JPH06264029A - Coating material comprising vinyl copolymer - Google Patents

Abstract

PURPOSE:To obtain a coating material improved in resistances to weather, solvents, acids, and staining, surface smoothness, etc., by copolymerizing a specific silicone compd., a vinyl compd., and a vinyl monomer. CONSTITUTION:This coating material comprising a vinyl copolymer having a number average mol.wt. of 1,000-200,000 is obtd. by copolymerizing 5-80wt.% silicone compd. which has structural units of formulae I and II [wherein R<1> is H, a 1-18C linear or branched alkyl group, or CH2=CH(R<3>)-Q-R<4>; R<3> is H or methyl; Q is an ester or ether group; R<4> is 2-10C alkylene, etc.; R<2> is a 1-18C linear or branched alkyl group or phenyl], has terminal groups each of which has an R<2>O structure when an Si atom is included in the terminal group or an R<2> structure when bonded to an oxygen atom, and has a number average mol.wt. of 800-200,000 and a ratio of R<1>/R<2> of 0.8-10 (A), 0.1-10wt.% vinyl compd. of formula III (wherein R<6> and R<8> are each H or 1-2C alkyl; R<7> is 1-2C alkyl; and X is O or imino) (B), and 10-94.9wt.% vinyl monomer other than compd. B (C).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a vinyl-based copolymer useful as a raw material for paints, coating agents, schilling agents, etc., which are excellent in weather resistance, acid resistance, solvent resistance, stain resistance and smoothness. Related to the paint material.

[0002]

2. Description of the Related Art A vinyl polymer having an alkoxysilyl group at a molecular end or a side chain and a coating composition using the same are disclosed, for example, in JP-A-54-36395 and JP-A-54-40893. It is known from JP-A-54-123129.

[0003]

However, recently,
In the fields of construction, automobiles, and metal coatings, there is a demand for coating materials that are more excellent in performance such as weather resistance, acid resistance, solvent resistance, stain resistance, and smoothness. In order to solve these problems, the present inventors can improve the above-mentioned problems by creating a silicone compound having a specific structure having a polymerizable double bond and a polymer thereof, and applying the same to a coating material. We have already applied for a patent (Japanese Patent Application No. 4-23447), and the weather resistance of this copolymer paint film is greatly improved in the long-term weather resistance test, but it has a further excellent durability. It is an object of the present invention to pursue.

[0004]

The present inventors have found that a silicone compound having a specific structure having a polymerizable double bond and a vinyl polymer containing a specific vinyl compound can solve the above problems. The present invention has been completed. That is,
The present invention is (A) a silicone compound, and 1) has a structure represented by the following general formulas (I) and (II) in the molecular structure,
2) It has a structure of R ² —O— when it is bonded to silicon as an end group and R ² — when it is bonded to oxygen (R ² is a linear or branched alkyl group having 1 to 18 carbon atoms, or phenyl). Group), 3) number average molecular weight of 800 to 200,000,
And 4) 5 to 80% by weight of a silicone compound having an R ¹ / R ² ratio of 0.8 to 10 (may be abbreviated as “specific silicone compound” hereinafter),

[0005]

[Chemical 3]

(B) Vinyl compound represented by the following general formula: 0.1 to 10% by weight;

[0007]

[Chemical 4]

(C) A vinyl-based monomer monomer other than the above (B) is a polysynthetic monomer component consisting of 10 to 94.9% by weight (however, the total of the components (A), (B), and (C)). Is 100% by weight) and has a number average molecular weight of 1,0.
It is a coating material comprising a vinyl copolymer of 00 to 200,000 (hereinafter sometimes abbreviated as "copolymer-I") as a main component.

The compound represented by the [specific silicone compound] which is the component (A) is described in, for example, Japanese Patent Application No. 2-1271.
No. 8, Japanese Patent Application No. 2-12720, Japanese Patent Application No. 3-4
As described in Japanese Patent No. 3382, the molecular structure has a structure represented by the following general formulas (D) and (E) (Si
The substituent of R ⁹ of —R ⁹ is H—, a straight-chain or branched alkyl group having 1 to 18 carbon atoms, and a phenyl group), and R ² —O— when bonded to a silicon terminal as an end group, an oxygen terminal. Has a structure of R ² — (wherein R ² is the same as the above R ² ), and has an R ⁹ / R ² ratio of 0.8 to 10
Silicone compound: [compound-I] (compound-
It is obtained by adding a carbon-carbon unsaturated bond compound to the Si-H group of (abbreviated as I) (hydrosilylation reaction).

[0010]

[Chemical 5]

This [Compound-I] is hydrolyzed and polycondensed by reacting trichlorosilane or a trichlorosilane / organotrichlorosilane mixture with water in a solvent such as dioxane as described in the above application. , Then obtained by reacting with alcohol. Structure of the thus obtained [compound -I] is R ⁹ is hydrogen, R ² is equal to or less than the illustrated relatively low molecular a typical taking the case of a methyl group (Me) (F) , (G) and (H).

[0012]

[Chemical 6]

[0013]

[Chemical 7]

[0014]

[Chemical 8]

Examples of the carbon-carbon unsaturated bond compound to be added to this [compound-I] are, for example, propylene, butene, 1-hexene, 1-octene, isobutene, 5-methyl-1-butene, cyclohexene. Allyl esters such as allylbenzene, olefins such as allylbenzene, allyl acetate, allyl propionate, allyl 2-ethylhexanoate and allyl benzoate, allyl methyl ether, allyl ethyl ether, allyl propyl ether, allyl hexyl ether, allyl cyclohexyl. Allyl ethers such as ether, allyl-2-ethylhexyl ether, allyl phenyl ether, allyl glycidyl ether, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-2 Ethylhex Sil, cyclohexyl (meth) acrylate, phenyl (meth) acrylate and other (meth) acrylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate and other carboxylic acid vinyl esters, Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, etc. Carbon such as styrene, (meth) acrylonitrile, crotonic acid ester, 2- (allyloxy) ethanol, allylamine, allylcyclohexylamine, allyl alcohol, allylthiourea -Carbon unsaturated bond compounds etc. are raised.

Of these, terminal olefins such as 1-hexene and 1-octene, allyl esters, and allyl ethers are preferable in terms of reactivity. Further, as the carbon-carbon unsaturated bond compound for introducing an epoxy group into the silicone compound represented by [Compound-I], for example, a carbon-carbon unsaturated bond such as allyl glycidyl ether or glycidyl methacrylate and an epoxy group And a compound having both in one molecule. Of these, allyl glycidyl ether is preferably used. Further, as the carbon-carbon unsaturated bond compound for introducing the polymerizable double bond into the silicone compound represented by [Compound-I], for example, allyl (meth) acrylate,
Two or more double bonds such as diallyl ether, diallyl phthalate, (meth) acrylic acid beer, vinyl crotonic acid, vinyl cinnamate, ethylene glycol di (meth) acrylic acid ester, butylene glycol di (meth) acrylic acid ester 1 The compound which has it together in the molecule is mentioned.
Of these, allyl (meth) acrylate is particularly preferable.

In the reaction of [Compound-I] with the unsaturated bond compound, it is preferable to use a platinum group VIII catalyst. As the platinum group VIII catalyst, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum chloride-olefin complex, solid platinum supported on a carrier such as alumina or silica, and rhodium-olefin complex are used. The amount used is usually 1 to 1000 relative to the reaction product.
Amounts in ppm are used.

This hydrosilylation reaction is carried out at 50 to 150
At a temperature of ° C a reaction time of 1 to 24 hours is achieved. When the reaction temperature is 50 ° C or lower, the reaction rate is slow and not practical.
If the temperature is higher than 150 ° C, a polymer may be generated or a gelation reaction may occur, which is not preferable. The molar ratio at the time of reacting the carbon-carbon unsaturated bond compound for introducing a polymerizable double bond to this [compound-I] is as follows: the molecular weight of the raw material [compound-I] and the amount of the polymerizable double bond to be introduced. Depends on It is preferable to react at a molar ratio of 0.3 to 1.5 per [specific silicone compound] molecule produced. More preferably, the reaction is carried out at a molar ratio of 0.5 to 1.3.
If it is less than 0.3, the amount introduced into the vinyl polymer will be small, and if it is more than 1.5, gelation may occur during the reaction with the vinyl monomer.

The molar ratio of the compound (I) with a carbon-carbon unsaturated bond compound other than the polymerizable double bond compound varies depending on the target [specific silicone compound], but it is usually Si-H. The total amount of unsaturated bond compounds other than the polymerizable double bond compound is 0.8 to 20 with respect to 1 mol of the group.
A molar range is preferred. A solvent may or may not be used in this reaction. As the solvent that can be used when a solvent is used, hydrocarbons such as toluene and xylene, ethers such as propyl ether, dioxane and tetrahydrofuran, butyl acetate, esters such as propyl acetate and the like used in ordinary hydrosilylation reaction are used. Can be used.

The thus obtained component (A) [specific silicone compound] may be used alone or in combination of two or more. In the present invention, it is used in an amount of 5 to 80% by weight based on the total amount of polymerizable monomer components. If the amount is less than 5% by weight, sufficient effects cannot be obtained with respect to the desired coating physical properties, and if the amount is more than 80% by weight, the coating film obtained becomes brittle and the coating properties are deteriorated.

The component (B) used in the present invention is
The following general formula

[0022]

[Chemical 9]

It was found that the vinyl compound represented by the formula (B), by including the component (B) as a copolymer component, the weather resistance improved by the introduction of the [specific silicone compound] is further dramatically improved. In particular, there is the essence of the present invention. Examples of the vinyl compound as the component (B) include 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meta). ) Acrylate, 4-
(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-
1,2,2,6,6-pentamethylpiperidine, 1,
2,2,6,6-Pentaethyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetraethyl-4
-Piperidyl (meth) acrylate, 4- (meth) acryloylamino-2,2,6,6-tetraethylpiperidine, 4- (meth) acryloylamino-1,2,2
6,6-pentaethylpiperidine, 1-methyl-2,
2,6,6-Tetraethyl-4-piperidyl (meth) acrylate, 1-ethyl-2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 4-crotonoyloxy-1,2,2 , 6,6-Pentamethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like. These may be used alone or in combination of two or more.

The amount of the component (B) used in the present invention is 0.1 to 10% by weight based on the total amount of the polymerizable monomer components. When the amount is less than 0.1% by weight, the cracking of the coating film for a long period of time is not sufficiently prevented, and when the amount is more than 10% by weight, the gloss and the durability of the coating film are deteriorated and the appearance of the coating film is deteriorated. Preferably, 0.2 to 5% by weight is used. The component (C) used in the present invention is not particularly limited, and a copolymerizable vinyl monomer copolymerizable with the components (A) and (B) can be used, but a preferable copolymerizable vinyl monomer is , For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, -2 ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, (meth) Isobornyl acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- (trimethoxysilyl) propyl (meth) acrylate, (meth ) Acrylic acid-3- (methyldimethoxysilyl) propyl, (meth) acrylic acid-3-
(Meth) acrylic acid esters such as (triethoxysilyl) propyl, (meth) acrylic acid, styrene and the like are used.

Upon copolymerization, solution polymerization using an organic solvent in the presence of a polymerization initiator such as a peroxide or an azo compound is preferably used in a conventional manner. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate, butyl acetate and 2-ethylhexyl acetate, alcohols such as propanol and butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Etc. are used. It is also possible to use compounds such as butyl mercaptan and dodecyl mercaptan, and chain transfer agents such as halogenated hydrocarbons.

The polymerization temperature varies depending on the type and amount of the polymerization initiator, but is selected from the range of room temperature to 150 ° C. The molecular weight of the resulting copolymer can be controlled by the kind and amount of the polymerization initiator and the polymerization temperature, and is selected from the range of the number average molecular weight of 1,000 to 200,000.

When the vinyl copolymer of the present invention is applied to a paint, it is diluted with an organic solvent as necessary and then applied and cured. Upon curing, it may be baked at a high temperature or may be cured using a curing catalyst, but it is preferable to use a curing catalyst. As the curing catalyst, commonly used tin-based, aluminum-based, titanium-based, amine-based curing catalysts and the like are used.

Examples of the tin-based curing catalyst include dibutyltin dilaurate, dibutyltin dimaleate, tin 2-ethylhexanoate, dimethyltin bis (isooctylmercaptoacetate), and (n-C ₈ H ₁₇ ) ₂ Sn = S. Can be mentioned. Examples of the aluminum-based curing catalyst include diisopropylate ethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, aluminum isopropoxide, monoethylacetoacetonate.
Examples include bis (acetylacetonate) aluminum.

Examples of the titanium-based curing catalyst include diisopropoxy bis (ethyl acetate) titanate and diisopropoxy bis (acetylacetonato) titanate. Examples of the amine-based curing catalyst include triethylamine, tributylamine, diethylenetriamine, isophoronediamine, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-
Aminopropyltrimethoxysilane and the like can be mentioned.

When the vinyl copolymer composition contains an epoxy group, phthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, polymercaptan, 2-methyl-4-ethylimidazole Epoxy curing catalysts and the like can also be used. You may use these catalysts 1 type (s) or 2 or more types. The amount of catalyst added is selected from the range of 0.05 to 5% by weight based on the resin. The curing temperature may be selected from the range of natural drying under atmospheric temperature to baking curing at about 200 ° C.

When used, additives such as antioxidants, light stabilizers, viscosity control agents, pigments, metal powders such as aluminum paste, etc. may be added, if necessary.

[0032]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples. The NMR analysis in the examples is JMX PMX.
As for 60Si and infrared absorption spectrum (IR), JASCO Corporation FT / IR5300 was used. The molecular weight was measured by gel permeation chromatography (GPC).

The coating film performance was evaluated according to the following method. 1) Mitsuzawa: JIS K5400-7.6 (60)
゜) ○: Specular gloss = 85% or more 2) Gel fraction ： Dip the cured coating film in acetone and
Retention rate of coating film weight after standing for 24 hours (%) 3) Pencil hardness: JIS K5400-8.4.1 (Scratch evaluation) 4) Adhesion: JIS K5400-8.5.2
○: 10 to 8 points, △: 6 to 4 points, ×: 2 to 0 points 5) Flexibility: JIS K5400-8.1 ○:
2 mmφ pass, Δ: 3 to 6 mmφ pass, x: 8 mmφ or more 6) Weather resistance: ASTM G-53 ○: Gloss retention rate = 90% or more, x: Gloss retention rate <90% 7) Acid resistance: JIS K5400-8.22 [Production Example 1] Synthesis of [Compound-I] A 2 liter four-necked flask equipped with a thermometer, a stirring rotor and a cooling tube was charged with 1200 g of dioxane and 1 mol of trichlorosilane and stirred. A dropping funnel containing 18 g of water and 18 g of dioxane was attached to the 4-necked flask, and the mixture was added dropwise while maintaining the temperature at 25 to 30 ° C. After the dropping, stirring was continued for another 30 minutes, and then a dropping funnel containing 3 mol of ethanol was attached, and the mixture was added dropwise while maintaining the temperature at 20 to 30 ° C. Then, the mixture was stirred for another 120 minutes. The reaction solution was taken out, and the solvent was completely distilled off under reduced pressure of about 60 ° C. or lower to obtain 79.3 g of a low-viscosity silicone compound. This liquid is dissolved in chloroform, and this solution is subjected to gel permeation chromatography (hereinafter abbreviated as GPC method).
The molecular weight was measured by. As a result, a number average molecular weight (hereinafter, abbreviated as MN) 840, a weight average molecular weight (hereinafter, MW)
1600). S by ¹ H-NMR measurement
the molar ratio of i-H and OC ₂ H ₅ was about 1.2. or,
When this silicone compound was added to 2N-NaOH and the hydrogen gas generated was measured for the Si-H content, 11.5 mmol / g of hydrogen gas was generated.

[Production Example 2] Synthesis of [Compound-I] 1060 g of dioxane and 0.931 mol of trichlorosilane were charged and stirred in a 2-liter four-necked flask equipped with a thermometer, a stirring rotor and a cooling tube. Water 16.76
A dropping funnel containing g and 67 g of dioxane was attached to the 4-necked flask, and the mixture was added dropwise while maintaining the temperature at 25 to 30 ° C.
After the dropwise addition, stirring was continued for another 30 minutes, and then methanol 2.
Attach a dropping funnel containing 79 mol, 20-30 ° C
It was dripped while keeping it. Then, the mixture was stirred for another 120 minutes. The reaction solution was taken out and the solvent was completely distilled off under reduced pressure of about 60 ° C. or lower to obtain 56.3 g of a low-viscosity silicone compound. This liquid was dissolved in chloroform, and the molecular weight of this solution was measured by the GPC method. As a result, M
It was N890 and MW2100. ^{According to 1} H-NMR measurement, the molar ratio of Si—H and OCH ₃ was about 1.1.
Moreover, when this silicone compound was added to 2N-NaOH and the content of Si-H was measured by the generated hydrogen gas, 13.6 mmol / g of hydrogen gas was generated.

[Synthesis Example 1] Synthesis of [specific silicone compound] which is the component (A) 9% was put in a 2 liter four-necked flask equipped with a thermometer, a stirring rotor, a cooling tube, and a nitrogen supply introducing tube. Isopropanol solution containing chloroplatinic acid of 0.88 g, allyl methacrylate 9.03 g, allyl glycidyl ether 55.
45 g, allyl acetate 30.34 g, toluene 154.4
g, 60.07 g of the silicone compound obtained in Production Example 1
Was charged. A small amount (about 5 ml / min) of nitrogen was poured and stirred, and the temperature was raised to 50 ° C. while monitoring the temperature inside the flask. After the temperature was maintained at 50 to 55 ° C for 30 minutes, the temperature was further raised to 60 ° C and the temperature was maintained at 60 to 65 ° C for 30 minutes. After that, the temperature was raised to 80 ° C., and the mixture was stirred at 80 to 85 ° C. for 1 hour. After that, 628.4 g of allyl acetate was placed in the dropping funnel and attached to the above 4-necked flask, and after dropping for 30 minutes, the temperature inside the flask was raised to 104 to 105 ° C. and the temperature was raised to 1
The mixture was stirred at 04 to 105 ° C for 11 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography (hereinafter, abbreviated as GC) to find that the reaction rate of allyl methacrylate was 74% and the reaction rate of allyl glycidyl ether was 70%.

The reaction solution was filtered through a 0.5 micron filter, and then the solvent was distilled off under reduced pressure at 60 ° C. or below.
26.5 g of a pale yellow transparent liquid was obtained. This liquid is G
When the molecular weight was measured by the PC method, it was MN2100. This liquid was added to 2N-NaOH to remove residual S
When i-H was measured, the reaction rate of Si-H was 97.8.
%Met. Also, the IR (infrared absorption spectrum) is 17
Absorption of carboxylic acid ester at 20 cm ^-1 , 1640 cm
There was absorption of vinyl group at ^-1 .

[Synthesis Example 2] Synthesis of [specific silicone compound] which is the component (A): 8% in a 1-liter four-necked flask equipped with a thermometer, a stirring rotor, a cooling pipe, and a nitrogen supply introduction pipe. Isopropanol solution containing chloroplatinic acid of 0.66 g, allyl methacrylate 4.18 g, allyl glycidyl ether 61.
2 g, 100.4 g of toluene, and 35 g of the silicone compound obtained in Production Example 2 were charged. In the same manner as in Synthesis Example 1, heating and raising the temperature to 80 to 8 with stirring while pouring a small amount of nitrogen.
The reaction was carried out at 5 ° C for 1 hour. Thereafter, 476.5 g of allyl glycidyl ether was added dropwise, and the mixture was stirred at the reflux temperature for 5 hours. When the reaction solution was analyzed after the reaction was completed, the reaction rate of allyl methacrylate was 87%.

The reaction solution was filtered through a 0.5-micron filter and the solvent was distilled off under reduced pressure at 70 ° C. or lower to obtain 88 g of a pale yellow transparent liquid. This liquid is GPC
When the molecular weight was measured by the method, it was MN2200. This liquid was added to 2N-NaOH to remove residual Si-
When H was measured, the reaction rate of Si—H was 95%. Also, IR (infrared absorption spectrum) is 1720 cm
^-1 to the absorption of the carboxylic acid ester, there is absorption of vinyl group in 1640 cm ^-1.

[0039]

Example I-1 A 300 ml four-necked flask equipped with a thermometer, a stirring rotor, a cooling tube, and a nitrogen supply introduction tube was charged with 59.6 g of p-xylene, and a dropping funnel was charged with methyl methacrylate. 31.8 g, acrylic acid n-
Butyl 20.3 g, 3-methacryloxypropyltrimethoxysilane 5.8 g, the silicone compound obtained in Synthesis Example 1 26.45 g, p-xylene 26.45 g, azobisisobutyronitrile (hereinafter abbreviated as AIBN) 0.
A mixed solution of 6 g, 1.7 g of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 1.2 g of n-dodecyl mercaptan was put therein and attached to the above 4-necked flask. Nitrogen was supplied into the 4-neck flask, and the inside of the reactor was sufficiently replaced with nitrogen. Stirring and heating were started, and the mixed solution was added dropwise while maintaining the inside of the 4-neck flask at 80 ° C. After the dropping was completed, the mixture was stirred at 80 ° C. for 5 hours.

After the reaction was completed, the reaction mixture was analyzed by GC. As a result, the reaction rate of methyl methacrylate was 100%, the reaction rate of n-butyl acrylate was 85%, and the reaction rate of 3-methacryloxypropyltrimethoxysilane was 100%. When the molecular weight was measured by the GPC method, MN6000, MW1600
It was 0. The viscosity of this reaction solution at 30 ° C. is 164
It was mPa · s.

[0041]

Example I-2 35 g of xylene was charged in the same reactor as in Example I-1, and a mixed solution having the following composition was added dropwise while stirring at 100 ° C. Then, the mixture was further stirred at 100 ° C. for 5 hours. Methyl methacrylate 18.5 g n-butyl acrylate 4.0 g Compound obtained in Synthesis Example 1 15.0 g Isobornyl acrylate 8.0 g 3-methacryloxypropyl 3.5 g Trimethoxysilane 1,2,2,6 6-pentamethyl 1.0 g-4-piperidyl methacrylate AIBN 0.5 g xylene 15.0 g After completion of the reaction, the molecular weight was measured and found to be MN6000.

Synthesis Example 3 Copolymer Not Containing Component (B) 58.6 g of xylene was charged in the same manner as in Example I-1, and 8
While stirring at 0 ° C, a mixed solution having the following composition was added dropwise at 80 ° C. Then, the mixture was stirred at 80 ° C. for 5 hours. Methyl methacrylate 32.5 g n-butyl acrylate 20.7 g Compound obtained in Synthesis Example 2 26.5 g 3-methacryloxypropyl 5.9 g Trimethoxysilane AIBN 0.85 g n-C ₁₂ H ₂₅ SH 1.70 g As a result, the molecular weight of the obtained polymer was MN6000.

[Synthesis Example 4] (A) and (B) Copolymer not Containing Both Components 70 g of toluene was charged in the same manner as in Example I-1, and the temperature was 80 ° C.
The mixed liquid having the following composition was added dropwise at 80 ° C. with stirring.
Then, the mixture was stirred at 80 ° C. for 5 hours. Methyl methacrylate 54 g n-butyl acrylate 34 g 3-methacryloxypropyl 12 g trimethoxysilane AIBN 1.0 g n-C ₁₂ H ₂₅ SH 2.0 g As a result, the molecular weight of the obtained polymer was MN5500.

[0044]

[Examples II-1 and II] The resin solutions obtained in Examples I-1 and I-2 were mixed with a curing catalyst in an amount of 1% by weight based on the resin component, and the viscosity was adjusted to 15 seconds with Ford cup # 4 using xylene as a thinner. Then, the coating film obtained by coating and heat curing at 150 ° C. for 30 minutes was evaluated. The results are shown in Table 1.

[0045]

Comparative Examples 1-2: On the other hand, (B) obtained in Synthesis Examples 3-4
A resin containing no vinyl compound as a component was used in Example II.
Coating was carried out in the same manner as in -1 to 2 and curing and evaluation were carried out to make a comparative example. The results are also shown in Table 1.

[0046]

[Table 1]

[0047]

The coating film using the coating material thus obtained has excellent gloss and weather resistance. In addition, since it exhibits acid resistance, solvent resistance, water repellency, and stain resistance, it has high performance applicable to fields such as new car middle coating and top coating, automobile repair, building exteriors, building materials, plastics, and various metal products. Used as paint.

Claims (1)

[Claims] 1. A (A) silicone compound, 1)
It has a structure represented by the following general formulas (I) and (II) in the molecular structure, and 2) R ² —O— when bound to silicon as an end group and R ² — when bound to oxygen. (R ² is a linear or branched alkyl group having 1 to 18 carbon atoms or a phenyl group), 3) number average molecular weight 800 to 20
, And 4) 5-80% by weight of a silicone compound having an R ¹ / R ² ratio of 0.8-10, (B) 0.1 to 1 vinyl compound represented by the following general formula
0% by weight and (C) Vinyl monomer other than (B) 10 to 10
94.9% by weight of a polymerizable monomer component (however,
The total number of components (A), (B), and (C) is 100% by weight), and the number average molecular weight is 1,000 to 2
A coating material consisting of a vinyl-based copolymer of 0,000.