JP2008150457A - Wiping-up type hydrophilic treatment agent, hydrophilic protective film forming method and hydrophilic protective film - Google Patents

Abstract

【選択図】なしThe present invention provides a wipe-up type hydrophilizing agent that forms a protective film excellent in hydrophilicity, aesthetics, hardness, adhesion, antifouling property and storage stability on the surface of a resin molded product or coating film.
SOLUTION: Hydrolysis condensate of mixture obtained by mixing organosilane compound represented by general formula (1) and silane coupling agent, nonionic surfactant, glycerin, polyalkylene glycol, polyether-modified silicone, etc. A wipe-type hydrophilic treatment agent comprising an aqueous organic compound and water or a mixed solvent of water and a hydrophilic organic solvent.

[Selection figure] None

Description

  The present invention relates to a wiping-up type hydrophilizing agent that hydrophilizes the surface of a hydrophobic resin molded article or coating film. Moreover, it is related with the formation method of the hydrophilic protective film for forming on the surface of a resin molded product or a coating film, and the hydrophilic protective film formed on the surface of a resin molded product or a coating film.

  Conventionally, automobile users have been coated with oil-based wax to protect the appearance of automobile coatings and maintain the gloss and aesthetics of the coatings. However, traces of water droplets remain on the surface of the oil-based wax film, dust components in the atmosphere are adsorbed, and various stains and oil-based wax are combined to adhere to the coating film. .

As a method for solving such a problem, a method of hydrophilizing a hydrophobic coating film surface has been proposed.
For example, Patent Document 1 proposes an antifouling coating solution containing a colloidal inorganic oxide and a surfactant. However, when the coating liquid described in Patent Document 1 is used, a film is formed immediately after application, and it has been difficult to correct the sagging and wiping lines of the liquid during application. In addition, there is a problem that it is difficult to obtain adhesion to the coating film.

  Patent Document 2 proposes a stain-resistant coating composition containing an aliphatic sulfonic acid compound, a carboxy group-containing compound, a specific organosilicate, and a resin component. However, the treatment method using the coating composition described in Patent Document 2 is a method that is applied to the manufacturing process of automobiles, adjusts the film thickness to several tens of μm, and performs heat treatment at 140 ° C. for 30 minutes. Since this method is not simple, it has been difficult for automobile users to perform. Furthermore, when an incomplete hydrolyzate is used as the organosilicate, the contact angle is not reduced and the coating may not be hydrophilized. Even when a completely hydrolyzed product is used, if the heating temperature is increased or the heating time is increased for condensation, the hydrophilic hydroxyl groups generated by hydrolysis are reduced by condensation reaction. As a result, the obtained coating film did not have the expected hydrophilicity, and the pencil hardness was high, which sometimes caused cracks.

  Patent Document 3 proposes a hydrophilization method using a photocatalyst. However, in order to apply the photocatalyst to the automobile coating film, it is necessary to provide a binder layer for protecting the organic coating film from the oxidative decomposition action of the photocatalyst. Moreover, since a heat treatment is required at the time of forming the hydrophilic coating film, it is not an easy method for an automobile user.

Patent Document 4 proposes a hydrophilizing agent containing a specific surfactant, silicate compound, silane coupling agent, organic solvent, catalyst and water. However, even when the hydrophilizing agent described in Patent Document 4 is used, a film is formed immediately after application, and thus it has been difficult to correct the sagging and wiping lines of the liquid during application. Furthermore, the product that has undergone hydrolysis and dehydration condensation reaction in an organic solvent is poorly soluble in the solvent, so that it is likely to be precipitated, the pot life is short, and the storage stability is low.
JP 2003-206416 A JP 2002-69374 A Japanese Patent No. 2917525 JP 2004-269629 A

The present invention has been made in view of the above problems, and an automobile user can easily form a protective film excellent in hydrophilicity, aesthetics, hardness, adhesion and antifouling property on a hydrophobic resin molded article or coating film surface. Another object of the present invention is to provide a wiping-up type hydrophilizing agent that is excellent in storage stability.
In addition, the present invention provides a method for forming a hydrophilic protective film by which an automobile user can easily form a protective film excellent in hydrophilicity, aesthetics, hardness, adhesion and antifouling property on a hydrophobic resin molded product or coating film surface. The purpose is to provide.
Moreover, an object of this invention is to provide the hydrophilic protective film which is excellent in aesthetics, hardness, adhesiveness, and antifouling property.

The present invention includes the following configurations.
[1] (A) An organosilane compound (a-1) represented by the following general formula (1) and a silane coupling agent represented by the following general formula (2) and / or the following general formula (3) ( a hydrolysis condensate of a mixture obtained by mixing a-2),
(B) a liquid aqueous organic compound,
(C) water or a mixed solvent of water and a hydrophilic organic solvent,
A wiping-up type hydrophilization treatment agent containing
The mixing ratio [(a-1) :( a-2)] of the component (a-1) and the component (a-2) in the component (A) is 1: 1 to 20: 1 by mass ratio, and A wipe-up type hydrophilization treatment characterized in that the mass ratio [(A) :( B)] of the content of the component (A) and the content of the component (B) is 1: 9 to 4: 1 Agent.

(In formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents an integer of 1 to 40. .)

(In Formula (2) and Formula (3), R ⁵ , R ⁹ and R ¹⁰ are each independently a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, a phenyl group, a ureido group and a carbon number. 1 to 4 represents a hydrocarbon group having one type of substituent selected from the group consisting of polyoxyalkylene groups or an alkyl group having 1 to 8 carbon atoms, R ^{6 to} R ^8. , R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n ₁ and n ₂ are each independently any one of 1 to 10 Represents an integer.)

[2] (A-1) Hydrolysis condensate of organosilane compound (a-1) represented by the following general formula (1),
(A-2) Hydrolysis condensate of a silane coupling agent (a-2) represented by the following general formula (2) and / or the following general formula (3),
(B) a liquid aqueous organic compound,
(C) water or a mixed solvent of water and a hydrophilic organic solvent,
A wiping-up type hydrophilization treatment agent containing
The mass ratio [(A-1) :( A-2)] of the content of the component (A-1) and the content of the component (A-2) is 1: 1 to 20: 1, and ( The mass ratio [(A-1) + (A-2) :( B)] of the total content of the component A-1) and the component (A-2) and the content of the component (B) is 1: A wipe-up type hydrophilizing agent characterized by being 9-4: 1.

(In formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents an integer of 1 to 40. .)

(In Formula (2) and Formula (3), R ⁵ , R ⁹ and R ¹⁰ are each independently a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, a phenyl group, a ureido group and a carbon number. 1 to 4 represents a hydrocarbon group having one type of substituent selected from the group consisting of polyoxyalkylene groups or an alkyl group having 1 to 8 carbon atoms, R ^{6 to} R ^8. , R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n ₁ and n ₂ are each independently any one of 1 to 10 Represents an integer.)

[3] The (B) liquid aqueous organic compound is at least one compound selected from the group consisting of nonionic surfactants, glycerols, polyalkylene glycols, and polyether-modified silicones. The wiping-up type hydrophilic treatment agent according to [1] or [2].
[4] A method for forming a hydrophilic protective film, wherein the wipe-up type hydrophilizing agent according to any one of [1] to [3] is applied to a substrate and wiped up.
[5] The method for forming a hydrophilic protective film according to [4], wherein a polisher having a soft buff or a soft pad is used for wiping.
[6] A hydrophilic protective film formed by the method for forming a hydrophilic protective film according to [4] or [5].

The wipe-type hydrophilization treatment agent of the present invention allows an automobile user to easily form a protective film excellent in hydrophilicity, aesthetics, hardness, adhesion and antifouling property on a hydrophobic resin molded product or coating film surface. Excellent storage stability.
According to the method for forming a hydrophilic protective film of the present invention, an automobile user can easily form a protective film excellent in hydrophilicity, aesthetics, hardness, adhesion, and antifouling property on a hydrophobic resin molded article or coating film surface. .
The hydrophilic protective film of the present invention is excellent in hydrophilicity, aesthetics, hardness, adhesion and antifouling property.

<Hydrophilic treatment agent>
(First embodiment)
A first embodiment of the wipe-up type hydrophilic treatment agent (hereinafter abbreviated as a hydrophilic treatment agent) of the present invention will be described.
The hydrophilization treatment agent of this embodiment is composed of (A) a hydrolytic condensate of a mixture obtained by mixing an organosilane compound (a-1) and a silane coupling agent (a-2), and (B) a liquid aqueous organic material. A compound and (C) a mixed solvent of water or water and a hydrophilic organic solvent (hereinafter referred to as (C) a mixed solvent of water or water and a hydrophilic organic solvent is referred to as (C) a solvent). Is.

[(A) Hydrolysis condensate]
The organosilane compound (a-1) is a compound represented by the following general formula (1).

R ^{1 to} R ⁴ in Formula (1) each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (specifically, a methyl group, an ethyl group, or a propyl group). In the case of an alkyl group having 4 or more carbon atoms, hydrolysis becomes insufficient, and the strength of the resulting hydrophilic protective film becomes insufficient. M represents an integer of 1 to 40, Preferably, it is an integer from 1 to 20. When m exceeds 40, it becomes difficult to control the hydrolysis-condensation reaction when obtaining the component (A).

Specific examples of the organosilane compound (a-1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, partial hydrolysates of these tetraalkoxysilanes, and partial hydrolyzed condensates of tetraalkoxysilanes. Is mentioned. These may be used alone or in combination of two or more.
Among these organosilane compounds, since the hydrophilicity of the hydrophilic protective film can be further increased, a partial hydrolysis condensate of tetraalkoxysilane is preferable, and a partial hydrolysis condensate of tetramethoxysilane is more preferable.

  The silane coupling agent (a-2) is a compound represented by the following general formula (2) or the following general formula (3).

In formula (2) and formula (3), R ⁵ , R ⁹ and R ¹⁰ are each independently a vinyl group, epoxy group, amino group, methacryl group, mercapto group, phenyl group, ureido group and carbon number 1 Represents a hydrocarbon group having one type of substituent selected from the group consisting of any one of -4 polyoxyalkylene groups, or an alkyl group having 1 to 8 carbon atoms. When R ⁵ , R ⁹ , and R ¹⁰ are alkyl groups having 9 or more carbon atoms, the hydrophilicity and antifouling property of the resulting hydrophilic protective film tend to decrease.
Further, as R ⁵ , R ⁹ , and R ¹⁰ , a hydrocarbon group having a substituent of any one of a polyoxyalkylene group, an epoxy group, an amino group, and a ureido group is obtained because a more hydrophilic protective film is obtained. Is preferred.
R ^{6 to} R ⁸ , R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In the case of an alkyl group having 4 or more carbon atoms, a decrease in crosslinking rate, a decrease in hydrophilicity, and a decrease in antifouling property are significant.
N ₁ and n ₂ each independently represents an integer of 1 to 10. When n ₁ and n ₂ exceed 10, it becomes difficult to form a hydrophilic protective film.

  Specific examples of the silane coupling agent represented by the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, n-hexyltrimethoxysilane, n- Hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, fe Lutriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane Emissions, isocyanate propyl triethoxysilane, silane coupling agents such as polyether-modified trialkoxysilane, partial hydrolysis condensate of partial hydrolyzate and a silane coupling agent of a silane coupling agent. These may be used alone or in combination of two or more.

  Specific examples of the silane coupling agent represented by the general formula (3) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and 3-glycid. Silane coupling agents such as xyloxymethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, polyether-modified dialkoxysilane, and the like of these silane coupling agents Examples thereof include partial hydrolysates and partial hydrolysis condensates of silane coupling agents. These may be used alone or in combination of two or more.

  Among the silane coupling agents represented by the general formula (2) or (3), polyether-modified silane coupling agent, vinyltrimethoxysilane, 3-glycidoxy from the viewpoint of controlling the hydrophilicity of the protective film obtained. Propyltrimethoxysilane, methyltrimethoxysilane, 3-ureidopropyltriethoxysilane, dimethyldiethoxysilane and the like are preferable.

(A) As a method of obtaining a hydrolysis-condensation product, it is 30-70 in presence of 3-100 mass times water with respect to the mixture of an organosilane compound (a-1) and a silane coupling agent (a-2). Hydrolysis condensation is preferably performed at 1 ° C. for 1 to 3 hours.
If the amount of water is 3 to 100 times, the reaction can be easily performed. If the reaction temperature is 30 ° C. or higher, the reaction rate can be increased, but if it exceeds 70 ° C., the effect of improving the reaction rate is saturated, so there is no practical benefit. If the reaction time is 1 hour or more, a sufficient yield can be secured, but there is no practical benefit because the yield does not increase even if the reaction is carried out for 3 hours or more.
In this reaction, a solvent (C) may be contained.

  The mixing ratio [(a-1) :( a-2)] of the organosilane compound (a-1) and the silane coupling agent (a-2) is 1: 1 to 20: 1 in terms of mass ratio. : It is preferable that it is 2-10: 1. When the component (a-1) is mixed so as to exceed 20: 1, the hydrophilic protective film becomes hard and brittle, and it becomes difficult to adhere to the surface of the resin molded product or the coating film. On the other hand, when the component (a-1) is mixed so as to be less than 1: 1, it becomes difficult to form a hydrophilic protective film, and durability is also lowered. Therefore, by mixing the organosilane compound (a-1) and the silane coupling agent (a-2) at the above ratio, the film-forming property and the adhesion on the surface of the resin molded product and the coating film are excellent. A durable hydrophilic protective film can be formed.

When hydrolyzing and condensing the mixture, it is preferable to use a catalyst because the reaction rate increases.
The catalyst for hydrolysis condensation is not particularly limited as long as the hydrolysis of the alkoxysilyl group can proceed. For example, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid , Organic acids such as oxalic acid, paratoluenesulfonic acid, monoalkyl phosphate ester, dialkyl phosphate ester, inorganic bases such as potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonia, monoethanolamine, diethanolamine, Organic bases such as ethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine; amine-based silane coupling agents such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; aluminum tris (acetylacetate) Ne ), Aluminum compounds such as zinc bis (acetylacetonate), titanium compounds such as titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), dibutyltin dilaurate, Examples thereof include tin compounds such as dibutyltin dioctiate and dibutyltin diacetate.

  It is preferable that the usage-amount of a catalyst is 0.1-20 mass% with respect to 100 mass% of total amounts of an organosilane compound (a-1) and a silane coupling agent (a-2). When the amount of the catalyst used is less than 0.1% by mass, hydrolysis does not proceed sufficiently, the crosslinking density becomes insufficient, and hydrophilicity tends to be hardly obtained. Moreover, when the usage-amount of a catalyst exceeds 20 mass%, formation of a hydrophilic protective film may be inhibited and sufficient film strength may not be ensured.

  The content of the (A) hydrolysis condensate in the hydrophilization treatment agent of this embodiment is preferably 0.1 to 10% by mass. (A) If the content of the hydrolysis-condensation product is less than 0.1% by mass, the antifouling property of the resulting hydrophilic protective film tends to decrease, and if it exceeds 10% by mass, The storage stability tends to decrease and the wiping work tends to be difficult.

[(B) Liquid aqueous organic compound]
(B) The liquid aqueous organic compound is a water-soluble or water-dispersible organic compound that is liquid at 25 ° C. and has a boiling point at atmospheric pressure exceeding 250 ° C.
(B) Specific examples of liquid aqueous organic compounds include glycerins such as glycerin, diglycerin, and triglycerin, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyethylene glycol polypropylene glycol copolymers, and polyalkylene glycol alkyl. Nonionic surfactants such as ethers, polyalkylene glycol alkyl esters, and polyglycerin alkyl esters, and polyether-modified silicones such as polyoxyethylene-modified dimethyl silicone are included.

  (B) The viscosity of the liquid aqueous organic compound at 25 ° C. is preferably 100,000 mPa · s or less. (B) When the viscosity of the liquid aqueous organic compound exceeds 100,000 mPa · s, the sagging and streaks during coating cannot be removed by wiping, and a uniform hydrophilic protective film is formed. Becomes difficult.

[(C) Solvent]
(C) The hydrophilic organic solvent in the solvent can dissolve the mixture of the organosilane compound (a-1) and the silane coupling agent (a-2) and its hydrolysis condensate (A), and at atmospheric pressure. Is a water-soluble or water-dispersible liquid organic compound having a boiling point of 250 ° C. or lower.
Specific examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol, n-propanol and isopropanol, glycols such as ethylene glycol and propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol. Examples thereof include glycol ethers such as monoethyl ether, and among these, alcohols and glycol ethers are preferable because they are excellent in volatility and handleability.

  The blending amount of the hydrophilic organic solvent is preferably less than 70 mass% when the solvent (C) is 100 mass%, in other words, water is preferably 30 mass% or more. When the blending amount of the hydrophilic organic solvent exceeds 70% by mass, the hydrolysis condensate (A) tends to be hardly soluble and precipitates, and the pot life tends to be shortened. There is a risk of dissolving the resin molded product or the coating film.

[Composition of each component]
The mass ratio of (A) hydrolysis condensate and (B) liquid aqueous organic compound in the hydrophilization treatment agent of the present embodiment is 1: 9 to 4: 1, and is 1: 4 to 2: 1. It is preferable. When the component (A) exceeds the upper limit, a hard hydrophilic protective film is formed immediately after the hydrophilic treatment agent is applied, so that correction by wiping is difficult. Unable to repair appearance defects caused by streaks and sagging. On the other hand, when the component (A) is contained below the lower limit, it is difficult to form a hydrophilic protective film.

  In the hydrophilization treatment agent of this embodiment, the total amount of (A) hydrolysis condensate and (B) liquid aqueous organic compound is 0.3 to 10 parts by mass, and (C) the solvent is 90 to 99. 0.7 parts by mass is preferable (however, the total is 100 parts by mass). When the total amount of the component (A) and the component (B) is less than 0.3 parts by mass, the hydrophilic protective film cannot be uniformly formed on the entire surface of the resin molded product or the coating film, and defects are generated. As a result, spots may appear and the durability and antifouling properties may not be sufficiently exhibited. When the total amount of the component (A) and the component (B) exceeds 10 parts by mass, a hydrophilic protective film is formed immediately after the hydrophilization treatment agent is applied. The streaks and sagging of the treatment agent are conspicuous and there is a tendency for poor appearance. Moreover, since the hydrophilic protective film surface is difficult to be smooth and adheres unevenly to the surface of the resin molded product or coating film, the hydrophilicity tends to be non-uniform.

[Other ingredients]
In the hydrophilic treatment agent of this embodiment, in addition to the essential components of (A) hydrolysis condensate, (B) liquid aqueous organic compound, and (C) solvent, resin components, fillers, dispersants, Additives such as a sticky agent, an organic ultraviolet ray inhibitor, an organic antioxidant, a leveling agent, and a preservative may be added.
Examples of the resin component include acrylic-urethane resin, epoxy resin, polyester, acrylic resin, urethane resin, alkyd resin, aminoalkyd resin, and silicon resin.
Examples of the filler include silica, organic pigments, inorganic pigments, ceramics, and metal oxides.
The content of the additive in the hydrophilic treatment agent is 30 parts by mass when the total amount of the components (A) to (C) is 100 parts by mass in terms of sufficiently securing the function as the hydrophilic protective film. The following is preferable.

As a result of investigation by the present inventors, according to the hydrophilization treatment agent of the present embodiment containing (A) a hydrolysis condensate, (B) a liquid aqueous organic compound, and (C) a solvent, a spray gun, Without requiring special equipment or technology such as heating equipment, an automobile user can form a uniform protective film on the surface of a hydrophobic resin molded product or the coating film by hand as easily as conventional waxing. The resulting protective film has high hydrophilicity and excellent antifouling properties.
In addition, the hydrophilic protective film obtained by the hydrophilic treatment agent is firmly adhered to the surface of the hydrophobic resin molded product or the coating film, and the pencil hardness is not excessively hard, so that cracks are hardly generated.
Moreover, in this hydrophilic treatment agent, since a film is formed after wiping up, the sagging of the liquid at the time of application | coating and the wiping stripe can be corrected, Therefore The hydrophilic protective film excellent in aesthetics can be formed easily.
Further, the hydrophilizing agent has a long pot life and excellent storage stability.

(Second Embodiment)
A second embodiment of the hydrophilic treatment agent of the present invention will be described.
The hydrophilization treatment agent of this embodiment example is (A-1) hydrolysis condensate of organosilane compound (a-1), (A-2) hydrolysis condensate of silane coupling agent (a-2), (B) It contains a liquid aqueous organic compound, (C) a solvent and, if necessary, an additive.
The organosilane compound (a-1), silane coupling agent (a-2), (B) liquid aqueous organic compound, (C) solvent and additive in the present embodiment are the same as those in the first embodiment. Things are used.

  The hydrolysis condensate of (A-1) and the hydrolysis condensate of (A-2) were prepared without mixing the organosilane compound (a-1) and the silane coupling agent (a-2). It can be obtained by hydrolysis and condensation in the same manner as in the first embodiment except that the hydrolysis and condensation are carried out independently.

  In the hydrophilic treatment agent of this embodiment, the mass ratio [(A-1) :( A-2)] of the content of the component (A-1) and the content of the component (A-2) is 1: 1 to 20: 1, preferably 3: 2 to 9: 1. When the component (A-1) is blended so as to exceed 20: 1, the hydrophilic protective film becomes hard and brittle, and it becomes difficult to adhere to the surface of the resin molded product or the coating film. On the other hand, when the component (A-1) is blended so as to be less than 1: 1, it becomes difficult to form a hydrophilic protective film, resulting in poor durability. Therefore, by mixing the component (A-1) and the component (A-2) at the above ratio, the hydrophilicity is excellent in film formation and adhesion on the surface of the resin molded product or the coating film, and has durability. A protective film can be formed.

  The total content of the component (A-1) and the component (A-2) in the hydrophilic treatment agent of the present embodiment is preferably 0.1 to 10% by mass. When the total content of the component (A-1) and the component (A-2) is less than 0.1% by mass, the antifouling property of the resulting hydrophilic protective film tends to decrease, and exceeds 10% by mass. And, the storage stability of the hydrophilizing agent tends to be reduced, and the wiping operation tends to be difficult.

  Moreover, in the hydrophilization treatment agent of this embodiment, the mass ratio of the total content of the component (A-1) and the component (A-2) and the content of the component (B) is 1: 9-4. : 1 and preferably 1: 4 to 2: 1. When the total ratio of the content of the component (A-1) and the component (A-2) exceeds the upper limit, a hard hydrophilic protective film is formed immediately after applying the aqueous hydrophilizing agent. It cannot be corrected by raising, and the appearance defect caused by streaks or sagging due to the treatment agent cannot be repaired. On the other hand, when the total ratio of the content of the component (A-1) and the component (A-2) is lower than the lower limit, the film-forming property is deteriorated, and a durable hydrophilic protective film can be obtained. It becomes difficult.

  Moreover, in the hydrophilic treatment agent of the present embodiment, the total amount of the component (A-1), the component (A-2) and the component (B) is 0.3 to 10 parts by mass, and the component (C) is 90 parts. It is preferably ˜99.7 parts by mass (however, the total is 100 parts by mass). When the total amount of the component (A-1), the component (A-2), and the component (B) is less than 0.3 part by mass, a hydrophilic protective film is uniformly formed on the entire surface of the resin molded product or the coating film. Since it cannot be performed and a defect is generated, spots are generated in hydrophilicity, and durability and antifouling properties may not be sufficiently exhibited. When the total amount of the component (A-1), the component (A-2), and the component (B) exceeds 10 parts by mass, a hydrophilic protective film is formed immediately after applying the hydrophilic treatment agent. Cannot be corrected, and the streaks and sagging of the hydrophilizing agent are conspicuous, and the appearance tends to be poor. Moreover, since the hydrophilic protective film surface is difficult to be smooth and adheres unevenly to the surface of the resin molded product or coating film, the hydrophilicity tends to be non-uniform.

  Also by the hydrophilization treatment agent of this embodiment containing (A-1) hydrolysis condensate, (A-2) hydrolysis condensate, (B) liquid aqueous organic compound, and (C) solvent. Similarly to the first embodiment, an automobile user can easily form a protective film excellent in hydrophilicity, aesthetics, hardness, adhesion and antifouling property on the surface of a hydrophobic resin molded product or coating film.

<Hydrophilic protective film and method for forming the same>
The formation method of the hydrophilic protective film of this invention is demonstrated. The method for forming a hydrophilic protective film of the present invention is a method for forming the hydrophilic protective film by applying the above-described hydrophilic treatment agent and wiping it.

In this method, examples of the method for applying the hydrophilizing agent include brush coating and spray coating.
The temperature at which the hydrophilizing agent is applied is preferably 0 to 100 ° C. When the temperature exceeds 100 ° C., the volatilization rate of the solvent is too high, so that it is difficult to spread the coating. When the temperature is less than 0 ° C., the solvent is difficult to volatilize, and thus the hydrophilic protective film formation time becomes long. .

  The hydrophilic treatment agent may be applied once, but may be re-applied after being dried to some extent. The recoating is more effective if it is applied again after a lapse of about one week, but it is preferable that the application is performed four times or less continuously in a short time of about 1 hour. This is because an improvement in the effect cannot be expected even if the coating is applied 5 times or more.

  After wiping, it is preferable to leave a aging period for allowing the condensation reaction to proceed sufficiently. If a ripening period is provided, a hydrophilic protective film having further excellent durability can be obtained. The aging temperature is not particularly limited, but is preferably about 10 to 80 ° C. The aging time is not particularly limited but is preferably about 10 minutes to one week.

  At the time of wiping, it is preferable to use a tool that does not damage the surface of the resin molded product or the coating film surface to which the hydrophilic treatment agent is applied. For example, it is preferable to use a cloth, paper, sponge or the like to wipe up manually. In addition, a polisher may be used. In that case, it is preferable to use a polisher provided with a soft buff or a soft pad in order to prevent the surface of the resin molded product or the surface of the coating film from being damaged.

  According to the method described above, an automobile user can easily form a protective film excellent in hydrophilicity, aesthetics, hardness, adhesion, and antifouling property on a hydrophobic resin molded product or a coating film surface.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further, this invention is not limited at all by these Examples.

(Example 1)
In a 1 L separable flask, 25 g of ion-exchanged water, 25 g of ethanol, and 0.1 g of acetic acid were mixed and stirred, and heated to 50 ° C. Next, 1.0 g of a polyether-modified silane coupling agent (manufactured by Nippon Unicar Co., Ltd .: trade name “A-1230”) as the component (a-2), a portion of tetramethoxysilane as the component (a-1) 6.0 g of hydrolyzed condensate (Mitsubishi Chemical Corporation: trade name “MKC silicate MS-51”) was added, and a primary hydrolytic condensation reaction was performed at 50 ° C. for 1 hour.
Next, 100 g of ion-exchanged water was added, and a ripening reaction was further performed at 50 ° C. for 1 hour to perform secondary hydrolytic condensation. Thereafter, 10.0 g of polyether-modified water-soluble dimethyl silicone (B) manufactured by Toray Dow Corning Co., Ltd .: trade name “SH-3746”) is added, and ion-exchanged water is further added to make the total amount 1000 g. A hydrophilic treatment agent was obtained.

  The obtained hydrophilic treatment agent was applied to the following test coating plate and wiped up to form a hydrophilic protective film. And the hydrophilic protective film was evaluated by the evaluation method shown below. The evaluation results are shown in Table 1.

[Method of manufacturing test plate (paint with blue pearl and clear)]
Cationic electrodeposition coating plate (Testpiece Co., Ltd., JIS G-3141 (SPCC SD), 70 mm × 150 mm × 0.8 mm), and intermediate coating (HS60, Kansai Paint Co., Ltd.) dried film thickness 30 μm Then, it was painted with a bar coater and baked at 140 ° C. for 20 minutes. Next, a blue pearl topcoat base coat paint (Magiclon HM32-1, paint number B-96P, manufactured by Kansai Paint Co., Ltd.) was applied with a bar coater to a dry film thickness of 20 μm and baked at 140 ° C. for 20 minutes. Furthermore, a blue pearl topcoat top coat (Luger Bake HK-4 Clear, manufactured by Kansai Paint Co., Ltd.) is applied with a bar coater to a dry film thickness of 30 μm, and baked at 140 ° C. for 20 minutes to contain blue pearl clear. A painted plate was obtained. Further, this coated plate is polished with a compound (Cut 1-L 5967, manufactured by Sumitomo 3M Co., Ltd.), and the polished surface is wiped off with a cotton wool moistened with isopropanol to degrease and paint the test plate (blue Pearl clear paint).

[Production method of test plate (white solid paint)]
Cationic electrodeposition coating plate (Testpiece Co., Ltd., JIS G-3141 (SPCC SD), 70 mm × 150 mm × 0.8 mm), and intermediate coating (HS60, Kansai Paint Co., Ltd.) dried film thickness 30 μm Then, it was painted with a bar coater and baked at 140 ° C. for 20 minutes. Next, a white solid paint (NH-578, manufactured by Kansai Paint Co., Ltd.) was applied with a bar coater to a dry film thickness of 30 μm, and baked at 140 ° C. for 20 minutes to obtain a white solid coated plate. Further, this coated plate was polished with a compound (Cut 1-L 5967, manufactured by Sumitomo 3M Co., Ltd.), and the polished surface was wiped with a cotton wool moistened with isopropanol to degrease, and a test coated plate ( White solid paint).

[Method of forming hydrophilic protective film (hydrophilic treatment method)]
Spray about 0.5 mL of the hydrophilizing agent uniformly onto the entire test piece (70 mm x 150 mm x 0.8 mm) on the above test plate, wipe it with a dry cloth, and finish it in a dry state. Wipe was done. Next, the test coating plate was allowed to stand at 20 ° C. for 30 minutes, rinsed with running water, and then naturally dried to form a hydrophilic protective film. Hereinafter, a coated plate provided with a hydrophilic protective film is referred to as a hydrophilic treatment plate.

[Hydrophilic]
The contact angle of ion-exchanged water was measured using a FACE contact angle measuring instrument (Kyowa Interface Science Instruments Co., Ltd.).
Compared with before and after the hydrophilization treatment, those in which a decrease in contact angle of 10 ° or more is observed: ○, those in which a decrease in contact angle of 5 ° or more and less than 10 ° is recognized; A case where a decrease in contact angle was observed was evaluated as Δ, and a case where an increase in contact angle was observed was evaluated as ×.

[Durable hydrophilicity]
5 mL of a 1% by mass aqueous solution of sodium dodecylbenzenesulfonate was taken in a sponge, and the hydrophilized plate was rubbed for 30 seconds. Next, the sample was rinsed thoroughly with running water, naturally dried, and the contact angle of ion-exchanged water was measured using a FACE contact angle measuring device (Kyowa Interface Science Instruments Co., Ltd.).
The contact angle after the scrubbing treatment is ◯ when the contact angle is decreased by 10 ° or more compared to that before the hydrophilization treatment. ○ The contact angle is decreased by 5 ° or more and less than 10 °. Δ, a case where a decrease in the contact angle of 0 ° or more and less than 5 ° was observed was evaluated as Δ, and a case where an increase in the contact angle was observed was evaluated as ×.

[Sliding water]
After 30 μL of ion-exchanged water was gently adhered on the test coating plate, the coating plate was tilted at a rate of 10 ° / second from the horizontal, and the angle at which the water droplets started to move was defined as the falling angle. . It can be judged that the smaller the angle, the better the water slidability.
Compared with before and after the hydrophilization treatment, a case where a decrease in the falling angle of 10 ° or more is observed, a case where a decrease or an increase in the falling angle of less than 10 ° is observed, and a case where a decrease or increase in the falling angle is observed is 10 ° or more. What was recognized or what spread | wetted and the fall of a water droplet is not recognized is set as x.
The water slidability is an index of the difficulty of remaining water droplets, and the higher the water slidability, the less likely it is to get dirt and the less the damage to the coating film caused by the lens effect of water droplets.

[Glossiness]
Using a micro-TRI-gloss (manufactured by Bic Gardner), the 20 ° gloss of the test coating plate was measured.
Compared with before and after hydrophilization treatment, 20 ° gloss improved by 3 points or more, ○, 20 ° gloss improved by 1 point or more and less than 3 points, ○ △, 20 ° gloss improved by less than 1 point Δ, and 20 ° gloss decreased by 1 point or more was evaluated as x.
Glossiness is an indicator of appearance.

[Anti-fouling]
On the roof of a five-story building in Fukui City, Fukui Prefecture, an exposure test was conducted at 45 ° southward for 30 days. The average temperature during the test period was 21.9 ° C., precipitation was 32 mm, and sunshine duration was 153 hours. The brightness before and after the exposure test was measured with a color difference meter (manufactured by Konica Minolta, CR-200).
A value where the decrease in brightness before and after the exposure test was less than 0.3 was evaluated as ◯, a value of 0.3 or more and less than 0.7 was evaluated as Δ, and a value of 0.7 or more was evaluated as ×.

In addition, the abbreviation in Table 1 represents the following compound.
MS-51: Partially hydrolyzed condensate of tetramethoxysilane (Mitsubishi Chemical Corporation: trade name “MKC silicate MS-51”)
TEOS: Tetraethoxysilane A-1230: Polyether-modified silane coupling agent (Nihon Unicar Co., Ltd.)
KBM-1003: Vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
SH-3746: Polyether-modified water-soluble dimethyl silicone (manufactured by Dow Corning Toray)
Softanol 70: nonionic surfactant (manufactured by Nippon Shokubai Co., Ltd.)

(Examples 2 to 12)
It is hydrophilic similarly to Example 1 except having changed the kind and compounding quantity of (a-1) component, (a-2) component, (B) component, (C) component as shown in Table 1 or 2. A chemical treatment agent was obtained. And it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 1 or 2.

In addition, the abbreviation in Table 2 represents the following compound.
M2-diethoxy: dimethyldiethoxysilane (Asahi Kasei Wacker Silicone Co., Ltd.)
TES40WN: Methyltrimethoxysilane partial hydrolysis condensate (Asahi Kasei Wacker Silicone Co., Ltd.)

(Example 13)
In a 300 mL separable flask, 20 g of ion-exchanged water, 30 g of isopropanol, and 0.05 g of phosphoric acid were mixed and stirred, and heated to 50 ° C. Next, 6.0 g of a partially hydrolyzed condensate of tetramethoxysilane as component (a-1) (manufactured by Mitsubishi Chemical Co., Ltd .: trade name “MKC silicate MS-51”) was added, and the mixture was stirred at 50 ° C. for 1 hour. A primary hydrolysis condensation reaction was performed.
Next, 50 g of ion-exchanged water was added, and an aging reaction was further performed at 50 ° C. for 1 hour, followed by secondary hydrolysis and condensation to obtain (A-1) a hydrolysis-condensation product.
Separately, 20 g of ion exchange water, 30 g of isopropanol, and 0.1 g of acetic acid were placed in a 300 mL separable flask, mixed and stirred, and heated to 50 ° C. Next, 1.0 g of a polyether-modified silane coupling agent (manufactured by Nippon Unicar Co., Ltd .: trade name “A-1230”), which is the component (a-2), is added, and primary hydration at 50 ° C. for 1 hour A decomposition condensation reaction was performed to obtain a hydrolysis condensate (A-2).
Next, 500 g of ion-exchanged water was placed in a 1 L separable flask and heated to 50 ° C., and the (A-1) hydrolysis condensate and (A-2) hydrolysis condensate were added and mixed and stirred. Then, 10 g of polyether-modified water-soluble dimethyl silicone (product of Toray Dow Corning Co., Ltd .: trade name “SH-3746”) as component (B) is added, and ion exchange water is added to make the total amount 1000 g hydrophilic. A treating agent was obtained. And it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 2.

(Comparative Examples 1-4)
A hydrophilic treatment agent is obtained in the same manner as in Example 1 except that the blending amounts of the component (a-1), the component (a-2), the component (B), and the component (C) are changed as shown in Table 3. It was. And it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 3.

(Comparative Example 5)
1. In a 1 L separable flask, 50 g of colloidal silica (manufactured by Nissan Chemical Industries, trade name “Snowtex 20”), surfactant sulfosuccinic acid di (2-ethylhexyl) ester sodium salt (active ingredient 70%) 5 g was mixed and stirred. Thereafter, water was added to make the total amount 1000 g to obtain a hydrophilic treatment agent. And it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 3.

(Comparative Example 6)
6.0 g of a partially hydrolyzed condensate of tetramethoxysilane as component (a-1) (manufactured by Mitsubishi Chemical Corporation: trade name “MKC silicate MS-51”) in a 1 L separable flask, component (a-2) Polyether-modified silane coupling agent (manufactured by Nippon Unicar Co., Ltd .: trade name “A-1230”) 1.0 g, polyether-modified water-soluble dimethyl silicone (B) component (Toray Dow Corning Co., Ltd.) (Product name: “SH-3746”) 10 g was mixed and stirred, and component (C) isopropanol was added to make the total amount 1000 g. Thereafter, 0.1 g of aluminum tris (acetylacetonate) was added and stirred for 10 minutes, and then 10 g of water was added and stirred at room temperature (25 ° C.) for 3 hours to obtain a hydrophilic treatment agent. Table 3 shows the results of the same evaluation test as in Example 1 using this hydrophilizing agent.

(Comparative Example 7)
A test piece coated with a commercially available carnauba wax (manufactured by Shuaraster: trade name “Impact Master Finish”) on the test plate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Comparative Example 8)
The test coating plate itself was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

In addition, the abbreviation in Table 3 represents the following compound.
D2EH-SS · Na: sulfosuccinic acid di (2-ethylhexyl) ester sodium salt

Example 1 containing hydrolysis condensate of mixture of organosilane compound (a-1) and silane coupling agent (a-2), (B) liquid aqueous organic compound and (C) solvent within specific range According to the hydrophilizing agent of -12, the protective film which was excellent in all of hydrophilic property, durable hydrophilic property, water slidability, glossiness, and antifouling property was able to be formed.
Further, the hydrolyzed condensate of organosilane compound (a-1), the hydrolyzed condensate of silane coupling agent (a-2), (B) a liquid aqueous organic compound and (C) a solvent are contained within a specific range. The hydrophilic treatment agent of Example 13 was able to form a protective film excellent in all of hydrophilicity, durable hydrophilicity, water slidability, glossiness and antifouling property.

On the other hand, in the hydrophilic treatment agent of Comparative Example 1 in which the mixing ratio of the organosilane compound (a-1) was less than the lower limit value, the durable hydrophilic property of the protective film was low.
In the hydrophilic treatment agent of Comparative Example 2 in which the mixing ratio of the silane coupling agent (a-2) was less than the lower limit value, the water slidability of the protective film was low.
(B) In the hydrophilic treatment agent of Comparative Example 3 in which the amount of the liquid aqueous organic compound was larger than the upper limit value, the hydrophilicity and durability hydrophilicity of the protective film were low.
(B) In the hydrophilizing agent of Comparative Example 4 in which the amount of the liquid aqueous organic compound was less than the lower limit, the water slidability of the protective film was low. Moreover, glossiness was low and appearance defect was seen.
In the hydrophilization treatment agent of Comparative Example 5 containing colloidal silica instead of containing the component (A), the component (A-1) and the component (A-2), the durable hydrophilic property, water slidability, and gloss of the protective film The sex was low.
(A) In the hydrophilic treatment agent of Comparative Example 6 containing no hydrolysis condensate, the hydrophilicity of the protective film was insufficient and the glossiness was low.
In Comparative Example 7, which is a conventional example using carnauba wax, a protective film having hydrophilicity and antifouling properties could not be obtained.
Further, Comparative Example 8 which is an untreated test coating plate does not exhibit hydrophilicity, durable hydrophilicity, water slidability, glossiness and antifouling property.

  The present invention is suitably used for protecting the appearance of automobile coatings and resin molded products.

Claims (6)

(A) An organosilane compound (a-1) represented by the following general formula (1) and a silane coupling agent (a-2) represented by the following general formula (2) and / or the following general formula (3) Hydrolyzed condensate of a mixture of
(B) a liquid aqueous organic compound,
(C) water or a mixed solvent of water and a hydrophilic organic solvent,
A wiping-up type hydrophilization treatment agent containing
The mixing ratio [(a-1) :( a-2)] of the component (a-1) and the component (a-2) in the component (A) is 1: 1 to 20: 1 by mass ratio, and A wipe-up type hydrophilization treatment characterized in that the mass ratio [(A) :( B)] of the content of the component (A) and the content of the component (B) is 1: 9 to 4: 1 Agent.

(In formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents an integer of 1 to 40. .)

(In Formula (2) and Formula (3), R ⁵ , R ⁹ and R ¹⁰ are each independently a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, a phenyl group, a ureido group and a carbon number. 1 to 4 represents a hydrocarbon group having one type of substituent selected from the group consisting of polyoxyalkylene groups or an alkyl group having 1 to 8 carbon atoms, R ^{6 to} R ^8. , R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n ₁ and n ₂ are each independently any one of 1 to 10 Represents an integer.) (A-1) Hydrolysis condensate of organosilane compound (a-1) represented by the following general formula (1),
(A-2) Hydrolysis condensate of a silane coupling agent (a-2) represented by the following general formula (2) and / or the following general formula (3),
(B) a liquid aqueous organic compound,
(C) water or a mixed solvent of water and a hydrophilic organic solvent,
A wiping-up type hydrophilization treatment agent containing
The mass ratio [(A-1) :( A-2)] of the content of the component (A-1) and the content of the component (A-2) is 1: 1 to 20: 1, and ( The mass ratio [(A-1) + (A-2) :( B)] of the total content of the component A-1) and the component (A-2) and the content of the component (B) is 1: A wipe-up type hydrophilizing agent characterized by being 9-4: 1.

(In formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents an integer of 1 to 40. .)

(In Formula (2) and Formula (3), R ⁵ , R ⁹ and R ¹⁰ are each independently a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, a phenyl group, a ureido group and a carbon number. 1 to 4 represents a hydrocarbon group having one type of substituent selected from the group consisting of polyoxyalkylene groups or an alkyl group having 1 to 8 carbon atoms, R ^{6 to} R ^8. , R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n ₁ and n ₂ are each independently any one of 1 to 10 Represents an integer.)   (B) The liquid aqueous organic compound is at least one compound selected from the group consisting of nonionic surfactants, glycerols, polyalkylene glycols, and polyether-modified silicones. Or the wipe-up type hydrophilization treatment agent of 2 or 2.   A method for forming a hydrophilic protective film, comprising applying a wipe-up type hydrophilic treatment agent according to any one of claims 1 to 3 to a substrate and wiping it up.   The method for forming a hydrophilic protective film according to claim 4, wherein a polisher having a soft buff or a soft pad is used for wiping.   A hydrophilic protective film formed by the method for forming a hydrophilic protective film according to claim 4.