JPH1060366A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating compsn. of which the resin soln. has a good storage stability and which can form a coating layer excellent in resistances to salt water and boiling and has good characteristics such as adhesive power, gloss, and surface hardness. SOLUTION: This compsn. comprises a silicate oligomer and an acrylic copolymer produced from 99-40wt.% (meth)acrylate, 1-20wt.% fluoroalkyl (meth) acrylate having a 3C or higher alkyl group of which at least three H atoms have been substd. by F atoms, 0-20wt.% alkoxysilylated (meth)acrylate. and O-59wt.% other comonomer. The amt. of the oligomer compounded is pref. 5-200 pts.wt. based on 100 pts.wt. copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition comprising a silicate oligomer and a specific acrylic copolymer, having good storage stability of a resin solution and having excellent salt water resistance and boiling resistance. It is.

[0002]

2. Description of the Related Art From the viewpoint of improving properties such as abrasion resistance,
Some proposals have been made for coating compositions using an acrylic copolymer containing an alkoxysilyl group. For example, JP-A-3-47871 discloses an acrylic polymer (X) containing at least one or more groups of an acid anhydride group, an epoxy group, an amino group and a carboxyl group and a hydroxyl group, and an acid anhydride. Polymer containing at least one or more of a group, an epoxy group, an amino group and a carboxyl group and an alkoxysilyl group
A thermosetting composition comprising (Y) and a curing catalyst (Z) is shown. JP-A-3-54278 discloses that a hydroxyl group-containing acrylic resin (X), an alkoxysilyl group-containing acrylic copolymer (Y), and a curing catalyst are used as a top coat layer.
The use of a siloxy- or siloxane-crosslinked thermosetting coating consisting of (Z) is disclosed.

[0003] Japanese Patent Application Laid-Open No. 8-600 filed by the present applicant
No. 75 discloses a coexisting polymer (X) obtained by copolymerizing (meth) acrylate and a hydroxyl group-containing (meth) acrylate in an organic solvent in the presence of a silicate oligomer, an acrylic resin (Y), Are shown. Japanese Patent Application Laid-Open No. Hei 7-331162, also filed by the present applicant, discloses that 100 parts by weight of an alkoxysilyl group-containing ethylenically unsaturated monomer is polymerized in an organic solvent in the presence of 5 to 500 parts by weight of a silicate oligomer. A method for producing a coating composition is shown.

JP-A-6-145453 discloses an alkoxysilyl group-containing acrylic copolymer (X), a tetraalkylsilicate or a condensate thereof (Y), and a curing catalyst.
(Z), wherein trifluorofluoroethyl (meth) acrylate and pentafluoropropyl (meth) acrylate are used as comonomer components of the alkoxysilyl group-containing acrylic copolymer (X). There is also a mention that fluoroalkyl (meth) acrylates such as perfluorocyclohexyl (meth) acrylate or fluorocycloalkyl (meth) acrylate can be used.

[0005]

SUMMARY OF THE INVENTION Japanese Patent Application Laid-Open Nos. 3-47871 and 3-54 relate to a mixture of a specific acrylic resin and an acrylic copolymer containing an alkoxysilyl group.
The composition disclosed in Japanese Patent No. 278 also has room for improvement in practical use in terms of storage stability, coating film hardness, salt water resistance and the like.

Japanese Patent Application Laid-Open No. 8-600 filed by the present applicant
The coating compositions disclosed in JP-A-75-75 and JP-A-7-331162 have room for further improvement in the storage stability of the resin solution, salt water resistance, boiling resistance, and the like.

The composition of JP-A-6-145453,
That is, an alkoxysilyl group-containing acrylic copolymer
(X) and a tetraalkyl silicate or a condensate thereof
(Y) and a curing catalyst (Z), the hydrophilic curable composition is, for example, an alkoxysilyl group-containing acrylic copolymer
Even when trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, or perfluorocyclohexyl (meth) acrylate is used as the comonomer component of (X), there is a limit that salt water resistance and boiling resistance are insufficient. .

Under such a background, the present invention provides a coating having good storage stability of a resin solution, excellent salt water resistance and boiling resistance, and excellent properties such as adhesion, gloss and surface hardness. It is an object to provide a coating composition capable of providing a layer.

[0009]

Coating composition of the present invention, in order to solve the problems] includes a silicate oligomer (A), (meth) acrylate (b ₁₎ 99 to 40 wt%, of the H of the alkyl group having 3 or more carbon atoms fluoroalkyl or 6 is substituted with F in (meth) acrylate (b ₂₎ 1 to 20 wt%, an alkoxysilyl group-containing (meth) acrylate (b ₃₎ 0 to 20 wt%, and a comonomer other than the above ( b ₄ ) 0-59% by weight
And an acrylic copolymer (B) containing as a copolymer component.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

<Basic Composition> The coating composition of the present invention basically comprises a composition obtained by mixing a silicate oligomer (A) and an acrylic copolymer (B).

<Silicate Oligomer (A)> As the silicate oligomer (A), those represented by the above formula (i) are used. As described in the formula (i), R is H, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is an integer of 1 to 20. Silicate oligomer
Specific examples of (A) are obtained by hydrolyzing tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane or tetraphenoxysilane.
n is adjusted by controlling the hydrolysis rate during hydrolysis.

[0013]

(Equation 1)

In the hydrolysis reaction, for example, a predetermined amount of water is added to tetraalkoxysilane or tetraphenoxysilane to distill off alcohol or phenol by-produced in the presence of a catalyst (often using an acid catalyst). The reaction is carried out at room temperature to 100 ° C. while the reaction is being carried out. By this reaction, tetraalkoxysilane or tetraphenoxysilane is hydrolyzed, and a liquid silicate oligomer having two or more hydroxyl groups is obtained as a hydrolyzate by a condensation reaction. Although the degree of polymerization varies, the average degree of polymerization is usually about 2 to 8, preferably 3 to 6. Although the degree of hydrolysis can be appropriately adjusted depending on the amount of water used, it is usually 40 to 90%, preferably 60 to 90% for use of the coating composition of the present invention.
An appropriate value is 80%.

The silicate oligomer (A) thus obtained usually contains about 2 to 10% of a monomer. Since this monomer reduces the storage stability of the coating composition, the monomer content is 1% or less, preferably
It is desirable to remove the monomer by flash distillation or vacuum distillation until the content becomes 0.3% or less.

<Acrylic Copolymer (B)> The acrylic copolymer (B) is composed of 99 to 40% by weight of (meth) acrylate (b ₁ ) and 6 or more of H of an alkyl group having 3 or more carbon atoms. Is a fluoroalkyl (meth) acrylate substituted with F
(b ₂ ) 1 to 20% by weight containing an alkoxysilyl group (meth)
Acrylate (b ₃₎ 0 to 20 wt%, and other than these comonomers (b ₄₎ is intended to be 0-59 wt% of a copolymerizable component.

As the (meth) acrylate (b ₁ ), first, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate,
C2-C12 such as lauryl acrylate, benzyl (meth) acrylate, and cyclohexyl acrylate
Acrylate having a degree of 4 to 1 carbon atoms such as butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, and cyclohexyl methacrylate.
About two acrylates. These are soft segments that give polymers with a low glass transition point. Examples of the (meth) acrylate include hard segments that give a polymer having a high glass transition point, such as methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and isopropyl methacrylate.

The (meth) acrylate (b ₁ ) is composed of a (meth) acrylate that gives a soft segment and a (meth) acrylate that gives a hard segment, on a weight basis.
It is desirable to use a ratio of 2: 8 to 9: 2, particularly 3: 7 to 7: 3. Of these, at least a part of the (meth) acrylate that provides the latter hard segment can be replaced with a hard component such as styrene or vinyl acetate among other monomers described below.

Fluoroalkyl (meth) acrylate (b
₂ ) is 6 out of H of the alkyl group having 3 or more carbon atoms.
A fluoroalkyl (meth) acrylate substituted by F or more is used. Those in which 5 or less of H of the alkyl group are substituted with F have insufficient effect of improving salt water resistance, and those in which H of the cycloalkyl group is substituted with F, regardless of the number of substitution with F. However, the effect of improving salt water resistance is still insufficient. Among fluoroalkyl (meth) acrylates (b ₂ ), particularly preferred are fluoroalkyl (meth) acrylates in which 8 or more of H of an alkyl group having 5 or more carbon atoms are substituted with F. Are 13 of the H of alkyl groups having 8 or more carbon atoms.
Fluoroalkyl (meth) acrylate substituted by F or more, especially one of H of alkyl group having 10 carbon atoms.
7 is heptadecafluorodecyl (meth) acrylate substituted with F.

As the alkoxysilyl group-containing (meth) acrylate (b ₃ ), γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxydimethyl Dimethoxysilane, γ- (meth) acryloxytrimethoxysilane, γ- (meth) acryloxytriethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, vinyltri (ethoxymethoxy) silane, allyltri Examples include methoxysilane and p-vinylphenyltrimethoxysilane. Among them, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, vinyltriethoxysilane and the like are preferable.

Other comonomers (b ₄ ) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and diethylene glycol monomethacrylate. (Meth) acrylates containing hydroxyl groups such as (meth) acrylate; (meth) acrylates containing epoxy groups such as glycidyl (meth) acrylate; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; maleic acid, fumaric acid , Unsaturated dicarboxylic acids such as itaconic acid;
Anhydrides of these unsaturated dicarboxylic acids; half esters of maleic acid and itaconic acid; (meth) acrylamide, N
-Methylol (meth) acrylamide; (meth) acrylonitrile; dimethylaminoethyl (meth) acrylate; styrene, α-methylstyrene, chlorostyrene,
Styrene monomers such as vinyl toluene; vinyl acetate,
Vinyl esters such as vinyl propionate and saturated branched fatty acid vinyl; allyl glycidyl ether; acetoacetylated (meth) acrylate;

The proportion of each component constituting the acrylic copolymer (B) is such that (meth) acrylate (b ₁ ) is 99 to 40% by weight.
(Preferably 95 to 50% by weight, more preferably 90% by weight.
60 wt%), fluoroalkyl (meth) acrylate (b ₂₎ from 1 to 20 wt% (preferably 2 to 15 wt%), an alkoxysilyl group-containing (meth) acrylate (b
₃₎ 0 to 20 wt% (preferably 1-20 wt%, more preferably 2 to 15% by weight), other than these comonomers (b ₄₎ is 0 to 59 wt% (preferably 0-50 wt%,
More preferably, it is set to 0 to 40% by weight. Balanced in such a quantitative range, for example,
The ratio of the fluoroalkyl (meth) acrylate (b ₂ ) is 1
When the amount is less than 20% by weight, the effect of improving the salt water resistance is insufficient, while when the ratio exceeds 20% by weight, the effect of improving the salt water resistance does not increase with respect to the amount used, and the cost is disadvantageous.

The above acrylic copolymer (B) is usually used in the presence of a solvent such as a hydrocarbon, an ester, an ether, a ketone, an alcohol, a glycol or a glycol ether.
It is obtained by subjecting each monomer component to radical polymerization according to a conventional method. As the polymerization catalyst, various catalysts such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide and cumene hydroperoxide are used. The polymerization temperature is 60
About 150 ° C. is appropriate.

The polymerization is carried out by the silicate oligomer described above.
It can be performed in the coexistence of (A). Coexisting polymerization is preferred in terms of storage stability and the like. In the case of coexistence polymerization, as a part of the monomer component, an alkoxysilyl group-containing (meth) acrylate (b ₃ ) or / and other comonomers
It is preferable to use a small amount of a (meth) acrylate containing a hydroxyl group or an epoxy group in (b ₄ ). This is because the crosslinkability with the silicate oligomer (A) is ensured and the properties are positive. Polymerizing the monomer in the presence of the silicate oligomer (A) also has the advantage that the polymerization can be carried out in the absence of a solvent or in the presence of a small amount of a solvent.

<Coating Composition> The coating composition of the present invention comprises a mixture of the silicate oligomer (A) and the acrylic copolymer (B).

The mixing ratio of the silicate oligomer (A) to 100 parts by weight of the acrylic copolymer (B) is 5 to 200.
Parts by weight, preferably 10 to 150 parts by weight. By setting to such a range, a composition having balanced and preferable properties is obtained, and a storage composition having good storage stability of the resin solution and good adhesion to an object is obtained, Furthermore, the desired salt water resistance and boiling resistance can be obtained, and a coating layer having good properties such as adhesion, gloss and surface hardness can be obtained.

It is usual to add a curing catalyst to the composition thus obtained. The curing catalyst may be added at the time of use, or may be previously added to the composition.

Examples of the curing catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and boric acid; organic acids such as formic acid, maleic acid, phthalic acid, benzoic acid and p-toluenesulfonic acid; dibutyltin laurate and dibutyltin. Organic tin compounds such as octate, dibutyltin acetate and diacryltin laurate; organic titanium compounds such as tetrapropyl titanate and tetrabutoxy titanate; phosphate esters such as monomethyl phosphate and monoethyl phosphate; γ-aminopropyltrimethoxysilane; N-β-
Silane coupling agents such as aminoethyl-γ-aminopropyltrimethoxysilane and γ-ureidopropyltriethoxysilane; organic aluminum compounds such as aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate); tetrabutyl zirconate And organic zirconium compounds such as butoxytris (acetylacetonate) zirconium; amines such as ethylenediamine, diethylenetriamine, piperazine, metaphenylenediamine, diethanolamine and triethanolamine; alkali compounds such as sodium hydroxide and potassium hydroxide; epoxy compounds; Can be exemplified. Of these, inorganic acids, organic acids, organic tin compounds, and organic aluminum compounds are preferred.

The amount of the curing catalyst varies depending on the type thereof, and thus cannot be determined unconditionally. For example, when hydrochloric acid is used, the amount is about 0.1 to 2 parts by weight based on 100 parts by weight of the silicate oligomer (A) component. Often.

The coating composition described above may optionally contain a dehydrating agent or an alcohol having 1 to 10 carbon atoms in an appropriate amount. Examples of the former dehydrating agent include trialkyl orthocarboxylates such as trialkyl orthoformate, trialkyl orthoacetate, trialkyl orthopropionate, trialkyl orthoisopropionate, trialkyl orthobutyrate, and trialkyl orthoisobutyrate. Can be

In the above-mentioned coating composition, if necessary, various fillers and pigments can be blended in appropriate amounts. Also, if necessary, an ultraviolet absorber, an antioxidant, an antistatic agent, a conductivity imparting agent, a scratch resistance imparting agent, a compatibilizing agent, an adhesion imparting agent, a fluidity improving agent, a plasticizer, a rheology improving agent, a sedimentation Inhibitors, defoamers and the like can be added.

Although the coating composition of the present invention can be applied to any object, it is particularly important to apply it to a metal. Examples of application methods include brush coating, roll coating, spray coating, dipping, spin coating, and printing. The coating thickness is optional, but is often 2 to 100 μm.

<Function> The coating composition of the present invention has good storage stability of a resin solution, excellent salt water resistance and boiling resistance, and has various properties such as adhesion, gloss and surface hardness. A good coating layer can be provided.

[0034]

The present invention will be further described with reference to the following examples. Hereinafter, “parts” and “%” are expressed on a weight basis.

Example 1 <Preparation of silicate oligomer (A)> In a three-necked round bottom flask equipped with a stirrer, a reflux condenser and a thermometer, 234 parts of tetramethoxysilane and 74 parts of methanol were added and mixed. Thereafter, 22.2 parts of 0.05% hydrochloric acid was added, and a hydrolysis reaction was performed at an internal temperature of 65 ° C. for 2 hours. Then, the reflux condenser was replaced with an extraction tube, and the temperature was raised until the internal temperature reached 150 ° C.
Extraction was performed with methanol, and the mixture was further heated at 150 ° C. for 3 hours for condensation to obtain a hydrolyzate. Then this is 10
The monomer vaporized by boiling in a jacket heated to 0 to 150 ° C. was discharged to the outside of the system together with the inert gas so that the amount of the monomer became 0.2% or less. The tetramethoxysilane oligomer thus obtained has a degree of polymerization of 3 to 6.
The number of hydroxyl groups per molecule was 10 or more.

<Production of Acrylic Copolymer (B)> In a flask equipped with a nitrogen inlet tube, a reflux condenser, a thermometer and a stirrer, 40 parts of butyl methacrylate, 40 parts of methyl methacrylate, and a compound of the formula CH ₂ = C (CH ₃ ) -COOCH ₂ CH ₂ (CF ₂ ) ₇ Heptadecafluorodecyl methacrylate represented by CF ₃ (“Biscoat 17FM” manufactured by Osaka Organic Chemical Industry Co., Ltd.) 10
Part, γ-methacryloxytrimethoxysilane (“Shin-Etsu Silicone KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.) 10
, 66 parts of xylene, 16 parts of isopropanol, and 0.1 part of azobisisobutyronitrile, and polymerization was carried out at 90 ° C for 10 hours. As a result, an acrylic copolymer (B) solution having a resin content of 55% and a viscosity of 2000 cps / 25 ° C. was obtained.

<Coating composition> 20 parts of xylene and 36 parts of isopropanol were added to 100 parts of the obtained acrylic copolymer (B) solution to adjust the concentration to a resin content of 35%.
55 parts of the above silicate oligomer (A) was added (based on 100 parts of the acrylic copolymer (B),
The amount of (A) is 55 parts), 1 part of dibutyltin laurate is further added as a curing catalyst, and the mixture is mixed well, and then applied to the surface of the aluminum vapor-deposited film formed on the ABS resin plate using an applicator. After leaving it to dry for a time, a coating layer having a thickness of 20 μm was formed.

The storage stability of the coating composition, the adhesion, the gloss, the surface hardness, the salt water resistance and the boiling resistance of the coating layer after coating were measured by the following measuring methods.

Example 2 Octafluoropentyl methacrylate represented by the formula CH ₂ CC (CH ₃ ) -COOCH ₂ (CF ₂ ) ₄ H (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of 10 parts of heptadecafluorodecyl methacrylate. Acrylic copolymer (B) was obtained in the same manner as in Example 1 except that 10 parts of “Viscoat 8FM” was used.
Further, a coating composition was prepared in the same manner as in Example 1;
The coating was performed on the surface of the aluminum deposition film on the BS resin plate.

Comparative Example 1 An acrylic copolymer (B) was prepared in the same manner as in Example 1 except that 40 parts of butyl methacrylate was used, 45 parts of methyl methacrylate was used, and heptadecafluorodecyl methacrylate was omitted. Then, a coating composition was further prepared in the same manner as in Example 1, and applied to the surface of the aluminum vapor-deposited film on the ABS resin plate.

Comparative Example 2 An acrylic copolymer was prepared in the same manner as in Example 1 except that 10 parts of tetrafluoropropyl methacrylate was used instead of 10 parts of heptadecafluorodecyl methacrylate.
(B) was obtained, and a coating composition was prepared in the same manner as in Example 1, and applied to the surface of the aluminum vapor-deposited film on the ABS resin plate.

Comparative Example 3 An acrylic copolymer (B) was obtained in the same manner as in Example 1 except that 10 parts of perfluorocyclohexyl methacrylate was used instead of 10 parts of heptadecafluorodecyl methacrylate. A coating composition was prepared in the same manner as described above, and was applied to the aluminum vapor-deposited film surface on the ABS resin plate.

Example 3 The same silicate oligomer (A) as in Example 1 was placed in a flask equipped with a nitrogen inlet tube, a reflux condenser, a thermometer and a stirrer.
70 parts, butyl methacrylate 10 parts, methyl methacrylate 10 parts, heptadecafluorodecyl methacrylate represented by the formula CH ₂ CC (CH ₃ ) —COOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ (manufactured by Osaka Organic Chemical Industry Co., Ltd.) "Viscote 17FM")
10 parts, γ-methacryloxytrimethoxysilane (“Shin-Etsu Silicone KBM-50” manufactured by Shin-Etsu Silicone Co., Ltd.)
3 ") 10 parts and 0.04 part of azobisisobutyronitrile were charged and heated to 90 ° C. to initiate polymerization.

After a lapse of 2 hours from the polymerization, a mixed solution of 30 parts of butyl methacrylate, 30 parts of methyl methacrylate, 30 parts of the above silicate oligomer (A), 26.5 parts of xylene and 0.04 parts of azobisisobutyronitrile was mixed with 1 part.
It was charged dropwise over 6 hours, and the polymerization was further driven for 2 hours. Thereby, the resin content is 88% and the viscosity is 2500 cps / 25.
° C polymerization solution was obtained (acrylic copolymer (B) 100
The amount of silicate oligomer (A) per part is 100
Department).

Xylene 88 was added to 100 parts of the obtained polymerization solution.
After adding 1 part of 1N hydrochloric acid as a curing catalyst, the mixture was mixed well.
The aluminum vapor-deposited film formed on the BS plate was coated with an applicator and allowed to dry for 72 hours to form a coating layer having a thickness of 20 μm.

<Measurement Method> The storage stability was determined by measuring the viscosity after leaving the coating composition at 40 ° C. for one month, and calculating the ratio to the initial viscosity. Adhesion is evaluated by applying a Goban eye test to apply a cellophane adhesive tape and apply vigorously to the coating layer after applying a scratch on the coating layer to the target object at intervals of 1 mm vertically and horizontally. did. The gloss was measured according to JISK5400. Surface hardness is
It was measured by the pencil scratch value of JIS K5400. The salt water resistance was maintained for one week according to JIS K5400, and the appearance was visually determined. The boiling resistance was determined by visually observing the appearance after immersion in boiling water for 5 hours.

<Results> Examples 1 to 3 and Comparative Examples 1 to 3
Table 1 shows the results.

[0048]

[Table 1] Storage stability Adhesive strength Mitsuzawa Surface hardness Salt water resistance Boiling resistance Example 1 1.0 100/100 Excellent 2H No change No change Example 2 1.1 100/100 Excellent 2H No change No change Example 3 1.0 100/100 Excellent 2H Change None No change Comparative Example 1 2.0 100/100 Excellent 2H Rust clouding occurred Comparative Example 2 2.0 100/100 Excellent 2H Slight rust clouding Comparative Example 3 2.0 100/100 Excellent 2H Slight rust clouding

Example 4 <Production of acrylic copolymer (B)> A flask equipped with a nitrogen inlet tube, a reflux condenser, a thermometer and a stirrer was charged with 10 parts of butyl methacrylate, 25 parts of 2-ethylhexyl acrylate, and methyl methacrylate. 30 parts, styrene 15
Parts, heptadecafluorodecyl methacrylate represented by the formula CH ₂ = C (CH ₃ ) —COOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ (“Biscoat 17FM” manufactured by Osaka Organic Chemical Industry Co., Ltd.), 10 parts, γ
-Methacryloxytrimethoxysilane (“Shin-Etsu Silicone KBM-503” manufactured by Shin-Etsu Silicone Co., Ltd.) 10
, 60 parts of xylene, 16 parts of isopropanol and 0.1 part of azobisisobutyronitrile, and polymerization was carried out at 90 ° C. for 12 hours. As a result, an acrylic copolymer (B) solution having a resin content of 57% and a viscosity of 2500 cps / 25 ° C. was obtained.

Example 1 was repeated except that the above acrylic copolymer (B) was used. The storage stability of the obtained coating composition was 1.0, the adhesion was 100/100, the gloss of the coating layer after coating was excellent, the surface hardness was 2H, the salt water resistance was unchanged, and the boiling resistance was unchanged. Was.

[0051]

As described in the section of action, the coating composition of the present invention has good storage stability of the resin solution, excellent salt water resistance and boiling resistance, and has excellent adhesion and gloss. A coating layer having good characteristics such as surface hardness and surface hardness can be provided.

Embedded image

[Procedure amendment]

[Submission date] September 10, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

[0013]

[Formula 1]

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08F 220: 22 230: 08) (72) Inventor Akinohisa Oshita 2-chome Muroyama 2-chome, Ibaraki-shi, Osaka No. 1 In the Central Research Laboratory of Nippon Gosei Chemical Industry Co., Ltd. (72) Inventor Tomohisa Okuda 2-13-1, Muroyama, Ibaraki City, Osaka Pref.

Claims (3)

[Claims] 1. A silicate oligomer (A), 99 to 40% by weight of a (meth) acrylate (b ₁ ) and 3 carbon atoms
Fluoroalkyl (meth) acrylate (b ₂ ) 1 to 20 in which 6 or more of H in the above alkyl group are substituted with F
% By weight, (meth) acrylate containing alkoxysilyl group
(b ₃ ) 0 to 20% by weight, and other comonomers (b
₄ ) Acrylic copolymer containing 0 to 59% by weight of a copolymer component
(B) a coating composition comprising: 2. A fluoroalkyl (meth) acrylate (b)
The coating composition according to claim 1, wherein ₂ ) is a fluoroalkyl (meth) acrylate in which 8 or more of H of the alkyl group having 5 or more carbon atoms are substituted with F. 3. The coating composition according to claim 1, wherein the compounding ratio of the silicate oligomer (A) is 5 to 200 parts by weight based on 100 parts by weight of the acrylic copolymer (B).