JP2779657B2 - Anti-icing paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a permanent coating. More specifically, a resin containing a polysiloxane group is −10 ° C. or less,
In particular, it has little adhesion of ice even at -30 ° C or lower, and can easily remove ice even when it freezes, and has excellent sustainability of the effect. Ships, marine structures, aircraft, vehicles, houses, power transmission The present invention relates to a paint that is effectively used in various fields such as a steel tower to prevent damage caused by snow and icing.

[Prior Art] Conventionally, the use of organopolysiloxanes has been often proposed for anti-wear coatings. Organopolysiloxane has a low surface energy due to the arrangement of hydrocarbon chains on the surface and forms a water-repellent surface. Further, since the glass transition temperature of the organopolysiloxane is low, its molecular motion is not frozen even at −30 ° C. or lower, and it is difficult to form a hydrogen bond during freezing. This is why organopolysiloxanes are often used. As an example of this, Japanese Patent Application Laid-Open No. Sho 61-51069 proposes a permanent coating composition comprising an organopolysiloxane resin, an alkali metal compound and a carboxyl group-containing hydrophobic silicon compound.

[Problems to be Solved by the Invention] However, the permanent shear breaking strength of the coating film at -10 ° C of the conventional product is generally about 0.05 to 0.2 kg / cm ² immediately after film formation. Since the resin bleeds out with the passage of time, it increases to about 0.3 kg / cm ² after three months of exposure, and the durability of the anti-seizure effect is insufficient.
From a practical point of view in the technical field, the above-mentioned conventional products have problems with the anti-seizure property over time and the effective temperature range, and there has been a strong demand for a solution.

Means for Solving the Problems The present inventors have intensively studied to obtain an anti-permanent paint having good anti-permanence properties and excellent long-term durability of the effect, and as a result, have reached the present invention. .

That is, the present invention provides: [Wherein, X is an ethylenic polymerizable group such as a vinyl group, a (meth) acryloxy group, an allyl group, R ₁ is a divalent organic group, R ₂ ,
R ₃ and R ₄ are unsubstituted or substituted monovalent hydrocarbon groups, and m is 6 to 13
It is 0. 10 to 70 parts by weight of a siloxane-containing monomer represented by the formula (b): [Wherein X is the same as in the general formula (1), R ₅ is a divalent organic group or a direct bond, R ₆ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₇ is a carbon number. An alkyl group having 1 to 4, and n is an integer of 1 to 3. 20 to 70 parts by weight of a hydrolyzable silyl group-containing monomer represented by the formula (c): A copolymer [A] obtained by copolymerizing 0 to 70 parts by weight of another polymerizable monomer and 1 And a hydroxyl group-containing resin [B] having at least one hydroxyl group in the molecule.

In the present invention, (a) a general formula [In the formula, X is an ethylenic polymerizable group such as a vinyl group, a (meth) acryloxy group, or an allyl group, R ₁ is a divalent organic group, R ₂ ,
R ₃ and R ₄ are unsubstituted or substituted monovalent hydrocarbon groups, and m is 6 to 13
It is 0. Specifically, as the siloxane-containing monomer represented _{by], CH 2 = CHCOO (CH} 2) 3 [Si (CH 3) 2 O] p Si (CH 3) 3 CH 2 = C (CH 3) COOC 6 _{H 4 [Si (CH 3)} 2 O] p Si (CH 3) 3 CH 2 = C (CH 3) COO (CH 2) 3 [Si (CH 3) 2 O] p Si (C
H ₃ ) ₃ CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ [Si (CH ₃ ) (C ₆ H ₅ ) O] _p
Si (CH ₃ ) ₃ CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ [Si (C ₆ H ₅ ) ₂ O] _p Si (C
H ₃ ) ₃ [where p = 6 to 130. And mixtures of two or more of these.

(B) General formula [Wherein X is the same as in the general formula (1), R ₅ is a divalent organic group or a direct bond, R ₆ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₇ is a carbon number. An alkyl group having 1 to 4, and n is an integer of 1 to 3. Specific examples of the hydrolyzable silyl group-containing monomer represented by the formula (1) include vinylsilane having a hydrolyzable group, for example, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) Silanes; and (meth) acryloxyalkylsilanes having hydrolyzability, for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyl Examples include diethoxysilane and γ-acryloxypropyltriethoxysilane. Among them, preferred is (meth) acryloxyalkylsilane having a hydrolyzable group.

Other polymerizable monomers (c) include alkyl (meth) acrylates (alkyl groups having 1 to 22 carbon atoms) esters [alkyl esters having 1 to 22 carbon atoms such as methyl (meth) acrylate, (meth) Ethyl acrylate, (meth)
N-butyl acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc., hydrogen group-containing (meth) acrylate [2-hydroxy (meth) acrylate] Ethyl, 2-hydroxypropyl (meth) acrylate, etc.], perfluoroalkyl (meth) acrylate [perfluorooctyl (meth) acrylate], CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOC (CH ₃ ) _{= CH 2, C 8 F 17} (CH 2) 11 OCOC (CH 3) = CH 2, C 6 F 13 SO 2 N (CH 3) (CH 2) 2 OCOCH = CH 2 , etc.], (meth) acrylic acid , Aromatic vinyl monomers (styrene, α-
Methyl styrene, α-chlorostyrene, etc.), halogenated vinyl monomer (eg, vinyl chloride), alkyl or cycloalkyl vinyl ether (methyl vinyl ether), cyclohexyl vinyl ester, etc.), vinyl ether (eg, vinyl acetate), nitrile group-containing monomer (Acrylonitrile, etc.), amide group-containing monomer [(meth)
Acrylamide, crotonamide, N-methylolacrylamide, fumaric diamide, etc.], epoxy group-containing monomers [glycidyl (meth) acrylate], allyl alcohol, and the like. Preferred among these are alkyl (meth) acrylates, perfluoroalkyl (meth) acrylates and aromatic vinyl monomers,
Particularly preferred are methyl methacrylate, acrylate n
-Butyl, perfluorooctyl (meth) acrylate and styrene.

The amount of (a), (b) and (c) in the copolymer [A] of the present invention is such that (a) is usually 10 to 70 parts by weight, preferably 20 to 60 parts by weight, ) Is usually 20-70 parts by weight,
Preferably it is 30 to 60 parts by weight, and (c) is usually 0 to 70 parts by weight, preferably 10 to 60 parts by weight. If the content of (a) is less than 10 parts by weight, the shear breaking strength becomes large, and sufficient anti-seizure property cannot be obtained. When the amount exceeds 70 parts by weight, the shear breaking strength is not further reduced and the anti-seizure property is not improved, so that expensive chemicals are wasted. If the content of (b) is less than 20 parts by weight, the durability of the anti-wear property will be reduced. If the amount exceeds 70 parts by weight, the obtained coating film becomes hard and easily cracked, which causes a practical problem. If the amount of (c) exceeds 70 parts by weight, sufficient anti-wear property cannot be obtained, and the durability of the effect is reduced.

The copolymer [A] containing a silyl group and a siloxane group in the present invention comprises (a) and (b) and optionally (c)
It can be produced by subjecting a monomer giving each unit to bulk or solution polymerization according to radical polymerization such as thermal polymerization, photopolymerization or radiation polymerization. A preferred polymerization method is a radical polymerization using a radical initiator in an organic solvent [in the case of solution polymerization, the organic solvent used is an aromatic hydrocarbon (toluene, xylene, ethylbenzene, etc.), an aliphatic hydrocarbon (hexane, heptane, Cyclohexane, etc.), aliphatic esters (ethyl acetate, n-butyl acetate, etc.), aliphatic ketones (acetone, methyl ethyl ketone,
Methyl isobutyl ketone, di-n-butyl ketone, cyclohexane, etc., aliphatic ethers (dioxane, tetrahydrofuran, etc.), alcohols (isopropanol, n-butanol, etc.), cellosolve (ethyl cellosolve, n-butyl cellosolve, cellosolve acetate, etc.) And halogenated hydrocarbons (carbon tetrachloride, ethylene dichloride, etc.) and mixtures of two or more thereof. Preferred are toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, n-butyl acetate, isopropanol, cellosolve acetate and ethylene dichloride alone or a mixture of two or more thereof.

In the case of the organic solvent based on the total weight of the monomers providing the units (a), (b) and, if necessary, (c), the organic solvent can be arbitrarily selected, but is usually 0.2: 2 to 2: 1, preferably 0.5: 2. 1 ~
5: 1.

When a radical polymerization reaction is carried out, azo compounds (such as azobisisobutyronyl and azobisisovaleronitrile), peroxides (benzoyl peroxide, di-t-butyl peroxide) are used as radical polymerization initiators. ,
And redox compounds (benzoyl peroxide / N, N-dimethylaniline, etc.). Preferred are azo compounds.

The amount of the weight initiator to be added is usually 0.001 to 20%, preferably 0.1 to 10%, based on the total weight of the solid content of the monomers giving the units (a), (b) and if necessary (c). .

In some cases, the molecular weight can be adjusted by adding a chain transfer agent (such as n-laurylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane). .

The reaction temperature of the radical weight reaction is usually 50 to 150 ° C, preferably 70 to 130 ° C.

In the case of solution polymerization, the resin produced by the radical polymerization reaction is obtained in an organic solvent, in a solution state or in a state precipitated from the solvent. If necessary, the resin can be isolated by a method such as removal of the solvent by evaporation, filtration, washing, and drying.

The molecular weight of the obtained copolymer [A] is usually 500 to 30,000.
0, preferably 800 to 20,000.

Since the copolymer [A] has a silyl group at a terminal or a side chain, a siloxane bond is formed and cured at room temperature when exposed to the atmosphere. The curing speed varies depending on the atmospheric temperature, humidity and the type of the hydrolyzable group. Specifically, the curing rate increases as the temperature and humidity increase, and the curing rate increases as the number of hydrolyzable groups increases and the number of carbon atoms in the case of an alkoxy group decreases. A polymer having only one silyl group in one molecule usually has a lower curing rate than a vinyl polymer having two or more silyl groups in the molecule.

In the present invention, a hydroxyl group-containing resin [B] having at least one hydroxyl group in one molecule used together with the copolymer [A]
The resin is not particularly limited as long as it has one or more hydroxyl groups. For example, a hydroxyl group-containing vinyl polymer, a hydroxyl group-containing urethane resin, a hydroxyl group-containing amide resin, a hydroxyl group-containing epoxy resin, and the like, Mixtures are mentioned. Preferred is a hydroxyl group-containing vinyl polymer.

Examples of the hydroxyl group-containing vinyl polymer include a polymer composed of a monomer unit having a hydroxyl group and another vinyl monomer unit.

As the hydroxyl group-containing monomer, those similar to the hydroxyl group-containing (meth) acrylate ester (c) in the copolymer [A] can be used. Other vinyl monomers include monomers other than the hydroxyl group-containing (meth) acrylic acid ester of (c) in the copolymer [A] and monomers containing a hydrolyzable silyl group of (b) Is mentioned.

The content of the hydroxyl group-containing monomer in the hydroxyl group-containing vinyl polymer is usually 3 to 70%, preferably 5 to 30% based on the weight of the polymer.

The polymerization can be carried out in the same manner as in the case of the copolymer [A].

The molecular weight of the hydroxyl group-containing resin [B] is not particularly limited, but is usually 1,000 to 60,000, preferably 2,000 to 40,000.
It is.

The anti-deposition coating of the present invention is a coating containing the copolymer [A] and the hydroxyl group-containing resin [B] as essential components.
The mixing ratio of [A] and [B] is usually 1/99 to 50/5 by weight.
0, preferably 3/97 / to 30/70. If the blending ratio of the copolymer [A] is less than 1, the effect of preventing adhesion is reduced, and if it exceeds 50, the effect of preventing adhesion is not improved any more, and the expensive agent of [A] is wasted. Is also poor.

The coating composition of the present invention may further contain a liquid paraffin substance such as liquid paraffin conventionally used in addition to the components [A] and [B] to further reduce the permanent shear breaking force at the ice-coating film interface. it can. If necessary, a known pigment, extender or dye commonly used in paints can be added in an amount of 120% by weight or less based on the total weight of [A] and [B]. In addition, surfactants and additives (such as an ultraviolet absorber, a leveling agent, an anti-sagging agent, and a matting agent), a solvent, and the like can be appropriately added.

In addition, since [A] contains a moisture-curable silyl group, a silyl group curing catalyst, a storage stabilizer, and the like may be specifically added.

As the curing catalyst, those conventionally used as silanol condensation catalysts may be used, and organic titanate compounds (such as isopropyltriisostearoyl titanate), organic aluminum compounds (such as acetoalkoxyaluminum diisopropylate), and carboxylic acid type tin compounds (Tin dioctylate, dibutyltin dilaurate, dibutyltin malate, etc.), sulfur-containing organic tin compounds such as sulfide type, mercaptide type (dibutyltin sulfide, etc.), other carboxylic acid metal salts (sodium acetate, cobalt naphthenate, etc.), Acid phosphates (monomethyl acid phosphate, dimethyl acid phosphate,
Diethyl acid phosphate, monobutyl acid phosphate, etc.), carboxylic acid and its anhydride (maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, etc.), aminosilane (γ-aminopropyltriethoxysilane, etc.), amine And its salts (triethylamine,
Curing catalyst such as dibutylamine-2-hexoate, cyclic amidine and salts thereof). These catalysts may be used alone or in combination of two or more. The amount of the curing catalyst to be added is usually 0.1 to the silyl group-containing resin [A].
001-20% by weight.

Stabilizers include hydrolysable esters, alcohols and complete esters such as carbonic acid, boric acid, phosphoric acid, and phosphorous acid. As hydrolysable esters, trialkyl orthoformates (trimethyl orthoformate) and silanes (methyl trimethyl Methoxysilane, tetraethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, silicate and the like). Examples of the alcohol include methanol, ethanol, cellosolve and the like. Examples of complete esters such as carbonic acid, boric acid, phosphoric acid, and phosphoric acid without P-OH include diester carbonate (such as dimethyl carbonate), triester boric acid (such as tri-n-butyl borate), and phosphoric acid triester (such as tri-n-butyl phosphate). ), P-OH-free monoesters or diesters of phosphoric acid (such as diesters such as diphenyl phenyl phosphate or phenyl diphenyl phosphate). The amount of the stabilizer is preferably 1 to 30% based on the total silyl group-containing polymer.

The solvent may be the same as the solvent used when synthesizing the silyl group-containing polymer, and a solvent that is inert to the silyl group-containing polymer is used. It is also possible to dilute with a solvent. The amount of the solvent is usually from 0 to 60 based on the silyl group-containing polymer.
0% by weight.

The coating composition of the present invention reduces the permanent shear breaking force by the dimethylsiloxane in [A] and simultaneously reacts the hydrolyzable silyl group in [A] with the hydroxyl group in [B] to form a coating film. Because it can be firmly attached or adhered to the main body, it is possible to reduce the decrease in the ability to prevent permanent adhesion more than when the conventional dimethylsiloxane bleeds out and the ability to prevent permanent adhesion has been reduced. Things. Further, by introducing a perfluoroalkyl group into [A], it is possible to further reduce the permanent shear breaking force and exhibit the effect of preventing the permanent adhesion.

The coating amount of the paint of the present invention is usually 10 to 800 g / m ² , preferably 50 to 500 g / m ² .

The coating method of the anti-seizure coating of the present invention includes, for example, brush coating, roll coating, spray coating, flow coating or dipping, and is not particularly limited.

The paint of the present invention can be directly applied to metal, plastic, glass, woody material, and the like, in addition to being applied on the undercoat as an overcoat. Further, the paint can be used as a finished product after being laminated on the surface of the object.

[Examples] Hereinafter, the present invention will be further described with reference to Production Examples, Comparative Production Examples, and Examples, but the present invention is not limited thereto. Parts and percentages in the examples are on a weight basis.

Production Example 1 100 parts of toluene was placed in a kolben, the temperature was raised to 100 ° C., 30 parts of methyl methacrylate, CH ₂ ＣC (CH ₃ ) COOC (CH ₂ ) ₃ [Si (CH ₃ ) ₂ O] ₁₀ Si ( CH
_{3) 3} 50 parts, .gamma.-methacryloxypropyltrimethoxysilane 20 parts trimethoxysilane was added dropwise in 2 hours a mixed solution of 3 parts of azobisisobutyronitrile and toluene 5 parts, was then reacted for 2 hours at the same temperature. Furthermore, azobisisobutyronitrile 1
Part reacted at the same temperature for 2 hours after adding to obtain a polymer A _1. The of the polymer A ₁ IR (infrared absorption spectrum), carbon - there was no absorption of 1648 cm ^-1 due to carbon double bond. GPC
The molecular weight was measured at about 3000.

Production Example 2 100 parts of toluene was placed in a kolben, the temperature was raised to 100 ° C., 20 parts of n-butyl methacrylate, 15 parts of styrene, CH ₂ ＣC (CH ₃ ) COOC (CH ₂ ) ₃ [Si (CH ₃ ) ₂ O] ₁₀ Si (CH
_{3) 3} 50 parts, .gamma.-methacryloxypropyltrimethoxysilane 15 parts trimethoxysilane was added dropwise in 2 hours a mixed solution of 2 parts of azobisisobutyronitrile and toluene 5 parts, was then reacted for 2 hours at the same temperature. Furthermore, Asobisisobutyronitrile 1
Part reacted at the same temperature for 2 hours after adding to obtain a polymer A _2. The of the polymer A ₂ IR (infrared absorption spectrum), carbon - there was no absorption of 1648 cm ^-1 due to carbon double bond. GPC
The molecular weight was measured at 5,000.

Production Example 3 100 parts of toluene was placed in a kolben, the temperature was raised to 100 ° C., 30 parts of methyl methacrylate, CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ [Si (CH ₃ ) ₂ O] ₁₀ Si ( C
H _{3) 3} 30 _{parts, CF 3 (CF 2) 9} (CH 2) 2 COOC (CH 3) = CH 2 20
Parts, γ-methacryloxypyropyltrimethoxysilane 20
Part, 3 parts of azobisisobutyronitrile and 5 parts of toluene
A part of the mixed solution was added dropwise over 2 hours, and then reacted at the same temperature for 2 hours. To obtain a polymer A ₃ are reacted in the same temperature for 2 hours after further addition of azobisisobutyronitrile 1 part. The of the polymer A ₃ IR (infrared absorption spectrum), carbon - there was no absorption of 1648 cm ^-1 due to carbon double bond. The molecular weight measured by GPC was about 3200.

Production Example 4 100 parts of toluene was placed in a kolben, and the temperature was raised to 100 ° C., and 40 parts of n-butyl methacrylate, 10 parts of styrene, 15 parts of 2-hydroxyethyl methacrylate, and 25 parts of methyl methacrylate were used.
, A mixed solution of 0.5 parts of dodecanethiol and 2 parts of azobisisobutyronitrile was added dropwise over 3 hours, and then reacted at the same temperature for 30 minutes. Azobisisobutyronitrile
0.2 parts added 3 times every 30 minutes, and further reacted at the same temperature for 1 hour, a polymer was obtained B _1. The of the polymer B ₁ IR (infrared absorption spectrum), carbon - 1648 with carbon double bonds
^There was no absorption of ^-1 . Approximately 6500 when measuring molecular weight with GPC
Met.

Production Example 5 100 parts of toluene was placed in a kolben, the temperature was raised to 100 ° C., and 50 parts of n-butyl methacrylate, 10 parts of styrene, 5 parts of 2-hydroxyethyl methacrylate, and 15 parts of methyl methacrylate were used.
Parts, γ-methacryloxypropyltrimethoxysilane 10
, A mixed solution of 0.5 parts of dodecanethiol and 2 parts of azobisisobutyronitrile was added dropwise over 3 hours, and then reacted at the same temperature for 30 minutes. Further adding 3 times 0.2 parts of azobisisobutyronitrile every 30 minutes, and further reacted at the same temperature for 1 hour, a polymer was obtained B _2. The the polymer B ₂ IR (infrared absorption spectrum), carbon - due to carbon double bond 16
There was no absorption at 48 cm ^-1 . Approximately 5 when measuring molecular weight with GPC
900.

Examples 1 to 5 As shown in Table 1, a copolymer [A] and a hydrogen group-containing resin [B] were mixed to obtain a permanent coating of the present invention. The paint was polished on a mild steel plate by air spray to a thickness of about 150 g / m ² and dried at room temperature for 3 days to obtain a uniform coating film.

[A] and [B] represent the numbers of the production examples. The catalyst used was dibutyltin dilaurate.

Comparative Example 1 10 g of lithium acetate, 40 g of liquid paraffin according to JIS K-2331-80 and 50 g of xylene were placed in a 1-volume stainless steel container, and dispersed at a temperature of 50 ° C. for 30 minutes using glass beads as a medium. Obtained. The resulting paste
A coating was prepared by blending 50 g, 150 g of an organopolysiloxane resin [KE / 45T, Shin-Etsu Chemical Co., Ltd., nonvolatile content 50%], and 100 g of xylene. This paint is applied on a polished mild steel sheet which has been previously clear coated with an organopolysiloxane resin (described above) to a film thickness of about 150 g / m ² by air spray, and dried at room temperature for 8 hours to be uniform A good coating film was obtained.

Shearing breaking strength test method As shown in Fig. 1, the inner diameter is 23mm and the height is 20m on the coating film 1 of the test plate.
The stainless steel ring 2 having a thickness of 2 mm and a thickness of 2 mm is placed horizontally, and about 2.5 ml of pure water is poured into the ring and allowed to freeze at −20 ° C. for 3 hours or more. 3 is obtained. Next, a shock was applied to the ring 2 by a metal working rod (shaft) 4 driven by power, and the permanent shear fracture strength of the ice 3 was measured. (Unit: kg / cm ² ) Further, after the coated test plate was naturally exposed for three months, the shear fracture strength at −20 ° C. was determined using the same test method as described above. Table 2 shows the results.

[Effects of the Invention] The anti-permanent paint comprising the copolymer [A] and the hydroxyl group-containing resin [B] of the present invention has the following effects.

(1) It has low shear breaking strength against ice and good anti-seizure property at -10 ° C or lower, and has excellent effect continuity.

(2) It has excellent adhesion to various adherends.

(3) Room temperature curing type.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an apparatus for testing the icing property of the anti-seizure paint. 1 ... coating film, 2 ... stainless steel ring, 3 ... frozen layer (ice), 4 ... operating rod

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Takeshi Takagaki 3-1-1-15, Fuzhou, Koto-ku, Tokyo Ishikawa Shima-Harima Heavy Industries, Ltd. (72) Inventor Masaharu Takahashi 4-chome, Minamishinagawa, Shinagawa-ku, Tokyo No. 1-15 Nihon Paint Co., Ltd. Tokyo Office (72) Inventor Masataka Tanaka 4-1-1 Minami Shinagawa, Shinagawa-ku, Tokyo Nihon Paint Co., Ltd. Tokyo Office (72) Inventor Katsuya Sugawara Shinagawa-ku, Tokyo 4-1-1-15 Minamishinagawa Nihon Paint Co., Ltd. Tokyo Office (72) Inventor Satoshi Kuriyama 11 Sanyo Kasei Kogyo Co., Ltd., 11-11, Hitotsubashi-Honcho, Higashiyama-ku, Kyoto-shi, Kyoto (72) Inventor Shunichi Nakajima Kyoto 11 Sanyo Kasei Kogyo Co., Ltd., 11-11 Hitotsubashi-Honcho, Higashiyama-ku, Kyoto (58) Field surveyed (Int. Cl. ⁶ , DB name) C09D 5/00 C09D 155/00

Claims (3)

(57) [Claims] (1) General formula [In the formula, X is an ethylenic polymerizable group such as a vinyl group, a (meth) acryloxy group, or an allyl group, R ₁ is a divalent organic group, R ₂ ,
R ₃ and R ₄ are unsubstituted or substituted monovalent hydrocarbon groups, and m is 6 to 13
It is 0. 10 to 70 parts by weight of a siloxane-containing monomer represented by the formula (b): [Wherein X is the same as in the general formula (1), R ₅ is a divalent organic group or a direct bond, R ₆ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₇ is a carbon number. An alkyl group having 1 to 4, and n is an integer of 1 to 3. 20 to 70 parts by weight of a hydrolyzable silyl group-containing monomer represented by the following formula (c): A copolymer [A] obtained by copolymerizing 0 to 70 parts by weight of another polymerizable monomer with 1 And a hydroxyl group-containing resin [B] having at least one hydroxyl group in the molecule. 2. The permanent coating according to claim 1, wherein (c) contains an ethylenically polymerizable monomer containing a perfluoroalkyl group. 3. The compounding ratio of [A] and [B] is 1/99 by weight.
3. The anti-deposition coating according to claim 1, wherein the ratio is 50/50.