JP2000095833A - One-pack type self-curing water-repellent resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin showing excellent water drop slipperiness, water repellency and stain-proofness, sufficiently cross-linkable at a low temperature, having excellent maintainability of the performances in forming a film by making the resin include a blocked isocyanate, a hydroxy group and a polysiloxane chain. SOLUTION: This resin is obtained by copolymerizing (A) 5-40 wt.% of one terminal radical-polymerizable polysiloxane of formula I and/or II (R1 to R12 are H or a 1-10C hydrocarbon; (n) and (q) are each >=2; (p) is 0 to 10) with (B) 10-50 wt.% of a blocked isocyanate-containing radical-polymerizable monomer, (C) 3-50 wt.% of a hydroxy group-containing radical-polymerizable monomer and (D) 10-80 wt.% of a radical-polymerizable monomer not to be reacted with the blocked isocyanate and the hydroxy group. A monomer obtained by blocking isosyanate of methacryloyl isocyanate, etc., are preferable as the component B. p-Hydroxymethylstyrene, etc., etc., are preferable as the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-pack type self-curing water-repellent resin. The one-part self-curing water-repellent resin according to the present invention not only contains isocyanate groups and hydroxyl groups (in a state where the isocyanate groups are blocked) which are complementary reactive groups in the same molecule, but also has excellent water repellency. And a polysiloxane chain that imparts antifouling properties, and is useful mainly for coating applications.

[0002]

2. Description of the Related Art Conventionally, various polysiloxanes (silicone) have been used as a method for lowering the surface energy of an object surface and imparting surface characteristics such as excellent water repellency and antifouling property.
Have been proposed, and resins using these as raw materials have been studied. Among these, there is a method of applying a polysiloxane (silicone) resin to the surface of an object. However, there is a problem in adhesion between the polysiloxane resin and the surface of the base material, and problems such as peeling of the coating and lack of durability occur. There is. As a technique for solving this problem, for example, Japanese Patent Application Laid-Open No. 60-231720 describes a copolymer having a polysiloxane chain in a side chain, and the copolymer has water repellency and antifouling property. And maintainability of these properties is excellent. However, although this copolymer has a relatively large contact angle with water, it does not have sufficient dropping properties of water droplets and antifouling properties. In addition, the maintainability of these performances is not satisfactory.

[0003] Also, Japanese Patent Application Laid-Open No. 2-80415 discloses that
Methacryl-functional dimethylpolysiloxanes and copolymers obtained therefrom have also been described, the copolymers also comprising:
Similar to the above, it is said that it has excellent water repellency and antifouling properties, has a relatively small dynamic friction coefficient value with respect to stainless steel balls, and has good slipperiness. However, their dynamic friction coefficient values and slipperiness are only values for stainless steel, and the dropping property of water droplets and the antifouling property of the coating film are not satisfactory. In addition, performance retention, especially solvent resistance, has not been improved at all.

As a technique for solving these disadvantages, for example, a two-pack type water-repellent resin obtained by copolymerizing a hydroxyl group-containing monomer and curing with an isocyanate-based crosslinking agent, or a blocked isocyanate and a catalyst are generally used. It is conceivable to use a one-part type water-repellent resin to be cured by using the resin.

[0005] However, in the case of the two-pack type water-repellent resin, there is a problem of safety and hygiene at the time of mixing and coating of the isocyanate-based crosslinking agent, a problem at the time of mixing both components, and a pot life of the coating liquid after mixing. The problem is that the usage time is short. Further, in the one-pack type water-repellent resin, the compatibility between the blocked isocyanate compound serving as a crosslinking agent and the base resin is poor, or the dissociation temperature of the blocked isocyanate compound is high even when a catalyst is added, and the degree of crosslinking is sufficient. Or not
When the curing temperature is increased to improve the degree of crosslinking, there is a disadvantage that the coating film turns yellow. Therefore, there is a demand for the development of a resin having sufficient cross-linking at lower temperature and having excellent water-drop sliding property, water repellency and antifouling property.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned drawbacks in the prior art, to provide excellent water droplet slippage, water repellency and antifouling properties when formed into a coating film, and to achieve a low temperature. It is an object of the present invention to provide a novel one-pack type self-curing water-repellent resin which is capable of sufficient cross-linking and is excellent in maintaining the above-mentioned properties.

[0007]

According to the present invention, the above-mentioned object is achieved by (A) the general formula (1):

Embedded image (In the formula, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other. 1 to 1 atoms
Is a hydrocarbon group of 0, and n is an integer of 2 or more), and / or a radically polymerizable polysiloxane at one end and / or a general formula (2):

Embedded image (In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same or different from each other. 1 atom
A hydrocarbon group of 10, p is an integer of 0 to 10,
(q is an integer of 2 or more) 5 to 40% by weight of a radically polymerizable polysiloxane at one end, (B) a radically polymerizable monomer 10 having a blocked isocyanate group 10
50% by weight, (C) 3 to 50% by weight of a radical polymerizable monomer having a hydroxyl group, and (D) 10 to 80% by weight of a radically polymerizable monomer having no reactivity with a blocked isocyanate group and a hydroxyl group. Can be solved by a one-pack type self-curing water-repellent resin obtained by copolymerizing

[0008] The one-pack type self-curing water-repellent resin according to the present invention comprises a blocked isocyanate group in the same molecule,
Having both hydroxyl groups and polysiloxane chains, it shows excellent water droplet slippage, water repellency, and antifouling properties when formed into a coating film. Furthermore, sufficient cross-linking occurs at low temperatures, so the appearance is good. In addition, it is possible to obtain a coating film having sufficient performance for maintaining the above-mentioned performances.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the one-part self-curing water-repellent resin of the present invention, that is, the surface treating agent will be described in detail. In the present invention, the monomer represented by the general formula (1) can be used as the one-terminal functional polysiloxane (A) having a functional group at one terminal. R ¹ in the general formula (1) is a hydrogen atom or a group having 1 to 10 carbon atoms.
Is a hydrocarbon group. In the present specification, the number of carbon atoms is 1 to
The ten hydrocarbon groups include, for example, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group), and an aryl group having 6 to 10 carbon atoms. Group (for example, phenyl group) and cycloalkyl group having 3 to 10 carbon atoms (for example, cyclohexyl group). R ¹ is preferably a hydrogen atom or a methyl group. R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ in the general formula (1) may be the same or different from each other. R ² , R ³ , R ⁴ and R ⁵ are
Each is preferably independently a methyl group or a phenyl group, and R ⁶ is preferably a methyl group, a butyl group, or a phenyl group. Further, n in the general formula (1)
Is an integer of 2 or more, preferably an integer of 10 or more, more preferably an integer of 30 or more.

In the present invention, the monomer represented by the general formula (2) may be used as the one-terminal-functional polysiloxane (A) having a functional group at one terminal. In the general formula (2), R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group. Further, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² in the general formula (2) may be the same or different. R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are preferably each independently a methyl group or a phenyl group, and R ¹² is preferably a methyl group, a butyl group, or a phenyl group. Further, p in the general formula (2) is 0 to 0.
It is an integer of 10 and preferably 3. In the general formula (2), q is an integer of 2 or more, and preferably 1
It is an integer of 0 or more, more preferably an integer of 30 or more.

Such a one-terminal radically polymerizable polysiloxane (A) can be prepared by a known method.
Commercial products can also be used. As a commercially available product, for example, Silaplane FM-0711 (number average molecular weight 1,
000, manufactured by Chisso Corporation), Silaplane FM-0
721 (number average molecular weight 5,000, manufactured by Chisso Corporation), Silaplane FM-0725 (number average molecular weight 1
0000, manufactured by Chisso Corporation) or X-22-17
4DX (number average molecular weight 4,600, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

In the present invention, the one-terminal radical polymerizable polysiloxane represented by the general formula (1) may be used alone or in combination of two or more, or the one-terminal radical polymerizable polysiloxane represented by the general formula (2) may be used. The polymerizable polysiloxanes can be used alone or in combination of two or more. Further, one or more of the one-terminal radically polymerizable polysiloxanes represented by the general formula (1) can be used in combination with the general formula ( One or more of the one-terminal radically polymerizable polysiloxanes represented by 2) can be used as a mixture.

These one-terminal radically polymerizable polysiloxanes (A) are used in an amount of 5 to 40% by weight based on the total amount of the monomers used. If the amount is less than 5% by weight, the intended purpose of water drop slippage, water repellency, or antifouling property may be insufficient. If the amount exceeds 40% by weight, unreacted monomer components after polymerization increase. This may lead to unfavorable situations such as softening of the coating film and bleeding of the monomer component.

The radical polymerizable monomer (B) having a blocked isocyanate group is not particularly limited as long as it is a monomer containing a blocked isocyanate group and a moiety having radical polymerizability. It is preferable to use a radical polymer monomer having a blocked isocyanate group and no other functional group (for example, a hydroxyl group or a polysiloxane chain). Suitable monomer (B)
Is, for example, a general formula (3):

Embedded image [Wherein, R ³¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or a hexyl group), an aryl group having 6 to 10 carbon atoms (e.g., a phenyl group), or a 3 to 5 carbon atom.
10 cycloalkyl groups (for example, a cyclohexyl group, R ³² is an oxygen atom or a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, for example, 1 to carbon atoms;
10 alkylene groups (for example, a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group), an alkylidene group having 3 to 10 carbon atoms (for example, a propylidene group), or an arylene group having 6 to 10 carbon atoms (for example, , Phenylene group, tolylene group, or xylylene group),
Or a cycloalkylene group having 3 to 10 carbon atoms (e.g., cyclohexylene group), and R ³³ is a group that blocks an isocyanate group.] Or a general formula (4) :

Embedded image [Wherein, R ⁴¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or a hexyl group), an aryl group having 6 to 10 carbon atoms (e.g., a phenyl group), or a 3 to 5 carbon atom.
10 cycloalkyl groups (for example, a cyclohexyl group, and R ⁴² is an oxygen atom or a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, for example, a carbon atom having 1 to 10 carbon atoms;
10 alkylene groups (for example, a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group), an alkylidene group having 3 to 10 carbon atoms (for example, a propylidene group), or an arylene group having 6 to 10 carbon atoms (for example, , Phenylene group, tolylene group, or xylylene group),
Or a cycloalkylene group having 3 to 10 carbon atoms (for example, a cyclohexylene group), and R ⁴³ is a group that blocks an isocyanate group.] Is preferably used. The blocked isocyanate (—NHCO—R ³³ ) group in the general formula (3) or the blocked isocyanate (—NH) in the general formula (4)
The CO-R ⁴³ ) group is a known blocking agent (H-
R ³³ or HR ⁴³ ).

Examples of the radical polymerizable monomer (B) having a blocked isocyanate group include methacryloyl isocyanate, 2-isocyanatoethyl methacrylate, or m- or p-isopropenyl-α, α-
It is preferable to use one or more monomers obtained by blocking the isocyanate group of dimethylbenzyl isocyanate. The radically polymerizable monomer (B) having a blocked isocyanate group can be blocked by reacting the free isocyanate group of the corresponding radically polymerizable monomer having a free isocyanate group with a blocking agent in advance. And then used in the copolymerization reaction.

As the blocking agent, there can be used a compound generally used as a blocking agent for an isocyanate group. Specifically, for example, methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, phenyl cellosolve, methyl carbitol, benzyl alcohol,
Alcohol compounds such as cyclohexanol or furfuryl alcohol; phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert
-Octylphenol, nonylphenol, α-naphthol, β-naphthol, p-nitrophenol, or p
-A phenolic compound such as chlorophenol; an active methylene compound such as dimethyl malonate, diethyl malonate, acetylacetone, or ethyl acetoacetate; a mercaptan-based compound such as butylmercaptan, dodecylmercaptan, or thiophenol; acetanilide;
Acid amide compounds such as acetoanisidide, acetylamide or benzamide; diphenylamine, aniline,
Or an amine compound such as carbazole; imidazole;
Imidazole compounds such as 2-ethylimidazole or 2-ethyl-4-methylimidazole; imine compounds such as ethyleneimine; oxime compounds such as formaldoxime, acetoaldoxime, methylethylketoxime, or cyclohexanone oxime; or ε-caprolactam, δ-valerolactam, or β
-Lactams such as propiolactam and the like. Of these, alcohol compounds, phenol compounds, active methylene compound compounds, oxime compounds, and lactam compounds are preferred, and oxime compounds are more preferred.

Known blocking methods can be applied to the reaction between the free isocyanate group and the blocking agent. For example, the corresponding radical polymerizable compound having a free isocyanate group in a solvent-free or non-reactive solvent can be used. By dropping a blocking agent onto the monomer, the free isocyanate group can be converted to a blocked isocyanate group. The reaction temperature is not particularly limited, but is generally 0 to 100 ° C, preferably 20 to 60 ° C.
It is. In this blocking reaction, it is preferable not to use a catalyst. This is because if the catalyst remains in the system, the dissociation reaction of the blocked isocyanate group is also promoted in the next radical polymerization step, which may cause an undesirable situation such as gelation of the reaction mixture.

The radical polymerizable monomer (B) having a blocked isocyanate group is used in an amount of 10 to 50% by weight based on the total amount of the monomers used. If the amount is less than 10% by weight, the degree of crosslinking is too low, so that the coating film may be softened, or the slipperiness of water droplets, water repellency, or stain resistance may be insufficient.
On the other hand, if it is used in an amount exceeding 50% by weight, it may be difficult to adjust the glass transition point or the like of the copolymer because other monomer components are reduced. As the radical polymerizable monomer (B) having a blocked isocyanate group, one type can be used alone, or two or more types can be used in combination.

The monomer having a hydroxyl group (C) is not particularly limited as long as it is a monomer having a hydroxyl group. However, the monomer having a hydroxyl group and another functional group (for example, a blocked isocyanate group) Alternatively, a radical polymerizable monomer having no polysiloxane chain is preferably used.

Preferred specific examples of the monomer (C) having a hydroxyl group include p-hydroxymethylstyrene, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate. Acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or di-2-hydroxyethyl fumarate;
Polyethylene glycol or polypropylene glycol mono (meth) acrylate or their ε-caprolactone adducts; hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids; (meth) acrylic acid;
Adducts of α, β-ethylenically unsaturated carboxylic acids such as crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid with ε-caprolactone; or the above α, β-ethylenically unsaturated carboxylic acids Adducts with an epoxy compound such as butyl glycidyl ether, phenyl glycidyl ether or glycidyl monocarboxylate (Cadura E, manufactured by Shell Chemical Co., Ltd.) can be mentioned. Among them, monomers having a primary hydroxyl group are preferred from the viewpoint of curing reactivity. As the radical polymerizable monomer (C) having a hydroxyl group, one type may be used alone, or
Alternatively, two or more kinds can be used in combination.

The radical polymerizable monomer (C) having a hydroxyl group is used in an amount of 3 to 50% by weight (preferably 10 to 40% by weight) based on the total amount of the monomer. In addition,
The molar ratio (B / C) of the radical polymerizable monomer (B) having a blocked isocyanate group and the radical polymerizable monomer (C) having a hydroxyl group is preferably in the range of 0.5 to 2. , 0.8 to 1.2. When the molar ratio (B / C) is less than 1.0, a (co) polymer having a blocked isocyanate group is added to the copolymer of the present invention to obtain a coating composition. Conversely, the molar ratio (B / C) is 1.0
In the case where the ratio exceeds the above range, a (co) polymer having a hydroxyl group may be mixed with the copolymer according to the present invention to form a coating composition.

Examples of the (co) polymer having a blocked isocyanate group which can be used in producing a coating composition by mixing with the copolymer according to the present invention include, for example, an isocyanurate type of hexamethylene diisocyanate. Prepolymer block (Duranate MF-
B60X or Duranate MF-K60X, manufactured by Asahi Kasei Corporation; Sumidur BL-3175, manufactured by Sumitomo Bayer Urethane Co., Ltd .; a blocked product of an isocyanurate-type prepolymer of isophorone diisocyanate (Desmodur BL-4265, Sumitomo Bayer Urethane Co., Ltd.) ) Or Burnock D-500 (manufactured by Dainippon Ink and Chemicals, Inc.) or Burnock D-5
50 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

Examples of the (co) polymer having a hydroxyl group which can be used in producing a coating composition by mixing with the copolymer according to the present invention include, for example, acrylic polyols such as Acrydic A-801 (manufactured by Dainippon Ink and Chemicals, Inc.), Acrydic A-8
10 (manufactured by Dainippon Ink and Chemicals, Inc.), ACIDIC BU-995 (manufactured by Dainippon Ink and Chemicals, Inc.), Hitaloid 3008 (manufactured by Hitachi Chemical Co., Ltd.), Hitaroid 3020 (manufactured by Hitachi Chemical Co., Ltd.), Desmophen A160 (manufactured by Sumitomo Bayer Urethane Co., Ltd.) or Desmophen A260 (manufactured by Sumitomo Bayer Urethane Co., Ltd.); polyester polyols such as Burnock DE-140 (manufactured by Dainippon Ink and Chemicals, Inc.), Burnock D-150 (manufactured by Dainippon Ink and Chemicals, Inc.) Nippon Ink Chemical Industry Co., Ltd.) or Desmophen 680 (Sumitomo Bayer Urethane Co., Ltd.); fluororesin-based polyols, such as Lumiflon LF-200 (Asahi Glass Co., Ltd.), Cefral Coat PX-40 (Central Glass Co., Ltd.) ), Zeffle GK-51 (Manufactured by Daikin Industries, Ltd.), or Zafuron FC-220 (manufactured by Toagosei Co., Ltd.), and the like.

The radical polymerizable monomer (D) having no reactivity with the blocked isocyanate group and the hydroxyl group does not react with the blocked isocyanate group, does not react with the hydroxyl group, and further has a siloxane group. There is no particular limitation as long as the monomer is not used.

The radical polymerizable monomer (D) includes, for example, styrene compounds such as styrene, p-methylstyrene, p-chloromethylstyrene, and vinyltoluene; methyl (meth) acrylate, ethyl (meth) Acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-
Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, Or a (meth) acrylate compound having a hydrocarbon group such as benzyl (meth) acrylate; a (meth) acrylate compound in which these hydrogen atoms are substituted with a fluorine atom, a chlorine atom, or a bromine atom; vinyl acetate, benzoic acid Vinyl ester compounds such as vinyl ester of vinyl or branched monocarboxylic acid (manufactured by Beova Shell Chemical Co., Ltd.); acrylonitrile compounds such as acrylonitrile or methacrylonitrile; ethyl vinyl ether, n- Vinyl ether compounds such as tyl vinyl ether, i-butyl vinyl ether, or cyclohexyl vinyl ether; acrylamide compounds such as (meth) acrylamide, dimethyl (meth) acrylamide, or diacetone acrylamide; vinylpyridine, N, N-dimethylaminoethyl (meth) ) Acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide,
-(N, N-dimethylamino) styrene or N- ｛2
-Basic nitrogen-containing vinyl compound compounds such as-(meth) acryloyloxyethyl piperidine; epoxy groups such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-epoxyvinylcyclohexane Containing vinyl compound compound; (meth) acrylic acid, angelic acid, crotonic acid, maleic acid, 4-vinylbenzoic acid, p-vinylbenzenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, or mono {2- Acidic vinyl compound compounds such as (meth) acryloyloxyethyl diacid phosphate; silane compound compounds such as vinyltrimethoxysilane, γ-methacryloxyethyltrimethoxysilane, and γ-methacryloxyethylmethyldimethoxysilane; ethylene Or olefinic compounds such as propylene; vinyl chloride, vinylidene chloride, vinyl bromide,
Halogenated olefin compounds such as vinyl fluoride, tetrafluoroethylene, and chlorotrifluoroethylene; and other examples include maleimide and vinyl sulfone.

The above radical polymerizable monomers (D) can be used alone or in combination of two or more.
It is preferable to use (meth) acrylate monomers mainly from the viewpoint of copolymerizability. The radical polymerizable monomer (D) is used in an amount of 10 to 80% by weight (preferably 20 to 60% by weight) based on the total amount of the monomer. If the amount is less than 10% by weight, it may be difficult to adjust the glass transition point of the copolymer, and if it exceeds 80% by weight, the slipperiness of water droplets, water repellency or stain resistance may be insufficient.

In order to prepare a copolymer using the above-mentioned monomers (A), (B), (C) and (D), any known and commonly used arbitrary copolymer can be used. In particular, the use of a solution radical polymerization method or a non-aqueous dispersion radical polymerization method is the most convenient and particularly preferred.

Examples of the solvent used in the polymerization include aromatic hydrocarbon compounds such as toluene, xylene, and a mixture of aromatic hydrocarbons (Solvesso 100, manufactured by Esso Petroleum Co., Ltd.); n-hexane, cyclohexane ,
Aliphatic / alicyclic hydrocarbon compounds such as octane, mineral spirit or kerosene; ester compounds such as ethyl acetate, n-butyl acetate, i-butyl acetate or butyl cellosolve acetate; methanol, ethanol, n
-Propanol, i-propanol, n-butanol,
Examples thereof include alcohols such as i-butanol, ethylene glycol, propylene glycol, ethyl cellosolve, and butyl cellosolve, and these solvents can be used alone or in combination of two or more.

The above-mentioned polymerization can be carried out by a conventional method using various known and commonly used radical polymerization initiators, for example, azo or peroxide radical polymerization initiators.
The polymerization time is not particularly limited, but is usually selected from the range of 1 to 48 hours. The polymerization temperature is not particularly limited as long as the radically polymerizable monomer (B) having a blocked isocyanate group does not cause a spontaneous dissociation reaction, that is, a temperature at which the blocked isocyanate group is not deblocked. Usually 30 to 120 ° C, preferably 60 to 10 ° C
0 ° C. The above polymerization can be carried out by further adding a known and commonly used chain transfer agent such as butyl mercaptan, dodecyl mercaptan, or α-methylstyrene dimer, if necessary.

Although the molecular weight of the copolymer in the present invention is not particularly limited, its number average molecular weight is preferably about 5,000 to 1,000 by GPC (gel permeation chromatography) in terms of polystyrene.
000 range (more preferably 5,000 to 50,
000). If it is less than 5,000, the film-forming properties may be degraded, and if it exceeds 1,000,000, a large amount of solvent may be required to dilute to an appropriate viscosity during film formation.

When the one-pack type self-curing water-repellent resin of the present invention is used as a coating material, it is applied as it is on a substrate and forcedly dried at a temperature of about 40 ° C. to 200 ° C. for about 1 to 60 minutes. Can be painted. At the time of this coating treatment, a so-called curing catalyst (a catalyst that acts on both dissociation of the blocked product and curing of the free isocyanate), for example, an organic metal salt such as tin, zinc, or lead, or a tertiary amine is added. Can also.

The one-part self-curing water-repellent resin of the present invention comprises:
This may be used as it is as a clear paint, but further, if necessary, various additives, for example, a surfactant, a bulking agent, a coloring pigment, a rust preventive pigment, a fluororesin powder, a silicone resin powder, a rust preventive, a dye And / or a wax or the like may be added to use as a coating composition.

[0033]

EXAMPLES The present invention will be described below in more detail with reference to examples, but these examples do not limit the scope of the present invention. In the following production examples and the like, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

(A) Commercially available product names of the materials used in the following production examples are shown below. (1) One-terminal radically polymerizable polysiloxane component (A) Sylaprene FM-0711 (number-average molecular weight: 1,000
0; manufactured by Chisso Corporation) Thyraplane FM-0721 (number average molecular weight 5,000
0; manufactured by Chisso Corporation) Thyraplane FM-0725 (number average molecular weight 10,000
00; manufactured by Chisso Corporation. (2) Radical polymerization initiator perbutyl O (t-butylperoxy-2-ethylhexanoate; NOF Corporation)

(B) The test method of the physical property evaluation test in the following coating film forming examples is shown below. (1) Xylene spot test One drop of xylene was placed on the cured coating film, left at room temperature until the xylene evaporated, and the state of the cured coating film was observed. The evaluation was performed in the following three stages, and the results are shown in Table 2. That is, ◎ indicates no change was observed, △ indicates a ring-shaped mark, and × indicates swelling or dissolution of the cured coating film.

(2) Initial antifouling property A line was drawn on the cured coating film with a magic ink (red), and the repellency was examined. The evaluation was performed in the following three stages, and the results are shown in Table 2. In other words, those that repel oil droplets and can be easily wiped off with a cloth are marked with ◎, those that repel oil droplets and can be wiped off partly, but those that remain partially on the cured coating film without being wiped off. Are marked with x and those that cannot be wiped off with a cloth are indicated by x.

(3) Stain removal properties A line was drawn on the cured coating film with magic ink (blue, black, red, and green) and dried at room temperature for 24 hours.
The blue and black magic inks were wiped with a cloth soaked with ethanol, and the red and green magic inks were wiped with a cloth soaked with xylene. The results were evaluated in the following three stages and are shown in Table 2. That is, ◎, no trace of magic ink remains
○ Those with slight traces, × with clear traces
It was expressed by.

(4) Initial Water Drop Sliding Angle A water drop (20 μm) of deionized water was placed on the cured coating film held horizontally.
1 or 30 μl) was placed on each of them, and the cured coating film was gradually tilted from a horizontal state, and the angles at which the five water drops started to slide were measured. Of the measured values, the smallest measured value and the largest measured value are discarded, and the average of the remaining three measured values is evaluated in units of 10 °.

(5) Sliding angle of water droplet after solvent exposure Using a cloth impregnated with xylene, the surface of the cured coating film was wiped back and forth 100 times while changing the cloth occasionally. Then, while keeping the cured coating horizontal, 5 drops of deionized water (20 μl or 30 μl) are placed on each, and the cured coating is gradually tilted from the horizontal state, and the above-mentioned 5 drops of water begin to slide. Angles were measured respectively. Of the measured values, the smallest measured value and the largest measured value are discarded, and the average of the remaining three measured values is evaluated in units of 10 °.

[0040]

Reference Example 1 << Synthesis Example of Radical Polymerizable Monomer (B) Having Blocked Isocyanate Group >> Mechanical Stirrer,
In a glass reactor equipped with a thermometer, a condenser and a dry nitrogen gas inlet, n-butyl acetate (242 parts) and 2
-Isocyanatoethyl methacrylate (155 parts) was charged and heated to 40 ° C under a dry nitrogen atmosphere. Then, methyl ethyl ketoxime (87 parts) in a dropping funnel
Was added dropwise so that the internal temperature did not exceed 42 ° C. 1 at 40 ° C
After reacting for a time, it was confirmed by the infrared absorption spectrum of the sample that the absorption of isocyanate had disappeared, and the reaction mixture was taken out into a sealed bottle.

[0041]

[Production Example 1] In this example, a procedure for synthesizing a one-part self-curing water-repellent resin according to the present invention will be described. Toluene (83 parts) and n-butyl acetate (83 parts) were placed in a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser, and a dry nitrogen gas inlet, and heated to 90 ° C. in a nitrogen atmosphere. After that, the mixture was heated and stirred at 90 ° C. for 10 minutes to sufficiently drive off oxygen in the system. Then, at 90 ° C., n-butyl acetate (21 parts), methyl methacrylate (40 parts), n-butyl acetate
Butyl methacrylate (30 parts), lauryl methacrylate (30 parts), 2-hydroxyethyl methacrylate (34 parts), Thylaprene FM-0721 (46
Part), perbutyl O (7 parts), and a monomer (126 parts; including a solvent) synthesized in Production Example 1 were dropped from the dropping funnel over 3 hours. 90 after completion of dropping
50% non-volatile content by holding at 5 ℃
Thus, a solution of a target one-pack type self-curing water-repellent resin having a number average molecular weight of 9800 was obtained.

[0042]

Production Examples 2 to 7 and Comparative Production Examples 1 and 2 In this example, the procedure for synthesizing the one-part self-curable water-repellent resin according to the present invention and the procedure for synthesizing the one-part self-curable water-repellent resin for comparison were used. And The same procedure as in Production Example 1 was carried out except that the charged amounts of the solvent and the monomers were changed as shown in Table 1, to obtain a desired one-part self-curable water-repellent resin solution. Production Example 2
7, the one-component self-curing water-repellent resin according to the present invention is obtained. In Comparative Production Example 1, the amount of the one-terminal radically polymerizable polysiloxane (A) was set to 3% by weight of the total, and in Comparative Production Example 2, One-terminal radical polymerizable polysiloxane (A)
Was used at 50% by weight of the whole.

[0043]

[Table 1]

[0044]

[Coating film forming example 1] An amount of 1% by weight of the resin component of the one-pack type self-curing water-repellent resin obtained in Production Example 1 was 0.1% by weight.
% Dibutyltin dilaurate ethyl acetate solution,
Further, it was diluted with n-butyl acetate so that the nonvolatile content in the coating composition became 30% by weight. The coating composition was coated on a dry electroplated tin plate (66 × 100 mm) degreased with a mixed solvent of toluene / isopropyl alcohol (2/1) in advance using a bar coater # 20. This coating film was cured by heating at 140 ° C. for 30 minutes to obtain a cured coating film. The various physical property evaluation tests described above were performed. Table 2 shows the results.
Shown in The initial water droplet slipperiness of this cured coating film is 30 ° / 20.
It was good with less than μl and less than 20 ° / 30 μl, and the initial antifouling property and stain removal property were also good. In addition, even after exposure to the solvent, there was no change in the water droplet slipperiness, and good results were shown.

[0045]

[Coating film formation examples 2 to 7 and coating film formation comparative examples 1 and 2] The one-pack type self-curing water-repellent resin obtained in Production Examples 2 to 7 and Production Comparative Examples 1 and 2 was coated with the above coating film. A cured coating film was prepared in the same manner as in Formation Example 1, and various physical property evaluation tests were performed. Table 2 shows the results. In the coating film forming examples 2 to 7, good results were shown in all evaluation items, but in the coating film forming comparative example 1, difficult points were observed in the antifouling property and the water drop sliding property from the initial stage. In Comparative Example 2 of the coating film formation, bleeding of the unreacted residual monomer was observed on the surface of the cured coating film.

[0046]

[Table 2]

From the above data, it can be seen that the one-pack type self-curing water-repellent resin of the present invention imparts excellent water-drop sliding property, water-repellent property, and stain-proof property to the surface of the object to be coated, and has high performance maintaining property. It is clear that you are doing.

[0048]

The one-pack type self-curing water-repellent resin of the present invention can impart excellent water-drop sliding property, water-repellent property and antifouling property to the surface of a substrate when a film is formed. Since it has the feature of having excellent maintainability, it can be applied to surface treatment of various substrates. Specifically, cars,
Railway vehicles, other vehicles, or outer panels and walls of buildings (houses, buildings), etc., or water-related appliances such as toilets, washbasins, bathtubs, kitchen sinks, and heat from air conditioners or refrigerators The present invention can be applied to an exchanger, a road sign, a curved mirror, and the like, and is effective in improving antifouling property, visibility, and hardly ice and snow.

Claims (3)

[Claims] (A) General formula (1): (In the formula, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other. 1 to 1 atoms
Is a hydrocarbon group of 0, and n is an integer of 2 or more), and / or a radically polymerizable polysiloxane at one end and / or a general formula (2): (In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same or different from each other. 1 atom
A hydrocarbon group of 10, p is an integer of 0 to 10,
(q is an integer of 2 or more) 5 to 40% by weight of a radically polymerizable polysiloxane at one end, (B) a radically polymerizable monomer 10 having a blocked isocyanate group 10
50% by weight, (C) 3 to 50% by weight of a radical polymerizable monomer having a hydroxyl group, and (D) 10 to 80% by weight of a radically polymerizable monomer having no reactivity with a blocked isocyanate group and a hydroxyl group. One-part self-curing water-repellent resin obtained by copolymerizing 2. As the radical polymerizable monomer (B) having a blocked isocyanate group, methacryloyl isocyanate, 2-isocyanatoethyl methacrylate,
The one-component self-curing repellent according to claim 1, wherein one or more monomers obtained by blocking an isocyanate group of m- or p-isopropenyl-α, α-dimethylbenzyl isocyanate are used. Aqueous resin. 3. A radical polymerizable monomer having a blocked isocyanate group (B), which is obtained by reacting a radical polymerizable monomer having a free isocyanate group with a blocking agent in advance without radical polymerization before radical polymerization. The one-part self-curing water-repellent resin according to claim 1, wherein a monomer obtained by the reaction is used.