours. The mixture was stirred and mixed to prepare a coating liquid (7).

[Comparative Preparation Example 3]
In a 2 liter flask equipped with a stirrer, a condenser and a thermometer, 312 g (1.5 mol) of tetraethoxysilane and 450 g of ethanol were charged and mixed with stirring for 30 minutes. A silica sol solution was prepared by adding a mixture of 216 g (12 mol) of 0.004N nitric acid and 20 g of ethanol and stirring at room temperature for 15 hours.
A solution prepared by stirring and mixing 125 g of a 10% solution of 12.5 g (0.0032 mol) of the following organosilicon compound (vi) in ethyl acetate and 3,500 g of methyl ethyl ketone was added to the silica sol solution, The coating liquid (8) was prepared by stirring for 15 hours.

[Example 1]
To 100 g of coating liquid (1), 0.5 g of aluminum acetylacetonate as a curing catalyst and 4900 g of ethanol were added and diluted, and the mixture was sufficiently stirred and mixed to prepare treatment liquid (1). A glass plate whose surface was washed cleanly was immersed in this treatment solution, and the glass plate was pulled up at a speed of 250 mm / min and applied. After air drying for 10 minutes, heat curing was performed at 80 ° C. for 60 minutes to form a cured film on the glass substrate.
When the obtained hardened film was marked with black oil-based magic and then wiped with tissue paper, it was confirmed that it was wiped cleanly and contaminants could be easily removed. Subsequently, using the absorbent cotton impregnated with toluene, the operation of repeatedly rubbing the coating surface was performed 10 times. It replaced | exchanged for the absorbent cotton impregnated with new toluene, and performed the same operation 3 times in total. After that, the black magic ink test was performed again, but it was wiped cleanly, and it was confirmed that this film was durable.

When the water contact angle of this cured coating was measured, it showed a good water repellency of 103 °. This coating was subjected to the same toluene-impregnated absorbent cotton wiping treatment as described above, and the water contact angle was measured. The result showed the same value as 103 °. In addition, when a nell cloth was attached to a reciprocating scratch tester (manufactured by KT Corporation) and reciprocated 500 times under a load of 1.2 kgf / cm ² , the water contact angle was measured again. The value is shown. Thus, it was confirmed that this hardened film shows the durable and excellent water repellency.

[Examples 2 to 5, Comparative Examples 1 to 3]
Using the coating liquids (2) to (6) instead of the coating liquid (1), the same test as in Example 1 was performed based on the following formulation. The coating solutions (7) and (8) were coated as they were. The results are summarized in Table 1.

  In the table, Al in the catalyst column means aluminum acetylacetonate, and P means anhydrous phosphoric acid. However, the addition amount is the same amount.

  ○ in the column of magic ink resistance indicates that it was easily removed, and x indicates that it was not completely removed and a trace remained.

[Example 6]
An acrylic resin primer PC-7A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied and cured on a polycarbonate plate so that the cured film thickness was 3 μm. On top of this, the coating liquid (1) was diluted and blended in the same manner as in Example 1, and a coating treatment was performed using the newly prepared coating liquid. Table 2 shows the results of tests similar to those in Example 1.

Claims (11)

An antifouling coating agent comprising an organosilicon compound represented by the following general composition formula (I).

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and each R may be the same or different. X represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, An acyloxy group, an alkenoxy group, or an —NCO group, Y represents —O—, an alkylene group having 2 to 10 carbon atoms, an arylene group, or a group to which these are bonded, a represents an integer of 1 to 100, m, p and q are numbers satisfying 0.01 ≦ m <1, 0 ≦ p <1, 0.5 ≦ q <3, and 0.51 ≦ m + p + q <4.) The organosilicon compound (I) is (a) an organosilicon compound represented by the following general formula (II) and / or a (partial) hydrolyzate thereof; and (b) an organic represented by the following general formula (III). Using silicon compound and / or its (partial) hydrolyzate, component (a) and component (b) in molar ratio (a) / (b) = 1/99 to 99/1 The antifouling coating agent according to claim 1, wherein the antifouling coating agent is obtained by (partial) cohydrolysis and condensation.

(In the formula, R and a have the same meanings as described above, Z represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group, an alkenoxy group, or an —NCO group, and b represents 0, 1 or 2) And n is 0, 1 or 2.) The organosilicon compound (I) is
(I) hydrolyzing the organosilicon compound represented by the general formula (II);
(Ii) An organosilicon compound represented by the above general formula (III) and / or a (partial) hydrolyzate thereof is added thereto.
(Iii) The antifouling coating agent according to claim 2, which is prepared through a step of (partially) cohydrolyzing and condensing the mixture. Antifouling coating according to claim 1, wherein the polymerization degree a of from 1 to 50 - diorganosiloxy units (-O-SiR _2).   The antifouling coating agent according to any one of claims 1 to 4, wherein the organic substituent R is a methyl group.   Furthermore, the antifouling coating agent of any one of Claims 1-5 containing the condensation catalyst for silicone resins.   Furthermore, the antifouling coating agent of any one of Claims 1-6 containing an organic solvent.   A coated article, wherein the cured film of the antifouling coating agent according to any one of claims 1 to 7 is formed on the substrate directly or via another layer as an antifouling protective film.   The other layer contains a metal oxide layer or a Si-X group (X represents a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group, an alkenoxy group, or a -NCO group). The coated article according to claim 8.   The coated article according to claim 8 or 9, wherein the substrate is plastic, metal, glass or ceramic. The coated article according to claim 8, 9 or 10, which is a transparent article for optical parts.