JP5480664B2 - Hydrophilic coating material composition and outer housing member - Google Patents

Description

  The present invention relates to a hydrophilic coating material composition that imparts hydrophilicity by painting, and particularly relates to a hydrophilic coating material composition suitable for the outer periphery of a house and an outer housing member.

  In the exterior of a house, the use of various pollution prevention techniques improves the maintenance of the appearance, and further improves maintenance-free. As a contamination prevention technique, a water repellent treatment (for example, Patent Documents 1 and 2) is applied to the surface to suppress the adhesion of dirt substances to prevent deterioration of the appearance, and hydrophilic treatment (for example, Patent Documents 3 and 4) ) Is applied to the surface, and a technique for protecting the appearance by making it possible to easily remove dirt substances by running water such as rain is known.

JP 7-268245 A JP-A-6-002444 JP 2002-234105 A JP 2000-336336 A

  The water- and oil-repellent coatings and hydrophilic / lipophilic coatings described above have advantages and disadvantages, respectively, and may not be able to exhibit sufficient antifouling properties.

  For example, a water- and oil-repellent coating using a fluororesin has excellent weather resistance due to high binding energy, and has excellent low adhesion, so that contaminants are difficult to adhere. However, it is difficult to naturally remove the contaminants once adhered by rain or the like, so that when the dirt is generated, the appearance is deteriorated.

  In addition, hydrophilic lipophilic coating is excellent in easy washing with water, and is characterized by easy removal of contaminants due to rain or the like. However, in the technology for imparting hydrophilicity by adding hydrophilic additives such as surfactants to paints such as acrylic and silicone, the additives remain in the middle layer of the coating film, resulting in poor coating such as water whitening. May cause it. In addition, a technique for obtaining a hydrophilic surface by adding a hydrophilic coating to the surface of a coating film such as acrylic is also known, but the disadvantage is that the total cost increases due to an increase in the treatment process by coating. is there.

  The present invention has been made in view of the above points, and has hydrophilicity to form a film that has excellent weather resistance, hardly adheres to contaminants, and can be easily removed even if contaminants adhere. An object of the present invention is to provide a coating material composition.

  In order to solve the above problems, the present invention has the following configuration.

The first invention comprises (X) at least one selected from silicon alkoxides and partial hydrolysates thereof, and (Y) a component containing a fluoroalkyl group, a component containing an ethylene oxide chain, and a silicon alkoxy group. And a fluorine-containing oligomer obtained by copolymerization, and the component (Y) is 1 to 30 parts by mass in terms of solid content with respect to 100 parts by mass of the solid content of the component (X). The fluorine-containing oligomer of the component (Y) contains the following monomers (A), (B) and (C), and is in a mass ratio:
Monomer (A) / Monomer (B) = 1 / 99-60 / 40
{Monomer (A) + monomer (B)} / monomer (C) = 100/1 to 100/15
It is a hydrophilic coating material composition characterized by being copolymerized in the ratio shown by these .

Monomer (A) is
_{Rf-Q-OCOC (R 3} ) = CH 2
(In the formula, Rf represents a C1-C20 fluoroalkyl group. Q represents — (CH ₂ ) _n1 — or —CH ₂ CH ₂ CH (CH ₃ ) —, where n1 is 1 Represents an integer of ˜3, and R ₃ represents a hydrogen atom or a methyl group.)
It is.

Monomer (B) is
HO (C ₂ H ₄ O) ₁₁ (C ₃ H ₆ O) _{m 2} (C ₂ H ₄ O) n ₂ COC (R ₄ ) = CH ₂
(Wherein, _{R 4} is, .L1 represents a hydrogen atom or a methyl group, m2 and n2 represents an integer of 1 to 100.)
It is.

Monomer (C) is
_{CH 2 = C (R 5)} COO (CH 2) m3 Si (O (R 6)) 3
(In the formula, R ₅ represents a hydrogen atom or a methyl group. R ₆ represents the same or different alkyl group having 1 to 8 carbon atoms. M3 represents an integer of 0 to 10.)
It is.

A second invention is the hydrophilic coating material composition according to the invention having the above structure, wherein the silicon alkoxide of the component (X) includes the following components (D) and (E).

Ingredient (D)
(R ₇ ) _n3 SiX _4-n3 (wherein R ₇ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, X represents a hydrolyzable group, and n3 represents 0 to 0) 3 is an organosilane silica-dispersed oligomer obtained by dispersing hydrolyzable organosilane represented by the general formula (3) in at least one organic solvent and water and partially hydrolyzing in colloidal silica. It is a solution.

Ingredient (E)
(R ₈ ) _d Si (OH) _e O _{(4-de) / 2} (wherein R ₈ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and d and e represents an average composition formula of 0.2 ≦ d ≦ 2.0 and 0.0001 ≦ e ≦ 3 and d + e <4), and a polysiloxane containing silanol groups in the molecule. Organosiloxane.

3rd invention is the outer-circumpart housing member by which the hydrophilic coating material composition of the said structure was painted.

  According to the hydrophilic coating material composition of the present invention, it is possible to form a film that improves weather resistance, makes it difficult for contaminants to adhere, and easily removes the adhered materials when the contaminants adhere.

  The hydrophilic coating material composition includes (X) at least one selected from silicon alkoxide and a partial hydrolyzate thereof, and (Y) a component containing a fluoroalkyl group, a component containing an ethylene oxide chain, and silicon. And a fluorine-based oligomer obtained by copolymerization with a component containing an alkoxy group.

  In response to the above problems, the inventors have studied the development of a highly durable hydrophilic coating material. First, regarding durability, it is desirable to use an inorganic material as the binder resin, and it is desirable that the surface of the coating film is hydrophilic from the viewpoint of antifouling properties. Generally, as a silicone binder, a trifunctional or bifunctional silicon alkoxide (alkoxysilane) having a methyl group or a phenyl group is used as a raw material from the viewpoint of film formability and crack prevention. However, when trifunctional or bifunctional silicon alkoxide is used as a silicone binder, the surface becomes water-repellent. Therefore, it is conceivable to add a hydrophilizing agent. Even if a hydrolyzate of tetrafunctional silicon alkoxide is mixed in a trifunctional or bifunctional silicone binder as a hydrophilizing agent, the surface becomes water-repellent and the object is achieved. I can't.

  In view of these points, as a result of repeated studies, first, if a fluorine-based oligomer is used as a long-chain silicon group having a low surface free energy, a hydrophilic group component is formed in the vicinity of the coating film surface by a single coating. It was found that can be manifested. Here, as the fluorine-based oligomer, a copolymer of a component containing an ethylene oxide chain which is a hydrophilic group and a component containing a fluoroalkyl group is used. However, since this copolymer does not have a reactive site with the silicone resin, there is a problem that the water resistance is poor and the hydrophilicity cannot be maintained for a long time. Therefore, it was found that long-term sustainability can be ensured by copolymerizing silicon alkoxide with this copolymer.

  Furthermore, the blending ratio of each component was examined. When long-chain silicon groups or fluoroalkyl groups contained in the copolymer are present in a large amount on the surface of the coating film, the coating film has water repellency, so these groups are desirably as small as possible. On the other hand, in order to impart hydrophilicity to the coating film, it is desirable to have as many hydrophilic groups as possible. In addition, when there is a large amount of the reaction part of the copolymer, it is desirable that it is as small as possible since there is a risk that the storage stability of the copolymer may be impaired. Thus, the hydrophilic coating material composition is completed.

  And according to this hydrophilic coating material composition, since it is obtained by reacting a highly durable silicone resin with a fluorine-based oligomer, the above problems can be solved, and durability such as outdoors is required. It can be used in applications that are easily contaminated.

  Component (X) is a matrix resin that is a main component of the resin composition. The silicon alkoxide is preferably a compound represented by the following general formula.

(R ₁ ) _m Si (OR ₂ ) _4-m
(Wherein R ₁ represents a methyl group, an ethyl group or a phenyl group, and may be the same or different. R ₂ represents an alkyl group having 1 to 8 carbon atoms, and may be the same or different. M is an integer of 0, 1 or 2)
As the component (X), the above silicon alkoxide may be used, a partial hydrolyzate of the above silicon alkoxide may be used, and both the above silicon alkoxide and the hydrolyzate thereof may be used. It may be. This component (X) is an inorganic resin. Such component (X) functions as a silicon alkoxide binder.

  Usually, the silicon compound represented by the above general formula exhibits water repellency due to the influence of its functional group. In that case, it is preferable that said silicon alkoxide contains at least any 1 type (namely, m = 1, 2) of a trifunctional and bifunctional compound. In addition, the water repellency exerted can make it difficult to attach contaminants in the initial stage. However, when only the compound is used, contamination becomes conspicuous when observed over time. Therefore, the fluorine-based oligomer represented by (Y) can be added, and the hydrophilic group contained therein can be used to demonstrate hydrophilicity so that contaminants can be easily washed away by rain during outdoor use. is there.

  Component (Y) is contained in an amount of 1 to 30 parts by mass in terms of solid content with respect to 100 parts by mass of the solid content of component (X). When the ratio of (X) and (Y) is within this range, sufficient strength and durability are imparted to the coating film, and the coating film exhibits high easy cleaning properties. When the content of (Y) with respect to (X) is less than 1 part by mass, the coating film does not exhibit wettability and does not exhibit sufficient easy cleaning properties. In addition, when the content of (Y) with respect to (X) exceeds 30 parts by mass, the coating film becomes cloudy from the beginning or whitens with warm water, and sufficient strength and durability are imparted to the coating film. Disappear.

  In the component (Y), the component containing a fluoroalkyl group functions as a water repellent part. The water-repellent part has an excellent ability to lower the surface energy, and imparts water repellency to the coating to suppress adhesion of contaminants. Moreover, the component containing an ethylene oxide chain functions as a hydrophilic part. The hydrophilic portion makes the coating film hydrophilic and facilitates removal of contaminants attached thereto. Moreover, the component containing a silicon alkoxy group functions as a reaction part. The reaction part increases the reactivity with the component (X) to increase the long-term durability of weather resistance and contamination resistance. When the fluorinated oligomer contains these three components and is copolymerized, the weather resistance and stain resistance of the coating film are improved.

  The component (Y) is preferably a copolymer containing the monomer (A), the monomer (B) and the monomer (C). That is, the monomer (A), the monomer (B), and the monomer (C) are the raw materials for the copolymer.

  The monomer (A) is the following compound.

_{Rf-Q-OCOC (R 3} ) = CH 2
(In the formula, Rf represents a C1-C20 fluoroalkyl group. Q represents — (CH ₂ ) _n1 — or —CH ₂ CH ₂ CH (CH ₃ ) —, where n1 is 1 Represents an integer of ˜3, and R ₃ represents a hydrogen atom or a methyl group.)
This monomer (A) contains a fluoroalkyl group which is a water repellent group and functions as a water repellent part.

  The monomer (B) is the following compound.

HO (C ₂ H ₄ O) ₁₁ (C ₃ H ₆ O) _{m 2} (C ₂ H ₄ O) n ₂ COC (R ₄ ) = CH ₂
(Wherein, _{R 4} is, .L1 represents a hydrogen atom or a methyl group, m2 and n2 represents an integer of 1 to 100.)
This monomer (B) contains an ethylene oxide chain that is a hydrophilic group, and functions as a hydrophilic portion.

  The monomer (C) is the following compound.

_{CH 2 = C (R 5)} COO (CH 2) m3 Si (O (R 6)) 3
(In the formula, R ₅ represents a hydrogen atom or a methyl group. R ₆ represents the same or different alkyl group having 1 to 8 carbon atoms. M3 represents an integer of 0 to 10.)
This monomer (C) contains a silicon alkoxy group which is a reactive functional group, and functions as a reaction part.

  Rf in the monomer (A) is not particularly limited as long as it is a fluoroalkyl group (an alkyl group in which one or more of the hydrogen atoms are substituted with fluorine atoms), but has excellent ease of production and excellent surface tension reducing ability. From the viewpoint of properties, it is preferably a perfluoroalkyl group (an alkyl group in which all of the hydrogen atoms are substituted with fluorine atoms). Rf preferably has 4 to 18 carbon atoms, and particularly preferably 4 to 12 carbon atoms.

Monomer having a perfluoroalkyl group having 4 to 12 carbon atoms Specific examples of the (A) _{is, C 8 F 17 CH 2 CH} 2 OCOCH = CH 2, C 8 F 17 CH 2 CH 2 OCOC (CH 3) _{= CH 2, C 10 F 21} CH 2 CH 2 OCOCH = CH 2, C 10 F 21 CH 2 CH 2 OCOC (CH 3) = CH 2, C 12 F 25 CH 2 CH 2 OCOCH = CH 2, C 12 F ₂₅ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ , C ₆ F ₁₃ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , C ₈ F ₁₇ CH _{2 CH 2 CH 2 OCOCH = CH 2} , C 8 F 17 CH 2 CH 2 CH 2 OCOC (CH 3) = CH 2, C 8 F 17 CH 2 CH 2 CH ( _{H 3) OCOCH = CH 2,} C 8 F 17 CH 2 CH 2 CH (CH 3) OCOC (CH 3) = CH 2, C 4 F 9 CH 2 CH 2 OCOCH = CH 2, C 4 F 9 CH 2 CH ₂ OCOC (CH ₃ ) ═CH _{2 and the} like.

  The monomer (B) contains at least one polyoxyalkylene group of a polyoxyethylene group and a polyoxypropylene group as shown in the above formula, and of these, the monomer (B) may contain a polyoxyethylene group. preferable. When the polyoxyalkyl group is composed only of the polyoxypropylene group and the monomer (B) does not contain the polyoxyethylene group, the solubility of the copolymer in water is remarkably lowered and the wettability is lowered. There is a risk.

  In the monomer (B), l1, m2, and n2 are preferably integers of 5 to 60, particularly preferably 10 to 40. l1, m2, and n2 do not need to be the same number, and may be different numbers or the same number.

Examples of the monomer (B) include (meth) acrylates in which l1 is 4 to 10, m2 is 8 to 20, and n2 is 4 to 10. _{Specifically, HO (C 2 H 4 O} ) 4 (C 3 H 6 O) 8 (C 2 H 4 O) 4 COCH = CH 2, HO (C 2 H 4 O) 4 (C 3 H 6 O ) ₈ (C ₂ H ₄ O) ₄ COC (CH ₃ ) ═CH ₂ , HO (C ₂ H ₄ O) ₁₀ (C ₃ H ₆ O) ₂₀ (C ₂ H ₄ O) ₁₀ COCH═CH ₂ , HO _{(C 2 H 4 O) 10} (C 3 H 6 O) 20 (C 2 H 4 O) 10 COC (CH 3) = CH 2, HO (C 2 H 4 O) 20 (C 3 H 6 O) 40 (C ₂ H ₄ O) ₂₀ COCH═CH ₂ , HO (C ₂ H ₄ O) ₂₀ (C ₃ H ₆ O) ₄₀ (C ₂ H ₄ O) ₂₀ COC (CH ₃ ) ═CH ₂ , CH ₂ = _{CHCOO (C 2 H 4 O)} 4 (C 3 H 6 O) 8 (C 2 H 4 O) 4 COCH = CH 2, CH _{2 = C (CH 3) COO} (C 2 H 4 O) 4 (C 3 H 6 O) 8 (C 2 H 4 O) 4 COC (CH 3) = CH 2, CH 2 = CHCOO (C 2 H 4 O) ₁₀ (C ₃ H ₆ O) ₂₀ (C ₂ H ₄ O) ₁₀ COCH═CH ₂ , CH ₂ ═C (CH ₃ ) COO (C ₂ H ₄ O) ₁₀ (C ₃ H ₆ O) ₂₀ ( _{C 2 H 4 O) 10 COC} (CH 3) = CH 2, CH 2 = CHCOO (C 2 H 4 O) 20 (C 3 H 6 O) 40 (C 2 H 4 O) 20 COCH = CH 2, CH _{2 = C (CH 3) COO} (C 2 H 4 O) 20 (C 3 H 6 O) 40 (C 2 H 4 O) 20 COC (CH 3) = CH 2 and the like.

  The monomer (C) has a silicon alkoxy group (alkoxysilane group). It is preferable to use a trifunctional alkoxysilane as in the above formula. As the monomer (C), specifically, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Etc. In place of the monomer (C), 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, vinyltrichlorosilane, or the like may be used. Of these, 3-methacryloxypropyltrimethoxysilane is particularly preferable because of easy control of the reaction and easy availability.

  The fluorine-based oligomer is preferably one in which the monomers (A), (B) and (C) are copolymerized within a range of a polymerization ratio (mass ratio) satisfying the following two formulas.

[Formula showing polymerization ratio (Formula 1)]
Monomer (A) / Monomer (B) = 1 / 99-60 / 40
[Formula showing polymerization ratio (Formula 2)]
{Monomer (A) + monomer (B)} / monomer (C) = 100/1 to 100/15
As long as the polymerization ratio is copolymerized within this range, any structure such as block, random, alternating, or graft may be used. For example, the graft ratio of the graft copolymer, the random copolymer Randomness is not particular. Furthermore, the monomers (A), (B) and (C) can be used alone or in a mixture of two or more as long as each monomer is within the range represented by the above structural formula. It is.

  The copolymerization ratio (mass ratio) of the monomers (A) and (B) varies depending on the blending component in the composition in which the copolymer is blended and the level of the intended physical properties, but the above range. (Formula 1) is preferable, (A) / (B) = 1/99 to 50/50 is more preferable, and (A) / (B) = 1/99 to 12/88. More preferably. If the proportion of the monomer (A) is greater than the above range, the solubility of the copolymer in water may be reduced, and the coating may not exhibit wettability. On the contrary, when the proportion of the monomer (B) is larger than the above range, the ability of the copolymer to lower the surface tension decreases, the fluorine oligomer cannot be concentrated in the vicinity of the surface, and the film has wettability. May not develop.

  The monomer (C) is preferably polymerized with the monomers (A) and (B) in the above-mentioned range (formula 2). When the proportion of the monomer (C) is in excess of the above range, the fluorine-based oligomer is taken into the binder matrix before being oriented on the surface, and the desired hydrophilicity cannot be obtained in the coating film. There is a fear. In addition, the stability of the fluorinated oligomer may be impaired and gelation may be induced. On the other hand, when the proportion of the monomer (C) is less than the above range, the reaction with the binder matrix becomes insufficient, and the wettability due to the hot water test or the like may be reduced.

  The molecular weight of the fluorine-based oligomer is preferably 1,000 to 100,000, particularly preferably 2,000 to 100,000, as the weight average molecular weight Mw in terms of polymethyl methacrylate. When Mw is less than 1,000, sufficient surface tension lowering ability is difficult to be obtained, and conversely, when Mw exceeds 100,000, the compatibility with the blend in the composition may be reduced. . The molecular weight of the fluorine-based oligomer can be measured by GPC (gel permeation chromatography) in terms of standard polystyrene.

  There is no limitation on the production method of the fluorine-based oligomer, and based on a known method, that is, a polymerization method such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, etc., a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. Can be manufactured. That is, a method of polymerizing a carbon-carbon double bond can be employed. In particular, the monomers (A), (B) and (C) have an acryl group or a methacryl group. An appropriate method for polymerizing a group or a methacryl group can be employed. Of these, the radical polymerization method is particularly convenient and industrially preferable.

  In the case of radical polymerization, known polymerization initiators can be used, such as peroxides such as benzoyl peroxide, azo compounds such as azobisisobutylnitrile, transition metal catalysts that cause living radical polymerization, etc. Is mentioned.

  Furthermore, chain transfer agents such as octyl mercaptan and 2-mercaptoethanol can be used as necessary.

  The above polymerization can be carried out in the presence of a solvent or water or without a solvent, but the polymerization in the presence of a solvent is preferred from the viewpoint of workability. Solvents include alcohols such as ethanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate, methyl lactate, and butyl lactate, dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone Polar solvents such as methyl cellosolve, ethers such as butyl cellosolve and butyl carbitol, propylene glycols and esters such as propylene glycol and propylene glycol monoethyl ether acetate, halogen compounds such as chloroform and 1,1,1-trichloroethane , Aromatic hydrocarbons such as benzene, toluene, xylene, and fluorinated inner-trikids such as perfluorooctane. These may be used alone or in combination. It can be used.

  The silicon alkoxide of the component (X) preferably includes the following components (D) and (E).

Component (D) is partially hydrolyzed in colloidal silica by dispersing a hydrolyzable organosilane represented by the general formula (R ₇ ) _n3 SiX _{4-n3 in} at least one organic solvent and water. This is a silica-dispersed oligomer solution of organosilane. Here, in the general formula, R ₇ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, X represents a hydrolyzable group, and n3 represents an integer of 0 to 3. Show.

Component (E) is a polyorganosiloxane having an average composition formula represented by (R ₈ ) _d Si (OH) _e O _{(4-de) / 2} and containing a silanol group in the molecule. In the average composition formula, each R ₈ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. In the average composition formula, d and e indicate numbers satisfying the relations 0.2 ≦ d ≦ 2.0, 0.0001 ≦ e ≦ 3, and d + e <4, respectively.

Specific examples of R _{7 in} the hydrolyzable organosilane of component (D) include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; Aryl groups such as phenyl group and Tolyl group; Alkenyl groups such as vinyl group and allyl group; Chloromethyl group Halogen substituted hydrocarbon groups such as γ-chloropropyl group, 3,3,3-trifluoropropyl group; γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ -Substituted hydrocarbon groups such as a mercaptopropyl group can be exemplified. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable because of easy synthesis or availability.

  Examples of the hydrolyzable group X in the hydrolyzable organosilane of component (D) include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, and an amide group. Among these, an alkoxy group is preferable because it is easily available and a silica-dispersed oligomer solution can be easily prepared. Examples of such hydrolyzable organosilanes include mono-, di-, tri-, and tetra-functional alkoxysilanes, acetoxysilanes, and oxime silanes, where n3 is an integer of 0 to 3. Enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and a silica-dispersed oligomer solution can be easily prepared.

  In particular, examples of the tetraalkoxysilane having n3 = 0 include tetramethoxysilane and tetraethoxysilane. Further, n3 = 1 organotrialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane. Etc. can be illustrated. Examples of n3 = 2 diorganodialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Further, examples of the triorganoalkoxysilane with n3 = 3 include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane. Organosilane compounds generally called silane coupling agents can also be used as alkoxysilanes.

  Of these hydrolyzable organosilanes, 50 mol% or more is preferably a trifunctional compound represented by n3 = 1. More preferably, it is 60 mol% or more, and most preferably 70 mol% or more. If the n3 = 1 trifunctional compound is less than 50 mol%, sufficient coating film hardness may not be obtained, and the dry curability tends to be poor.

  As the colloidal silica used in component (D), water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used, which is the same as the colloidal silica used in the silicon alkoxide coating agent. Can be used. Generally, such colloidal silica contains 20 to 50% by mass of silica as a solid content, and the amount of silica can be determined from this value.

  When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used for hydrolysis of component (D). Water-dispersible colloidal silica is usually made from water glass, but such colloidal silica is readily available as a commercial product.

  The organic solvent-dispersible colloidal silica can be easily prepared by replacing the water in the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can also be easily obtained as a commercial product in the same manner as the water-dispersible colloidal silica. Examples of the organic solvent in which the colloidal silica is dispersed include, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. Examples include glycol derivatives; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether, and diacetone alcohol. As the organic solvent to be dispersed, one or two or more selected from the group consisting of these can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate , Methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, and the like can also be used.

  The colloidal silica in component (D) is used to increase the hardness of the cured film of the silicon alkoxide coating agent. In the component (D), the colloidal silica is preferably contained in the range of 5 to 95% by mass as the silica solid content. More preferably, it is 10-90 mass%, More preferably, it is the range of 20-85 mass%. If the content of the silica in the solid content is less than 5% by mass, the desired film hardness may not be obtained. If the content exceeds 95% by mass, uniform dispersion of the silica becomes difficult and the component (D) becomes a gel. There is a risk of inconvenience such as conversion.

  The silica-dispersed oligomer of organosilane as component (D) is usually a hydrolyzable organosilane represented by the above general formula in at least one of water-dispersible colloidal silica and organic solvent-dispersible colloidal silica. It can be obtained by partial hydrolysis. In the partial hydrolysis, the amount of water used relative to the hydrolyzable organosilane is preferably 0.001 to 0.5 mol of water relative to 1 mol of the hydrolyzable group. If the amount of water used is less than 0.001 mol, a sufficient partial hydrolyzate may not be obtained, and if the amount of water used exceeds 0.5 mol, the stability of the partial hydrolyzate May get worse. The method of partial hydrolysis is not particularly limited, and it is sufficient to mix a hydrolyzable organosilane and colloidal silica and add and mix a necessary amount of water. At this time, the partial hydrolysis reaction is performed at room temperature (for example, 25 ° C.), it may be heated to 60 to 100 ° C. in order to promote the partial hydrolysis reaction. Furthermore, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluene for the purpose of promoting partial hydrolysis reaction An inorganic acid such as sulfonic acid or oxalic acid or an organic acid may be used as a catalyst.

  The silica-dispersed oligomer solution of the organosilane component (D) has a pH value in the range of 2.0 to 7.0, more preferably 2.5 to 6.6, in order to obtain long-term stable performance. It is adjusted to a range of 5, even more preferably a range of pH 3.0 to 6.0. If the pH value is out of this range, particularly when the amount of water used is 0.3 mol or more with respect to 1 mol of the hydrolyzable group, the long-term performance degradation of the component (D) may be significant. . If the pH value of component (D) after preparation is outside this range, adjust the pH value to be within the above range by adding a basic reagent such as ammonia or ethylenediamine when the pH value is above this range. That's fine. Conversely, when the pH value is more basic than this range, an acidic reagent such as hydrochloric acid, nitric acid, or acetic acid may be used to adjust the pH value to be within the above range. The method for adjusting the pH is not particularly limited.

As R _{8 in} the silanol group-containing polyorganosiloxane of component (E), the same as R ₇ in component (D) can be exemplified, but in R ₈ , 5 to 50 mass in R ₈ % Is preferably a phenyl group. If the phenyl group is less than 5% by mass, the elongation of the coating film tends to be reduced and cracks are likely to occur, and if the phenyl group exceeds 50% by mass, curing may be too slow. In this case, the other R ₈ is preferably an alkyl group having 1 to 4 carbon atoms, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-aminopropyl group, 3,3,3- A substituted hydrocarbon group such as a trifluoropropyl group, more preferably a methyl group or an alkyl group of an ethyl group.

  Further, in the average composition formula, when d is less than 0.2 or e is more than 3, there is a possibility that inconveniences such as cracks occur in the cured film. Moreover, when d exceeds 2 and is 4 or less, or when e is less than 0.0001, curing may not proceed well.

  The silanol group-containing polyorganosiloxane of component (E) is, for example, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or one of alkoxysilanes in which the chloro group is substituted with an alkoxy group correspondingly. Or it can obtain by hydrolyzing 2 or more types of mixtures with a lot of water by a well-known method. In addition, in order to obtain silanol group containing polyorganosiloxane, when it hydrolyzes by a well-known method using alkoxysilane, the alkoxy group which is not hydrolyzed may remain in a trace amount. That is, a polyorganosiloxane in which a silanol group and a trace amount of an alkoxy group coexist may be obtained. However, polyorganosiloxane containing a trace amount of such alkoxy groups may be used as component (E).

  The molecular weight of the silanol group-containing polyorganosiloxane is preferably 700 to 20,000. This molecular weight is a weight average molecular weight by standard polystyrene conversion by GPC (gel permeation chromatography) measurement. When the molecular weight is less than 700, the curability of the formed coating film may be delayed, and cracks may easily occur. On the other hand, when the molecular weight exceeds 20000, the coating film formed by the coating agent to which the pigment is added may lose gloss, and the smoothness may be deteriorated.

  As a mixture ratio of the component (D) and the component (E), when the total amount of the component (D) and the component (E) is 100 parts by mass, the component (D) and the component (E) are 1 to 99 masses. It is preferable to blend in the range of parts. That is, component (D) and component (E) are preferably blended at a mass ratio of 99: 1 to 1:99. And it is more preferable that a component (D) and a component (E) are mix | blended by the mass ratio of 5: 95-95: 5. If the component (D) is less than 1 part by mass, the room temperature curability may be inferior and sufficient film hardness may not be obtained. On the other hand, when the component (D) exceeds 99 parts by mass, the curability becomes unstable and a good film may not be obtained.

  It is preferable that the hydrophilic coating material composition further contains a component (F) as a catalyst. Component (F) is a catalyst that accelerates the condensation reaction between component (X) and component (Y) and cures the coating when the hydrophilic coating material composition is used for painting. That is, it is a curing catalyst. As the component (F), an acidic catalyst, a basic catalyst, an organometallic catalyst, or the like can be used.

  Examples of such catalysts include metal salts of carboxylic acids such as alkyl titanates, tin octylate and dibutyltin dilaurate, dioctyltin dimaleate; amine salts such as dibutylamine-2-hexoate, dimethylamine acetate, and ethanolamine acetate; Carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyl Amine-based silane coupling agents such as dimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; alkali catalysts such as potassium hydroxide; tetraisopropyl titanate; Tiger butyl titanate, titanium compounds such as titanium tetraacetyl acetonate, methyltrichlorosilane, dimethyldichlorosilane, halogenated silane such as trimethyl monochloro silane, and the like. Of course, it is not limited to these catalysts, In addition to these, what is effective in the condensation reaction of component (X) and component (Y) can be used.

  It is preferable that content of a component (F) is 0.0001-10 mass parts with respect to a total of 100 mass parts of a component (X) and a component (Y). More preferably, content of a component (F) is 0.0005-8 mass parts, More preferably, it is 0.0007-5 mass parts. If the content of the component (F) is less than 0.0001 parts by mass, it may not be cured at room temperature, and if it exceeds 10 parts by mass, the heat resistance and weather resistance of the film may be deteriorated.

  The hydrophilic coating material composition is prepared by mixing the component (X), the component (Y), and the component (F) as necessary. At that time, a solvent, water, or the like may be appropriately added for the purpose of adjusting the viscosity. The component (F) may be prepared so as to be contained in one or both of the component (X) and the component (Y), and is prepared by adding separately from the component (X) and the component (Y). May be.

  Moreover, a pigment, a filler, etc. can be suitably added to a hydrophilic coating material composition as needed. Examples of pigments to be added include organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and hansa yellow, titanium oxide, barium sulfate, petal, calcium carbonate, alumina, iron oxide red, and composite metal oxide. An inorganic pigment such as a product is preferable, and one or more selected from these groups can be used in combination. Especially, it is preferable to mix | blend an inorganic pigment in order to improve a weather resistance. As the filler, silica powder, barium sulfate or the like can be used. One or more selected from the groups listed above as pigments may be used in combination as a filler. The particle diameter of the pigment or filler is not particularly limited, but is preferably about 0.01 to 4 μm in average particle diameter.

  The amount of pigment or filler added is not particularly limited because performance such as concealment properties varies depending on the type, and may be an appropriate amount. In the case of an inorganic pigment, the resin solid content is 100 parts by mass. The range which becomes 15-80 mass parts with respect to it is preferable. When the amount of the inorganic pigment is less than 15 parts by mass, the hiding property may not be sufficiently obtained, and when it exceeds 80 parts by mass, the smoothness of the coating film may be deteriorated. The pigment and filler can be dispersed by a usual method, and a dispersant, a dispersion aid, a thickener, a coupling agent, and the like can be used at that time.

  After applying the hydrophilic coating material composition as described above on the surface of an appropriate member such as an air spray, curtain coater, or roll coater, preferably a member used outdoors such as a building exterior material By forming a cured film, a target film can be formed. And preferably, the outer periphery housing member by which the hydrophilic coating material composition was painted is obtained. The temperature condition for the cured film formation may be room temperature or high temperature. Preferably, it is room temperature (for example, 25 ° C.) to 130 ° C. When the temperature is lower than this, curing does not proceed sufficiently, and the physical properties of the film may be lowered. Moreover, when temperature is higher than this, there exists a possibility that the hydrophilic part of a fluorine-type oligomer may react and wettability may fall. Although the film thickness of coating is not specifically limited, 2-15 micrometers is suitable from a viewpoint of leveling property.

  By forming a film in this way, it is possible to localize a fluorine-based oligomer having a hydrophilic group on the surface and impart hydrophilicity with one coat. In addition, by introducing a functional group capable of reacting with an inorganic resin as a binder into a fluorine-based oligomer, it is possible to improve hydrophilic maintenance and realize easy washing with excellent durability outdoors. Become.

  Accordingly, it is possible to provide a coating material that forms a film that has improved weather resistance, is less likely to adhere to pollutants, and that can easily remove adhering substances when the pollutants adhere, and an outer housing member coated with the coating material. It is.

  Hereinafter, the present invention will be described in more detail by way of examples.

  In Examples and Comparative Examples, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise specified. Needless to say, the present invention is not limited to these examples.

[Component (X): Preparation of Silicon Alkoxide Coating Agent (Inorganic Binder)]
[Inorganic binder (I)]
Materials were charged in the following proportions in a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and a partial hydrolysis reaction was performed.

Methyl silicate MS-51 (manufactured by Colcoat Co.) 100 parts Ethyl alcohol 50 parts Distilled water 19 parts 0.2% HCl aqueous solution 2 parts Thereby, an inorganic binder (I) having a resin solid content of 11% was obtained.

[Inorganic binder (II)]
In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, materials were charged in the following proportions, and a partial hydrolysis reaction was carried out by adjusting the molecular weight Mw to 1200 in a thermostatic bath at 60 ° C.

100 parts of methyltrimethoxysilane,
Tetraethoxysilane 20 parts Isopropyl alcohol organosilica sol (“COSCAL Chemical Industry Co., Ltd.“ OSCAL1432 ”, SiO ₂ content 30%) 150 parts Dimethyldimethoxysilane 40 parts Isopropyl alcohol 100 parts Ion-exchanged water 200 parts 25% of inorganic binder (II) was obtained.

[Inorganic binder (III)]
Inorganic binder (III) is prepared by component (D), component (E) and component (F).

<Component (D)>
Into a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer, the materials were charged at the ratio shown below, and subjected to a partial hydrolysis reaction at a temperature of 80 ° C. for about 3 hours with stirring, followed by cooling. A silica-dispersed oligomer solution of organosilane was obtained.

Isopropyl alcohol-dispersed colloidal silica sol (“IPA-ST” manufactured by Nissan Chemical Industries, Ltd., particle size 10-20 μm, solid content 30%, H ₂ O content 0.5%) 100 parts methyltrimethoxysilane 68 parts dimethyldimethoxysilane 18 parts Water 2.7 parts Acetic anhydride 0.1 part This organosilane silica-dispersed oligomer solution had a solid content of 36% when allowed to stand at room temperature for 48 hours.

Moreover, the preparation conditions of this silica dispersion oligomer solution of organosilane are as follows:
-Number of moles of water relative to 1 mol of hydrolyzable group-0.1 mol-Silica content-40.2%
-Mol% of trifunctional (n3 = 1) hydrolyzable group-containing organosilane ... 77 mol%
It is.

<Ingredient (E)>
To a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, 1000 parts of water and 50 parts of acetone were weighed. In the mixed solution, 59.7 parts (0.4 mol) of methyltrichlorosilane, 51.6 parts (0.4 mol) of dimethyldichlorosilane, and 42.3 parts (0.2 mol) of phenyltrichlorosilane were added to toluene 200. What was melt | dissolved in the part was dripped, stirring, and the hydrolysis reaction was performed. Stirring was stopped 40 minutes after the dropping, and the reaction solution was transferred to a separating funnel and allowed to stand, and then the lower layer hydrochloric acid separated into two layers was separated and removed. Next, the remaining water and hydrochloric acid were removed by distillation together with excess toluene from the upper layer solution of organopolysiloxane in toluene by vacuum stripping. As a result, a 60% toluene solution of silanol group-containing organopolysiloxane having an average molecular weight of 3000 was obtained. This organopolysiloxane had an average composition formula (R ₈ ) _d Si (OH) _e O _{(4-de) / 2} , and the amount of phenyl groups in R ₈ was 14%. In the average composition formula (R ₈ ) _d Si (OH) _e O _{(4-de) / 2} , d = 1 and e = 3/5.

<Preparation of inorganic binder (III)>
N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane was used as component (F) which is a component of the curing catalyst. It mixed and stirred in the ratio of 56 parts of components (D) prepared above, 43 parts of components (E), and 1 part of components (F). As a result, an inorganic binder (III) having a resin solid content of 24% was obtained.

[Example 1]
<Preparation of component (Y)>
Materials were charged in a pressure-resistant sealed reaction vessel equipped with a stirrer, a condenser, and a thermometer at the ratio shown below, purged with nitrogen, and then reacted at 65 ° C. for 15 hours to obtain a fluorine-based oligomer.

_{CH 2 = C (CH 3)} COOC 2 H 4 C 6 F 13 4 parts _{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 2 H 25 parts _{CH 2 = C (CH 3)} COO (CH 2 ) ₃ Si (OCH ₃ ) ₃ 1.5 parts HSCH ₂ CH (OH) CH ₂ OH 1.7 parts 2,2′-azobis (2,4′-dimethylvaleronitrile) 0.4 part 1-methoxy-2 -Propanol 30 parts This fluorine-based oligomer had a number average molecular weight of 2821, a weight average molecular weight of 8205, and a solid content of 50%.

In the above _{components, CH 2 = C (CH 3} ) COOC 2 H 4 C 6 F 13 are the monomer _{(A), CH 2 = C} (CH 3) COO (CH 2 CH 2 O) 2 H is the monomer (B), and CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ is the monomer (C). That, Rf is a _C 6 _{F 13,} Q is - _{(CH 2) 2} - and _is, both _{R 3, R 4, R 5} , R 6 is a methyl group.

  As the GPC apparatus, HCL-8220GPC manufactured by Tosoh Corporation was used, and the weight average molecular weight was measured.

<Preparation of coating material composition>
To 100 parts of the inorganic binder (I), 2.2 parts of the prepared fluorine-based oligomer was added and stirred well to obtain a coating liquid.

[Example 2]
To 100 parts of the inorganic binder (II), 5 parts of the fluorine-based oligomer prepared in Example 1 was added and stirred well to obtain a coating liquid.

[Example 3]
To 100 parts of the inorganic binder (III), 4.8 parts of the fluorine-based oligomer prepared in Example 1 was added and stirred well to obtain a coating liquid.

[Example 4]
<Preparation of component (Y)>
Materials were charged in a pressure-resistant sealed reaction vessel equipped with a stirrer, a condenser, and a thermometer at the ratio shown below, purged with nitrogen, and then reacted at 65 ° C. for 15 hours to obtain a fluorine-based oligomer.

_{CH 2 = C (CH 3)} COOC 2 H 4 C 6 F 13 11 parts of _{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 2 H 18 parts _{CH 2 = C (CH 3)} COO (CH 2 ) ₃ Si (OCH ₃ ) ₃ 1.5 parts HSCH ₂ CH (OH) CH ₂ OH 1.7 parts 2,2′-azobis (2,4′-dimethylvaleronitrile) 0.3 part 1-methoxy-2 -Propanol 30 parts This fluorine-based oligomer had a solid content of 50%.

<Preparation of coating material composition>
To 100 parts of the inorganic binder (III), 4.8 parts of the prepared fluorine-based oligomer was added and stirred well to obtain a coating liquid.

[Example 5]
<Preparation of component (Y)>
Materials were charged in a pressure-resistant sealed reaction vessel equipped with a stirrer, a condenser, and a thermometer at the ratio shown below, purged with nitrogen, and then reacted at 65 ° C. for 15 hours to obtain a fluorine-based oligomer.

_{CH 2 = C (CH 3)} COOC 2 H 4 C 6 F 13 15 parts of _{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 2 H 14 parts _{CH 2 = C (CH 3)} COO (CH 2 ) ₃ Si (OCH ₃ ) ₃ 1.5 parts HSCH ₂ CH (OH) CH ₂ OH 1.7 parts 2,2′-azobis (2,4′-dimethylvaleronitrile) 0.3 part 1-methoxy-2 -Propanol 30 parts This fluorine-based oligomer had a solid content of 50%.

<Preparation of coating material composition>
To 100 parts of the inorganic binder (III), 4.8 parts of the prepared fluorine-based oligomer was added and stirred well to obtain a coating liquid.

[Example 6]
<Preparation of component (Y)>
Materials were charged in a pressure-resistant sealed reaction vessel equipped with a stirrer, a condenser, and a thermometer at the ratio shown below, purged with nitrogen, and then reacted at 65 ° C. for 15 hours to obtain a fluorine-based oligomer.

CH ₂ ═C (CH ₃ ) COOC ₂ H ₄ C ₆ F ₁₃ 2.7 parts CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) _α H 26 parts CH ₂ ═C (CH ₃ ) COO ( _{CH 2) 3 Si (OCH 3} ) 3 1.5 parts _{HSCH 2 CH (OH) CH 2} OH 1.7 part of 2,2'-azobis (2,4'-dimethylvaleronitrile) 0.4 parts of 1-methoxy 2-Propanol 30 parts This fluorine-based oligomer had a number average molecular weight of 2821, a weight average molecular weight of 8205, and a solid content of 50%. In addition, in said monomer (B), it is a mixture whose ethylene oxide chain is (alpha) = 4-5.

<Preparation of coating material composition>
To 100 parts of the inorganic binder (III), 4.8 parts of the prepared fluorine-based oligomer was added and stirred well to obtain a coating liquid.

[Example 7]
As component (X), an inorganic coating agent “Fressera NA-100” (solid content 20%) manufactured by Panasonic Electric Works Co., Ltd. was used. This coating agent is a coating agent containing a partial hydrolyzate of silicon alkoxide.

  Then, 4 parts of the fluorine-based oligomer prepared in Example 1 was added to 100 parts of this coating agent and stirred well to obtain a coating solution.

[Example 8]
To 100 parts of the inorganic binder (III), 2.4 parts of the fluorine-based oligomer prepared in Example 1 was added and stirred well to obtain a coating liquid.

[Example 9]
To 100 parts of the above inorganic binder (III), 9.6 parts of the fluorine-based oligomer prepared in Example 1 was added and stirred well to obtain a coating liquid.

[Example 10]
To 100 parts of the inorganic binder (III), 12 parts of the fluorine-based oligomer prepared in Example 1 was added and stirred well to obtain a coating liquid.

[Example 11]
<Preparation of component (Y)>
Materials were charged in a pressure-resistant sealed reaction vessel equipped with a stirrer, a condenser, and a thermometer at the ratio shown below, purged with nitrogen, and then reacted at 65 ° C. for 15 hours to obtain a fluorine-based oligomer.

_{CH 2 = C (CH 3)} COOC 2 H 4 C 6 F 13 4 parts _{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 2 H 23 parts _{CH 2 = C (CH 3)} COO (CH 2 ) ₃ Si (OCH ₃ ) ₃ 3 parts HSCH ₂ CH (OH) CH ₂ OH 1.2 parts 2,2′-azobis (2,4′-dimethylvaleronitrile) 0.3 part 1-methoxy-2-propanol 30 parts This fluorine-based oligomer had a solid content of 50%.

<Preparation of coating material composition>
To 100 parts of the inorganic binder (III), 4.8 parts of the prepared fluorine-based oligomer was added and stirred well to obtain a coating liquid.

[Example 12]
<Preparation of fluorinated oligomer>
Materials were charged in a pressure-resistant sealed reaction vessel equipped with a stirrer, a condenser, and a thermometer at the ratio shown below, purged with nitrogen, and then reacted at 65 ° C. for 15 hours to obtain a fluorine-based oligomer.

_{CH 2 = C (CH 3)} COOC 2 H 4 C 6 F 13 18 parts of _{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 2 H 11 parts _{CH 2 = C (CH 3)} COO (CH 2 ) ₃ Si (OCH ₃ ) ₃ 1.5 parts HSCH ₂ CH (OH) CH ₂ OH 1.7 parts 2,2′-azobis (2,4′-dimethylvaleronitrile) 0.3 part 1-methoxy-2 -Propanol 30 parts This fluorine-based oligomer had a solid content of 50%.

<Preparation of coating material composition>
To 100 parts of the inorganic binder (III), 4.8 parts of the prepared fluorine-based oligomer was added and stirred well to obtain a coating liquid.

[Example 13]
<Preparation of fluorinated oligomer>
Materials were charged in a pressure-resistant sealed reaction vessel equipped with a stirrer, a condenser, and a thermometer at the ratio shown below, purged with nitrogen, and then reacted at 65 ° C. for 15 hours to obtain a fluorine-based oligomer.

CH ₂ = C (CH ₃ ) COOC ₂ H ₄ C ₆ F ₁₃ 4 parts CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _α H 22 parts CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ 5 parts HSCH ₂ CH (OH) CH ₂ OH 1.2 parts 2,2′-azobis (2,4′-dimethylvaleronitrile) 0.3 part 1-methoxy-2-propanol 30 parts This fluorine-based oligomer had a solid content of 50%. In addition, in said monomer (B), it is a mixture whose ethylene oxide chain is (alpha) = 4-5.

<Preparation of coating material composition>
To 100 parts of the inorganic binder (III), 4.8 parts of the prepared fluorine-based oligomer was added and stirred well to obtain a coating liquid.

[Comparative Example 1]
<Preparation of oligomer>
Materials were charged in a pressure-resistant sealed reaction vessel equipped with a stirrer, a condenser, and a thermometer at the ratio shown below, and after purging with nitrogen, they were reacted at 65 ° C. for 15 hours to obtain an oligomer containing no fluorine.

_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 2 H 29 parts _{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 3) 3 1.5 parts HSCH ₂ CH (OH) CH ₂ OH 1.2 parts 2,2′-azobis (2,4′-dimethylvaleronitrile) 0.3 part 1-methoxy-2-propanol 30 parts This non-fluorine-containing oligomer has a solid content of 50%. there were.

<Preparation of coating material composition>
To 100 parts of the above inorganic binder (III), 4.8 parts of the prepared oligomer was added and stirred well to obtain a coating liquid.

[Comparative Example 2]
<Preparation of fluorinated oligomer>
Materials were charged in a pressure-resistant sealed reaction vessel equipped with a stirrer, a condenser, and a thermometer at the ratio shown below, purged with nitrogen, and then reacted at 65 ° C. for 15 hours to obtain a fluorine-based oligomer.

_{CH 2 = C (CH 3)} COOC 2 H 4 C 6 F 13 2.6 parts of _{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) α H 27.5 parts HSCH ₂ CH (OH) CH ₂ OH 1.2 parts 2,2′-azobis (2,4′-dimethylvaleronitrile) 0.5 part 1-methoxy-2-propanol 30 parts This fluorinated oligomer had a solid content of 50%. In addition, in said monomer (B), it is a mixture whose ethylene oxide chain is (alpha) = 4-5.

<Preparation of coating material composition>
To 100 parts of the inorganic binder (III), 4.8 parts of the prepared fluorine-based oligomer was added and stirred well to obtain a coating liquid.

[Comparative Example 3]
An acrylic resin “ACRYDIC A190” manufactured by DIC was used as the acrylic resin. To 100 parts of this acrylic resin, 5 parts of the fluorinated oligomer prepared in Example 1 was added and stirred well to obtain a coating solution.

[Comparative Example 4]
A polyol resin “Olestar Q164” manufactured by Mitsui Chemicals, Inc. was used as the polyol resin, and “Olestar P-49-75S” manufactured by Mitsui Chemicals, Inc. was used as the curing agent. 7.7 parts of the fluorine-based oligomer prepared in Example 1 was added to a mixed liquid of 85 parts of a polyol resin and 15 parts of a curing agent, and stirred well to obtain a coating liquid.

[Comparative Example 5]
To 100 parts of the inorganic binder (III), 0.24 part of the oligomer prepared in Example 1 was added and stirred well to obtain a coating liquid.

[Comparative Example 6]
To 100 parts of the inorganic binder (III), 16.8 parts of the oligomer prepared in Example 1 were added and stirred well to obtain a coating solution.

[Preparation of painted plate]
Each coating solution obtained as described above was applied to a glass plate using a bar coater # 10. Then, it left still at room temperature for 30 minutes as a setting. Furthermore, a glass plate coated with the coating liquid was obtained by performing forced drying at 90 ° C. for 30 minutes using an electric dryer.

[Evaluation]
The following items were evaluated for each painted glass plate.

<Film forming properties>
Judgment was made visually.

○: No cracks or peelings Δ: Some cracks or peelings ×: Cracks or peelings were found on the entire surface.

<Hardness>
Determination was made according to JIS K5600-5-4 scratch hardness pencil method.

<Water wettability (hydrophilicity)>
Water was sprayed on the surface by spraying, and the wet area (%) after 30 seconds was visually determined.

○: Wet area 90% or more Δ: Wet area 70% or more to less than 90% ×: Wet area 70% or less

<Water wettability after immersion in hot water>
After dipping in warm water at 60 ° C. for 40 hours, it was air-dried for 24 hours, and water was sprayed on the surface by spraying, and the wetted area (%) after 30 seconds was visually determined.

○: Wet area 90% or more Δ: Wet area 70% or more to less than 90% ×: Wet area less than 70% −: Judged as not testing because of poor initial wettability.

<Appearance after immersion in hot water>
After dipping in warm water at 60 ° C. for 40 hours, it was air-dried for 24 hours, and the surface was visually determined.

○: No cracks or peelings Δ: Some cracks or peelings ×: Cracks or peelings were found on the entire surface.

<Weather resistance test>
The appearance after 1000 hours was visually determined using an Isuper tester W231 tester manufactured by Iwasaki Electric.

○: No abnormality in appearance ×: Judged as cracking or peeling.

<Anti-fouling>
A test piece (glass plate) was installed vertically outdoors, and the appearance after 3 months was visually determined.

○: No rain streak ×: Rain streak was judged.

[result]
The results are shown in Table 1.

  In Comparative Example 1 in which the oligomer did not contain a fluoroalkyl group and Comparative Example 2 in which no silicon alkoxy group was contained, the antifouling property was poor. Moreover, the comparative example 3 which used the acrylic resin instead of the component (X), and the comparative example 4 which used the polyol resin were bad in antifouling property, and the wettability after warm water immersion and a weather resistance were bad. Comparative Example 5 having a low content of component (Y) had poor wettability. Comparative Example 6 having a large content of component (Y) had a poor appearance after immersion in hot water and poor weather resistance.

  On the other hand, when the coating liquid of Examples 1-13 was used, it was excellent in film forming property, hardness, wettability, wettability and appearance after hot water immersion, weather resistance, and antifouling property.

Claims (3)

(X) at least one selected from silicon alkoxide and its partial hydrolyzate, and (Y) a component containing a fluoroalkyl group, a component containing an ethylene oxide chain, and a component containing a silicon alkoxy group Including a fluorine-based oligomer obtained by copolymerization, with respect to 100 parts by mass of the solid content of the (X) component, the (Y) component is contained in an amount of 1 to 30 parts by mass in terms of solid content ,
The fluorine-based oligomer of the component (Y) includes the following monomers (A), (B) and (C), and is in a mass ratio:
Monomer (A) / Monomer (B) = 1 / 99-60 / 40
{Monomer (A) + monomer (B)} / monomer (C) = 100/1 to 100/15
A hydrophilic coating material composition characterized by being copolymerized at a ratio indicated by
Monomer (A):
_{Rf-Q-OCOC (R 3} ) = CH 2
(In the formula, Rf represents a fluoroalkyl group having 1 to 20 carbon atoms. Q represents — (CH ₂ ) _n1 — or —CH ₂ CH ₂ CH (CH ₃ ) —, where n1 is 1 Represents an integer of ˜3, and R ₃ represents a hydrogen atom or a methyl group.)
Monomer (B):
HO (C ₂ H ₄ O) ₁₁ (C ₃ H ₆ O) _{m 2} (C ₂ H ₄ O) n ₂ COC (R ₄ ) = CH ₂
(Wherein, _{R 4} is, .L1 represents a hydrogen atom or a methyl group, m2 and n2 represents an integer of 1 to 100.)
Monomer (C):
_{CH 2 = C (R 5)} COO (CH 2) m3 Si (O (R 6)) 3
(In the formula, R ₅ represents a hydrogen atom or a methyl group. R ₆ represents the same or different alkyl group having 1 to 8 carbon atoms. M3 represents an integer of 0 to 10.) The hydrophilic coating material composition according to claim 1 , wherein the silicon alkoxide as the component (X) includes the following components (D) and (E).
Component (D):
(R ₇ ) _n3 SiX _4-n3 (wherein R ₇ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, X represents a hydrolyzable group, and n3 represents 0 to 0) 3 is an organosilane silica-dispersed oligomer obtained by dispersing hydrolyzable organosilane represented by the general formula (3) in at least one organic solvent and water and partially hydrolyzing in colloidal silica. Solution Component (E):
(R ₈ ) _d Si (OH) _e O _{(4-de) / 2} (wherein R ₈ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and d and e represents an average composition formula of 0.2 ≦ d ≦ 2.0 and 0.0001 ≦ e ≦ 3 and d + e <4), and a polysiloxane containing silanol groups in the molecule. Organosiloxane Outer loop housing member hydrophilic coating composition of claim 1 or 2 is coated.