JPH083247A - Method for producing coating composition - Google Patents

Abstract

PURPOSE:To produce a coating composition excellent in adhesion, hardness, boiling water resistance, transparency and storage stability. CONSTITUTION:An alkoxysilyl-containing ethylenically unsaturated monomer is copolymerized with a hydroxy (meth)acrylic ester and an unsaturated epoxy monomer in the presence of a silicate oligomer represented by the general formula (wherein (n) is an integer of 1-20; and R is hydrogen, a 1-4C alkyl or phenyl) in an organic solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a coating composition. More specifically, the surface of metal such as iron, plastic, wood, concrete, etc. has scratch resistance, transparency,
The present invention relates to a method for producing a coating composition capable of forming a coating film having excellent boiling water resistance, heat resistance, weather resistance, and adhesion.

[0002]

2. Description of the Related Art Conventionally, various coating compositions containing a silicon compound have been investigated for the purpose of improving scratch resistance. For example, as a method using an alkoxysilane hydrolyzate, Japanese Patent Laid-Open Nos. 53-2565 and 56-56 are available.
22365, JP-A-61-166824 and the like. Further, as a coating composition containing organoalkoxysilane and colloidal silica or colloidal alumina as main components, JP-B-52-39691 and JP-B-5
3-5042, JP-A-54-87736, JP-A-55-
94971, JP-A-56-99236, JP-A-59-6.
It is proposed in Japanese Patent No. 8377. Furthermore, coating compositions using an acrylic copolymer containing an alkoxysilyl group are disclosed in JP-A-3-47871 and JP-A-3-3787.
It is proposed in Japanese Patent Laid-Open No. 54278. Furthermore, in order to exert the respective characteristics of both, it has been noted that a composition obtained by mixing the above-mentioned hydrolyzate of alkoxysilane and an acrylic copolymer is used for coating.

[0003]

However, the coating composition comprising the above mixture has room for improvement in the transparency and boiling water resistance of the resulting coating film. An object of the present invention is to form a coating film having good transparency and boiling water resistance on the surface of metals such as iron, plastics, wood, concrete, etc., and further scratch resistance which the composition originally has. sex,
It is intended to provide a coating composition having heat resistance, weather resistance and adhesion.

[0004]

[Means for Solving the Problems] As a result of extensive studies to solve the above problems, the physical properties of the coating film can be improved by allowing a specific silicate oligomer to coexist during the polymerization of an alkoxysilyl group-containing ethylenically unsaturated monomer. They have found that they can be improved and have reached the present invention. That is, the present invention provides an alkoxysilyl group-containing ethylenically unsaturated monomer, a hydroxyl group-containing (meth) acrylic ester and an epoxy group in the presence of a silicate oligomer represented by the following general formula [I] in an organic solvent. A method for producing a coating composition, which comprises copolymerizing a contained unsaturated monomer and, if necessary, a (meth) acrylic acid alkyl ester.

Embedded image (In the formula, n is an integer of 1 to 20, R is hydrogen or a carbon number of 1 to
4 represents an alkyl group or a phenyl group)

The present invention will be described in detail below. The silicate oligomer used in the present invention is not particularly limited as long as it is represented by the following general formula [I].

Embedded image (In the formula, n is an integer of 1 to 20, R is hydrogen or a carbon number of 1 to
4 represents an alkyl group or a phenyl group)

The silicate oligomer can be obtained, for example, by hydrolyzing tetraalkoxysilane or tetraphenoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane. n can be adjusted by controlling the hydrolysis rate in this case

The hydrolysis reaction itself can be carried out by a known method. For example, a predetermined amount of water is added to the above tetraalkoxysilane in the presence of an acid catalyst to distill off the alcohol by-produced, usually at room temperature. The reaction is performed at about -100 ° C. The alkoxysilane is hydrolyzed by this reaction, and a liquid silicate oligomer having two or more hydroxyl groups by a condensation reaction (usually an average degree of polymerization of about 2 to 8,
Preferably 3-6) is obtained as a hydrolyzate. The degree of hydrolysis can be appropriately adjusted depending on the amount of water used, but in view of the physical properties of the coating composition or the curing of the coating film, it is usually 40 to 90 in the present invention.
%, Preferably about 60 to 80%. When it is more than the above range, the adhesiveness is lowered, and when it is less than the above range, n is 0, which is not preferable because the hardness is lowered.

The tetraalkoxysilicate oligomer thus obtained usually contains about 2 to 10% of a monomer. If this monomer is contained, the storage stability of the coating composition is lacking, the viscosity increases during storage, and it becomes difficult to form a thin film. Therefore, the monomer content should be 1% or less, preferably 0.3% or less. This monomer removal is carried out by flash distillation and vacuum distillation so that

The amount of the silicate oligomer used is 5 to 500 parts by weight, preferably 10 to 400 parts by weight, particularly preferably 10 to 30 parts by weight, based on 100 parts by weight of the monomer to be polymerized.
0 parts by weight. If it is less than this, the hardness of the coating film is remarkably lowered, and if it is more than this, the adhesiveness to the substrate is remarkably lowered.
Incidentally, when the amount of the acrylic monomer in the above range is large, alkali resistance and storage stability are improved, and when the content of the silicate oligomer is large, hardness, solvent resistance, weather resistance, and adhesion tend to be improved. is there.

The alkoxysilyl group-containing ethylenically unsaturated monomer used in the present invention means γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth). Acryloxydimethyldimethoxysilane, γ- (meth) acryloxytrimethoxysisilane, γ- (meth) acryloxytriethoxysisilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, vinyltri (ethoxymethoxy) ) Silane, allyltrimethoxysilane, P-vinylphenyltrimethoxysilane and the like. Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, vinyltriethoxysilane and the like are preferably used.

As the hydroxyl group-containing (meth) acrylic acid ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Examples include 3-hydroxypropylpropyl (meth) acrylate and 4-hydroxylbutyl (meth) acrylate.

As the epoxy group-containing unsaturated monomer,
Examples include glycidyl (meth) acrylate and (meth) allyl glycidyl ether. As needed, aromatic monomers such as styrene and vinyltoluene, vinyl compounds such as vinyl acetate and vinyl propionate, dialkylaminoethyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate. ) One or more acrylic esters are used in combination.

In the co-polymerization, only an alkoxysilyl group-containing ethylenically unsaturated monomer, a hydroxyl group-containing (meth) acrylic acid ester and an epoxy group-containing unsaturated monomer may be copolymerized. Copolymerization with acrylic acid alkyl ester is also possible. (Meta)
The carbon number of the alkyl group of acrylic acid alkyl ester is
There is no particular limitation, and any one having about 1 to 20 can be used, but use of a combination of an alkyl group having 1 to 3 carbon atoms and an alkyl group having 4 or more carbon atoms is not preferable. It is preferable in terms of the balance of physical properties of the film. (A) Alkyl group-containing (meth) acrylic acid alkyl esters having 1 to 3 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate and the like. Are used alone or in combination of two or more.

Examples of (b) alkyl ester of (meth) acrylic acid having 4 or more carbon atoms in the alkyl group include butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and (meth) acrylate. ) Acrylic acid t
-Butyl, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth)
Examples thereof include octyl acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate, which may be used alone or in combination of two or more.

In the case of copolymerizing only an ethylenically unsaturated monomer containing an alkoxysilyl group, a (meth) acrylic acid ester containing a hydroxyl group and an unsaturated monomer containing an epoxy group, a unit amount in 100 parts by weight of the monomer is obtained. As for the proportion of the body, the alkoxysilyl group-containing ethylenically unsaturated monomer is 1 to 30% by weight, preferably 5 to 25% by weight, and the hydroxyl group-containing (meth) acrylic acid ester is 0.5 to 50% by weight, preferably 1 to 30% by weight, 0.5 to 30% by weight, preferably 1 to 25% by weight, of the epoxy group-containing unsaturated monomer are advantageous.

Further, when the (meth) acrylic acid alkyl ester is used in combination, the ratio of the alkoxysilyl group-containing ethylenically unsaturated monomer in 100 parts by weight of the total amount of the monomers is 1 to 30% by weight, preferably 5 to 25% by weight, hydroxyl group-containing (meth) acrylic acid ester 0.5 to 50
% By weight, preferably 1-30% by weight, 0.5-30% by weight of epoxy group-containing unsaturated monomer, preferably 1-25
% By weight, 40% of (meth) acrylic acid alkyl ester
Advantageously, it is 98% by weight, preferably 50 to 95% by weight. In addition, in the (meth) acrylic acid alkyl ester, an alkyl group (meth) acrylic acid alkyl ester (a) having 1 to 3 carbon atoms and an alkyl group (meth) acrylic acid alkyl ester (b) having 4 or more carbon atoms are included. The ratio of (a) / (b) is preferably 2/8 to 8/2, and more preferably 3/7 to 7/3 on a weight basis.

By using such a monomer, the crosslinkability with the silicate oligomer is improved. Also, when the coating film is cured, it contracts, internal stress may occur, and problems such as cracks may occur, but to avoid this,
It is preferable to set the glass transition point low depending on the composition ratio of the polymer. A specific temperature range of a suitable glass transition point (Tg) is −20 to 60 ° C.

A feature of the present invention is that an alkoxysilyl group-containing ethylenically unsaturated monomer, a hydroxyl group-containing (meth) acrylic ester and an epoxy group-containing unsaturated monomer are added in the presence of the silicate oligomer in an organic solvent. This is the point of co-polymerization. The method of such coexisting polymerization is not particularly limited, but for example, it can be produced by mixing each component and by a usual radical polymerization method.

The organic solvent used in the present invention is not particularly limited, and those capable of dissolving the raw material monomer and polymer and the silicate oligomer can be used, and can be appropriately selected depending on the substrate to be coated or the coating method. Is.
Specific examples of usable organic solvents include methanol, ethanol, isopropyl alcohol, n-butanol, and
Alcohol such as octanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-
Glycol derivatives such as propyl ether and ethylene glycol mono-n-butyl ether, benzene, kerosene,
Hydrocarbons such as toluene and xylene, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and ethyl ether, butyl ether, methyl cellosolve , Ethers such as ethyl cellosolve, dioxane, furan, and tetrahydrofuran. These organic solvents can be used either individually or in combination.

The amount of the solvent used is 20 to 2 with respect to 100 parts by weight of the total amount of the monomer and the silicate oligomer.
It is possible in the range of 00 parts by weight. This composition ratio can be appropriately selected according to the purpose of use. If the amount is less than the above range, there may occur problems during coating, such as difficulty in obtaining a uniform coating film.

As the polymerization catalyst, known radical polymerization catalysts such as azobisisobutyronitrile, benzoyl peroxide, ditertiary butyl peroxide,
Cumene hydroperoxide and the like are used. A suitable temperature for the polymerization is 60 to 150 ° C., and a practical polymerization time is about 6 to 20 hours. The composition of the present invention is
As described above, the organic solvent used at the time of polymerization can be put to practical use as a coating material in the state of being used as it is, but if necessary, it may be used by substituting it with an arbitrary solvent.

Further, it is desirable to use a curing catalyst in the coating composition of the present invention thus obtained. The curing catalyst should be added before use (two-pack type)
It is also possible to store in the state of being added from the beginning (one-pack type). Specific examples of the curing catalyst include hydrochloric acid, nitric acid, phosphoric acid, inorganic acids such as boric acid, acetic acid, formic acid, maleic acid, phthalic acid, benzoic acid, organic acids such as paratoluenesulfonic acid, dibutyltin laurylate, dibutyltin octoate, Dibutyltin acetate, organotin compounds such as dioctyltin laurate, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetrabutoxy titanate, monomethyl phosphate, phosphate esters such as monoethyl phosphate, γ
-Aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-
There are silane coupling agents such as ureidopropyltriethoxysilane.

In addition, organoaluminum compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum, tetrabutylzirconate, organozirconium such as butoxytris (acetylacetonato) zirconium, ethylenediamine, diethylenetriamine, piperazine , Amines such as metaphenylenediamine, diethanolamine and triethanolamine, alkali compounds such as sodium hydroxide and potassium hydroxide, and epoxy compounds.
Inorganic acids, organic tin compounds, organic acids and organic aluminum compounds are particularly preferable. The amount of these catalysts used varies depending on the catalyst, but when hydrochloric acid is used, it is preferably about 0.1 to 2 parts by weight with respect to 100 parts by weight of the silicate oligomer.

The method of using the composition of the present invention will be described more specifically. The polymer composition obtained by the above co-polymerization is usually adjusted in concentration, then a curing catalyst is added, and then the composition is applied to a substrate and dried by heating. When R of the silicate oligomer is an alkyl group or a phenyl group, it may be hydrolyzed if necessary. As the base material in this case, iron, stainless steel, aluminum, other metals, alloys,
Applicable to plastic, wood, cement, concrete, etc. Examples of the coating method include brush coating, spin coating, spray coating, depping, roll coating, and gravure printing. The film thickness at this time is preferably 0.1 to 200 μm, more preferably 1 to 100 μm. The composition of the present invention is particularly effective for thickening the coating film, and the conventional one had a high possibility of causing cracks and the like at a thickness exceeding 50 μm, but the present invention made it possible to further thicken the film. When it is thinner than the above range, it is difficult to obtain sufficient scratch resistance, and when it is thicker than the above range, cracks may occur, which is not preferable.

In addition, when preparing a coating composition using the composition of the present invention, it is necessary to add a dehydrating agent or an alkyl alcohol having an alkyl group having 1 to 10 carbon atoms in consideration of the stability of the coating composition. There is. As the dehydrating agent in this case,
Trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, trimethyl orthopropionate, trimethyl orthopropionate, trimethyl orthoisopropionate, triethyl orthoisopropionate, orthobutyric acid Trimethyl, triethyl orthobutyrate, trimethyl orthoisobutyrate, orthocarboxylic acid esters such as triethyl orthoisobutyrate are used, and the addition amount is 0 to 30 parts by weight, preferably 100 parts by weight of the co-polymerized alkoxysilyl group-containing polymer. 0.
5 to 30 parts by weight, particularly preferably 5 to 25 parts by weight.

Further, as pigments used in the paint, white pigments such as titanium oxide, calcium carbonate, talc, lithobon, barium sulfate, calcium sulfate, alumina and clay, black pigments such as carbon black and iron black, phthalocyanine blue, Blue pigments such as navy blue and ultramarine blue, yellow pigments such as lake yellow, yellow lead, oak yellow and Hansa yellow, red pigments such as red iron oxide and lake red, orange pigments such as chrome vermillion, green pigments such as phthalocyanine green and chromium oxide. And so on.

Further, other additives for resins can be added to the composition of the present invention as long as the curing of the invention is not impaired. For example, ultraviolet stabilizer, antioxidant, antistatic agent, conductivity imparting agent, scratch resistance imparting agent, compatibilizer, adhesiveness imparting agent, colorant, fluidity improving agent, plasticizer, anti-sagging agent, precipitation Examples include an inhibitor and an antifoaming agent. A sand mill, a disper, a ball mill and the like which are usually used are used for preparing the paint. This paint can be used as a top coat paint for exterior materials such as concrete, mortar buildings, roof tiles and siding boards, and also as a paint for interiors and floors of buildings, and in particular, it has excellent weather resistance in exterior applications. It can be used as paint.

[0028]

In the present invention, a coating composition which gives a coating film excellent in scratch resistance, transparency, boiling water resistance and storage stability can be obtained.

[0029]

The present invention will be described in more detail based on the following examples and comparative examples, but the invention is not limited to the following examples as long as the gist thereof is not exceeded. The coating film was evaluated by the following methods. (1) Cellotape peeling: In order to evaluate the adhesive strength of the coating film, 11 parallel and 11 horizontal and vertical lines perpendicular to the center of the coating film were drawn at 1 mm intervals until reaching the substrate surface, and 1 in 1 cm ²
I added a grid to make 00 squares. A cellophane adhesive tape (trade name: “Cellotape” made by Nichiban) was strongly adhered to the cross of the grid, and the number of squares without peeling was measured when the tape was rapidly peeled in the direction of 90 degrees.

(2) Pencil hardness: The degree of scratches is determined by JIS K
It was evaluated by a pencil hardness test according to 5400. (3) Boiling water resistance of coating film: The coating film was immersed in hot water at 100 ° C for 5 hours together with the base material, and the state of gloss and cracking of the coating film was visually observed. The case where the coating film was not glossy or cracked was rated as ◯, and the one where slight glossiness was recognized was rated as Δ. (4) Transparency (haze): Measured according to JIS K-7105.

[Preparation of Silicate Oligomer] Silicate Oligomer A 500 equipped with a stirrer, reflux condenser and thermometer
Tetramethoxysilane 2 was added to a 3 ml round bottom flask.
After adding 34 g and 74 g of methanol and mixing, 0.0
22.2 g of 5% hydrochloric acid was added, and a hydrolysis reaction was carried out at an internal temperature of 65 ° C. for 2 hours. Next, the condenser was replaced with an extraction tube, the internal temperature was raised to 150 ° C., the mixture was extracted with methanol and further heated at 150 ° C. for 3 hours to condense to obtain a hydrolyzate. The degree of polymerization was 3 to 6 and the hydroxyl group was 10 or more. The amount of monomers in the tetramethoxysilane oligomer was 5%.

Silicate oligomer B Subsequent to the above, the jacket heated to 100 to 150 ° C. is boiled with tetramethoxysilane oligomer, and the vaporized monomer is discharged out of the system together with the inert gas. The amount of monomers in the tetramethoxysilane oligomer thus obtained was 0.2%. Silicate Oligomer C Tetraethoxysilane is used instead of the above tetramethoxysilane, and the amount of monomers in the oligomer is 0.3% or less. Tetraethoxysilane oligomer (degree of polymerization 3 to 6)
I got

Examples 1 to 3 In a flask equipped with a nitrogen inlet tube, a reflux condenser, a thermometer and a stirrer, 100 parts by weight of γ-methacryloxypropyltrimethoxysilane, 50 parts by weight of 2-hydroxyethyl methacrylate and methacryl were added. Glycidyl acidate 50 parts by weight, methyl methacrylate 450 parts by weight, acrylic acid n
-Butyl 350 parts by weight, silicate oligomers A to C
500 parts by weight (in terms of pure content) and xylene 42
0 parts by weight, 80 parts by weight of isopropyl alcohol, and 2 parts by weight of benzoyl peroxide were charged and heated to 90 ° C. to start polymerization. Two hours after the initiation of the polymerization, the polymerization was continued for 10 hours while adding a solution of 8 parts by weight of benzoyl peroxide in 30 parts by weight of xylene. A co-polymerized product having a resin content of 72% by weight and a viscosity of 2100 cps (25 ° C.) was obtained. Tg was 20 ° C. To the above co-polymerized product, 600 parts by weight of xylene was added to make the resin content 54% by weight. 0.95 g of 1N hydrochloric acid is added to this solution, and the mixture is stirred at 65 ° C. for 30 minutes. Add this solution to a glass plate (70 mm × 150 mm × 0.5 m
m) with an applicator and then at 110 ° C for 30
Heat treatment was performed for a minute. The physical properties of this coating film (100 μ) were evaluated by the methods described above, and the results are shown in Table 1.

Examples 4 to 5 In the monomer composition of Example 2, 200 parts by weight of γ-methacryloxypropyltrimethoxysilane, 100 parts by weight of 2-hydroxyethyl methacrylate and 50 parts by weight of allylglycidyl ether. Parts, 300 parts by weight of methyl methacrylate, 200 parts by weight of n-butyl acrylate, 150 parts by weight of styrene (Example 4), 50 parts by weight of γ-methacryloxypropyltriethoxysilane, 2-methacrylate 100 parts by weight of hydroxyethyl, 100 parts by weight of glycidyl methacrylate, 300 parts by weight of methyl methacrylate, 3 parts of n-butyl acrylate.
50 parts by weight and styrene were changed to 100 parts by weight (Example 5). Tg of Example 4 is 40 ° C., Example 5
Was 7 ° C. The results are shown in Table 1. Examples 6 to 7 In Example 2, the amount of silicate oligomer used was 1
000 parts by weight (Example 6) and 1500 parts by weight (Example 7). The results are shown in Table 1. Example 8 The same operation as in Example 2 was performed except that dibutyltin dilaurate was used instead of hydrochloric acid. The results are shown in Table 1.

Example 9 The same operation as in Example 2 was carried out except that tris (acetylacetate) aluminum was used instead of hydrochloric acid. The results are shown in Table 1. Control Example 1 In Example 2, the use of the silicate oligomer was omitted during the copolymerization, and the silicate oligomer was mixed after the polymerization. The results are also shown in Table 1. The haze was measured immediately after the mixture was manufactured.

[0036]

[Table 1] Oligomer Cellotape Peeling Pencil Hardness Water Resistance Water Resistance Transparency (Haze) Example 1 A 100/100 HB ○ 0.2 〃 2 B 100/100 HB ○ 0.2 〃 3 C 100/100 HB ○ 0. 2 〃 4 B 100/100 H ○ 0.2 〃 5 B 100/100 F ○ 0.2 〃 6 B 100/100 2H ○ 0.2 〃 7 B 100/100 3H ○ 0.2 〃 8 B 100 / 100 F ○ 0.2 〃 9 B 100/100 F ○ 0.2 Control Example 1 B 100/100 F △ 24.6

[0037]

EFFECTS OF THE INVENTION The coating composition of the present invention can form a coating film having high adhesion to each substrate, sufficient hardness, good boiling water resistance and excellent transparency. Further, it is a coating composition which has excellent storage stability and coating performance and is extremely easy to handle.

Claims (7)

[Claims] 1. In the presence of a silicate oligomer represented by the following general formula [I] in an organic solvent, an alkoxysilyl group-containing ethylenically unsaturated monomer, a hydroxyl group-containing (meth) acrylic acid ester and an epoxy group-containing A method for producing a coating composition, which comprises copolymerizing an unsaturated monomer. Embedded image (In the formula, n is an integer of 1 to 20, R is hydrogen or a carbon number of 1 to
4 represents an alkyl group or a phenyl group) 2. A silicate oligomer 5 to 500 per 100 parts by weight of the total amount of the alkoxysilyl group-containing ethylenically unsaturated monomer, the hydroxyl group-containing (meth) acrylic acid ester and the epoxy group-containing unsaturated monomer. The manufacturing method according to claim 1, wherein a weight part is used. 3. A silicate oligomer is added to 10 parts by weight of a total amount of 100 parts by weight of an alkoxysilyl group-containing ethylenically unsaturated monomer, a hydroxyl group-containing (meth) acrylic acid ester and an epoxy group-containing unsaturated monomer. The manufacturing method according to claim 1, wherein 400 parts by weight is used. 4. The total amount of the alkoxysilyl group-containing ethylenically unsaturated monomer, the hydroxyl group-containing (meth) acrylic acid ester and the epoxy group-containing unsaturated monomer is 100.
The ratio of the alkoxysilyl group-containing ethylenically unsaturated monomer in the parts by weight is 1 to 30% by weight, the ratio of the hydroxyl group-containing (meth) acrylic acid ester is 0.5 to 50% by weight, and the epoxy group-containing unsaturated unit amount Body ratio is 0.5 to 30
It is weight%, The manufacturing method of Claim 2 or 3 characterized by the above-mentioned. 5. A total amount of 100 parts by weight of an alkoxysilyl group-containing ethylenically unsaturated monomer, a hydroxyl group-containing (meth) acrylic acid ester, an epoxy group-containing unsaturated monomer, and a (meth) acrylic acid alkyl ester. The ratio of the alkoxysilyl group-containing ethylenically unsaturated monomer in 1 is 1
To 30% by weight, the proportion of hydroxyl group-containing (meth) acrylate ester is 0.5 to 50% by weight, the proportion of epoxy group-containing unsaturated monomer is 0.5 to 30% by weight, alkyl (meth) acrylate The method according to claim 1, wherein the proportion of the ester is 40 to 98% by weight. 6. The production method according to claim 2, wherein tetramethoxysilane partial hydrolyzate is used as the silicate oligomer. 7. The silicate oligomer, which is a partial hydrolyzate of tetramethoxysilane and has a monomer amount of 1% by weight or less, is used.
Any one of the manufacturing methods.