KR20010093635A - Room Temperature Curable Paint Composition - Google Patents

Abstract

PURPOSE: Provided is an ordinary temperature curable coating composition capable of forming coating films which have excellent weather resistance, coating film gloss, storability, initial dryability, double coating workability and alkali resistance. CONSTITUTION: The composition comprises 5-95 wt.% of an oxidative curable silicon modified vinyl-based resin(A) which is obtained by combining an epoxy group containing vinyl copolymer(a) with an unsaturated fatty acid-containing fatty acid component(b) and a silicon resin(c); and 5-95 wt.% of a polymer dispersion. The vinyl copolymer(a) is a copolymer of an epoxy group-containing polymerizable unsaturated first monomer and a polymerizable unsaturated second monomer copolymerizable with the first monomer. The silicon resin(c) contains a silicon atom and a hydroxy group and/or an alkoxy group which is bonded to the silicon atom. The polymer dispersion is obtained by polymerizing a polymerizable unsaturated monomer in the presence of a dispersion stabilizer(d) soluble in an organic liquid in the organic liquid which dissolves the polymerizable unsaturated monomer and does not dissolve the polymer formed from the monomer.

Description

Room Temperature Curable Paint Composition

The present invention relates to an oxidation-curable silicone-modified vinyl-based resin and a room temperature-curable coating composition capable of forming a coating film excellent in weather resistance, initial dryness, and alkali resistance using the modified vinyl resin.

Alkyd resins using unsaturated fatty acids are well known as conventional paint resins that have room temperature curing properties and are stable over a long period of time in a solution state, and are widely used as paints for building interior and exterior coatings, but these alkyd resins may cause weathering deterioration due to ultraviolet rays. It was easy and insufficient in performance for outdoor use. As a method of solving this weatherability problem, the acrylic resin formed by denaturation with a fatty acid is proposed, for example in Unexamined-Japanese-Patent No. 793,776. However, the fatty acid-modified acrylic resin, although slightly improved in weatherability, contains a fatty acid which is a soft component with low polarity, so that the coating film performances such as weather resistance, water resistance, acid resistance and alkali resistance are still not sufficient. .

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said problem, by using the resin which modified | denatured the fatty acid modified acrylic resin further into silicone resin as a resin for coatings, it is excellent in storage stability and painting workability, and it is excellent in the weather resistance and initial stage of a coating film. It was found that the alkali resistance of the coating film was also improved by being excellent in the drying property and using non-aqueous polymer particles of the oxidative curing type, and came to complete the present invention.

That is, the present invention relates to a fatty acid component (b) and a silicon atom containing an unsaturated fatty acid in an epoxy group-containing vinyl copolymer (a) which is a copolymer of an epoxy group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the monomer. An oxidation-hardening type silicone-modified vinyl-based resin formed by bonding a silicone resin (c) containing a hydroxyl group and / or an alkoxyl group to be directly bonded, and a room temperature-curable coating material comprising the above-mentioned oxidation-curable silicone-modified vinyl-based resin (A) as a resin component The presence of the dispersion stabilizer (d) which is soluble in this composition, and also in this organic liquid which melt | dissolves this oxidation-hardening type silicone modified vinyl-type resin (A) and a polymerizable unsaturated monomer, and the polymer formed from this monomer does not melt | dissolve. The polymer dispersion (B) obtained by polymerizing the polymerizable unsaturated monomer under a high total of (A) and (B) It is providing the normal temperature curable coating composition containing 5 to 95 weight% of (A) and 5 to 95 weight% of (B) based on mold weight.

The oxidation-curable silicone-modified vinyl-based resin (A) of the present invention contains a fatty acid component (b) containing an unsaturated fatty acid and a hydroxyl group and / or alkoxyl group directly bonded to a silicon atom in the epoxy group-containing vinyl copolymer (a). It is resin which silicone resin (c) combines.

As an epoxy group containing polymerizable unsaturated monomer which is a copolymerization component of the said epoxy group containing vinyl copolymer (a), For example, (meth) acrylic acid glycidyl, (meth) acrylic acid (beta) -methylglycidyl, and (meth) acrylic acid 3,4 -Epoxycyclohexylmethyl, (meth) acrylic acid 3,4-epoxycyclohexylpropyl, allyl glycidyl ether, etc. are mentioned.

As another polymerizable unsaturated monomer copolymerizable with the said epoxy group containing polymerizable unsaturated monomer, For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, ( T-butyl methacrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, C1-C24 alkyl ester of acrylic acid or methacrylic acid, such as cyclohexyl (meth) acrylic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( Hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as meth) acrylate and 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Hydroxyl group-containing monomers such as α, β-ethylenically unsaturated carboxylic esters having an alkylene oxide chain such as acrylate and a hydroxyl group; Isobornyl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidyl (meth) acrylate, 2,2,6,6-tetramethylpiperidinyl (meth) acrylate, 2- (2 '-Hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, styrene and the like.

In the epoxy group-containing vinyl copolymer (a), the copolymerization ratio of the epoxy group-containing polymerizable unsaturated monomer and the other polymerizable unsaturated monomer is usually 3 to 70% by weight, preferably 5 to 40% by weight of the epoxy group-containing polymerizable unsaturated monomer. Addition reaction when the other polymerizable unsaturated monomer is in the range of 30 to 97% by weight, preferably 60 to 95% by weight, when reacting with an unsaturated fatty acid (b), the resulting epoxy group-containing vinyl copolymer ( It is suitable in terms of solubility in the solvent of a).

In the epoxy group-containing vinyl copolymer (a), the amount of the hydroxyl group-containing monomer is determined so that the gelation by the reaction with the glycidyl group in the vinyl copolymer (a) and the gelation by the reaction with the silicone resin do not occur. Must be determined. Usually, it is suitable that the usage-amount of a hydroxyl-containing monomer is 50 weight part or less in the monomer component which comprises a vinyl copolymer (a).

The copolymerization method for obtaining the epoxy group-containing vinyl copolymer (a) is not particularly limited, but is carried out in the presence of a radical polymerization initiator in an organic solvent in view of ease of reaction with a fatty acid component (b) and a silicone resin (c). Solution polymerization is preferred.

As a radical polymerization initiator used at the time of the synthesis | combination by solution polymerization of the said epoxy group containing vinyl copolymer (a), it is 2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4-, for example). Azo polymerization initiators such as dimethylvaleronitrile); Peroxide type polymerization initiators, such as lauryl peroxide, t-butyl peroxy-2-ethylhexanoate, and benzoyl peroxide, etc. are mentioned. Moreover, as an organic solvent used at the time of synthesis | combination by solution polymerization, aliphatic hydrocarbons, such as n-hexane, n-octane, 2,2,2- trimethyl pentane, isooctane, n-nonane, cyclohexane, methylcyclohexane, etc. System solvents; Aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene; Petroleum solvents such as mineral spirit, "Swasol 1000" (manufactured by Cosmo Seiki Co., Ltd.), petroleum ether, petroleum benzine, petroleum naphtha; Ketone solvents such as methyl isobutyl ketone; Ester solvents such as isobutyl acetate; Alcohol solvents, such as isopropanol, etc. can be used individually or in mixture of 2 or more types as needed.

The epoxy group-containing vinyl copolymer (a) has a number average molecular weight in the range of 1, OOO to 100,000, particularly 2,000 to 50,000, and the resin having a glass transition temperature (Tg) in the range of 0 ° C to 100 ° C is used. It is preferable from the viewpoint of the coating film physical property and quick drying property of the coating film formed.

The fatty acid component (b) is a fatty acid component which essentially contains an unsaturated fatty acid and optionally contains a saturated fatty acid, and an iodine value is suitably in the range of about 50 to 200. When the iodine value is less than about 50, the curability of the coating film is lowered. On the other hand, when the iodine value exceeds about 200, it is not preferable because the gelation may occur during resin production.

Representative examples of unsaturated fatty acids which are essential components of the fatty acid component (b) include fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, perilla oil fatty acid, hempseed oil fatty acid and grape kernel oil. Fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber oil fatty acid, etc. are mentioned. An unsaturated fatty acid is a fatty acid which has an oxidation hardening type polymerizable unsaturated group, and provides oxidation hardening property to the silicone modified vinyl resin of this invention.

As a saturated fatty acid which a fatty acid component (b) may contain further in addition to the said unsaturated fatty acid as needed, For example, Undried oil fatty acids, such as palm oil fatty acid, hydrogenated palm oil fatty acid, palm oil fatty acid; Caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like.

The use ratio of a fatty acid component (b) is 1-60 weight part with respect to 100 weight part of resin solid content of the said epoxy group containing vinyl copolymer (a), The curability of the coating film obtained that it exists in 5-30 weight part, and It is preferable in terms of weather resistance and the like.

The silicone resin (c) is a silicone resin containing a hydroxyl group and / or an alkoxyl group directly bonded to a silicon atom, and for example, a silicone resin represented by the following formula can be preferably used.

R ¹ _a (R ² O) _b SiO _{(4-ab) / 2}

In formula, R <^1> represents the same or different C1-C8 alkyl group or an aryl group, R <^2> represents H or a C1-C8 alkyl group, a is 0 <= a <= 3.5 and b is 0.0005 <= b <4.0 Is in the range of.

In said formula, as a specific example of a C1-C8 alkyl group in R <^1> , a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example. A phenyl group, a tolyl group, etc. are mentioned as a specific example of the aryl group in R <^1> . As R <^1> , a methyl group, an ethyl group, and a phenyl group are preferable among these from a viewpoint of availability, reactivity, etc.

Specific examples of H and / or an alkyl group having 1 to 8 carbon atoms as R ² include, for example, a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Especially, hydrogen, a methyl group, and an ethyl group are preferable.

In the above formula, a is within the range of 0 ≦ a ≦ 3.5 and b is within the range of 0.0005 ≦ b ≦ 4.0. The epoxy group-containing vinyl copolymer (a) or the copolymer (a) and the fatty acid component (b) It is preferable from the viewpoint of the reactivity with the hydroxyl group in the reaction product, the physical properties of the coating film obtained, curability, weather resistance and the like.

In addition, the silicone resin (c) is preferable in view of physical properties, curability, and the like of the coating film formed by using a silicone-modified vinyl resin obtained in which the polystyrene reduced number average molecular weight is in the range of 90 to 100,000.

As a commercial item of a silicone resin (c), For example, SH-6018, DC3074, DC3037, SR2402 (all are the Toray Dow Corning Corporation make); Examples include KR9218, X-40-9220 (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.), TSR165, and XR-31B1763 (all of which are manufactured by Toshiba Silicone Co., Ltd.).

Silicone resin (c) contains the partial hydrolysis-condensation product, hydroxyl group, or alkoxyl group of 1 type, or 2 or more types of silicone resin containing hydroxyl group or alkoxyl group, such as the said commercial item, and this 1 type or 2 or more types of mixture And partial hydrolysis and condensation products of the silicone resin with the organo dialkoxysilane or trialkoxysilane. Examples of the diorgano dialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and the like. Methoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like.

The use ratio of a silicone resin (c) is 1-370 weight part with respect to 100 weight part of resin solid content of the said epoxy group containing vinyl copolymer (a), Preferably it is 1-200 weight part, More preferably, it is 1-100 weight part It is preferable that it exists in the negative range from a viewpoint of hardenability, weather resistance, etc. of the coating film obtained.

In the present invention, the reaction order of the epoxy group-containing vinyl copolymer (a), the fatty acid component (b) and the silicone resin (c) for producing the oxidation-curable silicone-modified vinyl-based resin (A) is not particularly limited. Although three may be reacted simultaneously, it is easy to control reaction of the said epoxy-group containing vinyl copolymer (a) and fatty acid component (b), and then making a silicone resin (c) react with the fatty acid modified copolymer which is this reaction product. It is preferable in terms of the back.

The reaction of the epoxy group-containing vinyl copolymer (a) with the fatty acid component (b) is based on an esterification reaction between the epoxy group in the copolymer (a) and the carboxyl group in the fatty acid component (b). A class hydroxyl is produced.

In this reaction, if necessary, tertiary amines such as N, N-dimethylaminoethanol; Reaction catalysts, such as quaternary ammonium salts, such as tetrabutylammonium bromide, can be used. When using a reaction catalyst, the usage-amount is suitable in the range of 0.01 to 100 weight part based on 100 weight part of total of a copolymer (a) and a fatty acid component (b).

The reaction conditions of a copolymer (a) and a fatty acid component (b) should just be conditions which can react the epoxy group in a copolymer (a) and the carboxyl group in a fatty acid component (b), without causing a reaction problem, such as gelation, Usually, conditions for heating at about 100 to 170 ° C. for about 2 to 10 hours are suitable.

The reaction between the fatty acid modified copolymer obtained as described above and the silicone resin (c) can be carried out by heating in the presence of a reaction catalyst, if necessary, by dehydration or dealcohol condensation reaction. The dehydration or dealcohol condensation reaction is caused by the reaction of the hydroxyl group in the fatty acid modified copolymer with the hydroxyl group or alkoxysilyl group in the silicone resin (c). The hydroxyl group in the said fatty acid modified copolymer includes the hydroxyl group which exists from the beginning in copolymer (a), and the hydroxyl group produced by reaction of copolymer (a) and fatty acid component (b).

As the reaction catalyst in the dehydration and dealcohol condensation reaction, metal alkoxide compounds, metal chelate compounds, metal ester compounds and the like are used. As the metal alkoxide compound, for example, aluminum trimethoxide, aluminum triethoxide, aluminum tri n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum Aluminum alkoxides such as tri-sec-butoxide and aluminum tri-tert-butoxide; Tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetra-n- Titanium alkoxides such as hexyl titanate, tetraisooctyl titanate and tetra-n-lauryl titanate; Tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra -n-pentyl zirconate, tetra-tert-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl Zirconium alkoxides such as zirconate; Dibutyltin dibutoxide, and the like. Examples of the metal chelate compound include tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, tris (n- Butyl acetoacetate) aluminum, isopropoxy bis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (proponylacetonato) aluminum, diisopropoxypropionyl acetonate aluminum, acetylacetonate Earth bis (propionylacetonate) aluminum, monoethylacetoacetate bis (acetylacetonate) aluminum, acetylacetonate aluminum di sec-butylate, methyl acetoacetate aluminum di tert-butylate, bis (Acetylacetonato) aluminum mono sec-butylate, di (methyl) Seto acetate), aluminum chelate compounds such as aluminum mono tert- butylate; Titanium chelate compounds such as diisopropoxy bis (ethylacetoacetate) titanate, diisopropoxy bis (acetylacetonato) titanate and di n-butoxy bis (acetylacetonato) titanate; Zirconium chelate compounds such as tetrakis (acetylacetonato) zirconium, tetrakis (n-propylacetoacetate) zirconium, and tetrakis (ethylacetoacetate) zirconium; Dibutyltin bis (acetylacetonate) etc. are mentioned, As a metal ester compound, for example, dibutyltin diacetate, dibutyltin di (2-ethylhexylate), dibenzyltin di (2-ethylhexylate). ), Tin ester compounds such as dibutyltin dilaurate, dibutyltin diisooctyl maleate, and the like. These reaction catalysts can be used 1 type or in combination of 2 or more types.

The reaction catalyst is suitable to use 0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight based on 100 parts by weight of the total fatty acid modified copolymer and the silicone resin (c) in view of the effect of promoting the reaction.

The reaction conditions in the reaction between the fatty acid-modified copolymer and the silicone resin (c) are not particularly limited as long as the dehydration and dealcohol condensation reaction proceeds. Usually, the reaction temperature is 60 to 250 ° C, preferably 80 to 200 ° C. It is the range of 100 degreeC, More preferably, it is 100-180 degreeC, and reaction time is 0.5 to 24 hours, It is preferable to exist in the range of 1 to 12 hours preferably. In addition, in the said reaction, reaction can be advanced smoothly by removing the water and alcohol produced | generated by reaction in a system.

As long as the said reaction can perform dehydration and de-alcohol condensation reaction until the resin obtained can exhibit performance as a resin for coating materials, a part of hydroxyl groups may react and all hydroxyl groups may react. The progress of the reaction can be known by measuring the absorption intensity due to hydroxyl groups by infrared absorption spectrum (IR) measurement, or by measuring the amount of water and alcohol produced by the reaction, increasing the viscosity of the system, and the like.

The oxidation-curable silicone-modified vinyl-based resin (A) of the present invention obtained as described above can be suitably used as a resin for coating, and in the present invention, a room temperature-curable coating containing the oxidative-curable silicone-modified vinyl-based resin (A) as a resin component. It is to provide a composition.

In the present invention, the presence of a dispersion stabilizer (d) that is soluble in the organic liquid in the organic liquid in which the polymerizable unsaturated monomer is dissolved in the oxidation-curable silicone-modified vinyl-based resin (A), and the polymer formed from the monomer does not dissolve. The polymer dispersion (B) obtained by superposing | polymerizing the said polymerizable unsaturated monomer can be used together.

Examples of the organic liquid include aliphatic hydrocarbon solvents such as n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane, cyclohexane and methylcyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene; Petroleum solvents such as mineral spirit, "Swasol 1000" (manufactured by Maruzen Seki Oil Co., Ltd.), petroleum ether, petroleum benzine, petroleum naphtha; Ketone solvents such as methyl isobutyl ketone; Ester solvents such as isobutyl acetate; Alcohol solvents, such as isopropanol, These can be mentioned, These can be used individually or in mixture of 2 or more types.

Conventionally known resins can be variously applied to the dispersion stabilizer (d) soluble in the organic liquid, and resins having a number average particle amount of about 1,000 to 100,000 are common. Especially as said dispersion stabilizer (d), it is preferable at the point of the curability of the film | membrane in which resin which has an oxidatively polymerizable double bond was formed. The resin having an oxidative polymerizable double bond is usually 5 to 70% by weight, preferably 15 to 50% by weight, of a polymerizable unsaturated monomer having an oxidative polymerizable double bond, and another polymerizable unsaturated monomer copolymerizable with this monomer. 30 to 95% by weight, preferably 50 to 85% by weight is a copolymer obtained by radical polymerization in the presence of a radical polymerization initiator in the organic liquid.

The polymerizable unsaturated monomer having the oxidative polymerizable double bond has a structural formula in a molecule. It is to have a site represented by.

As a specific example, for example, dihydrodicyclopentadiene such as dihydrodicyclopentadiene mono (meth) acrylate, dihydrodicyclopentadieneethyl mono (meth) acrylate and dihydrodicyclopentadiene monoallyl ether. Derivatives.

As another polymerizable unsaturated monomer copolymerizable with the said monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t- (meth) acrylate Butyl, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclo (meth) acrylate Hexyl, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, styrene, etc. are mentioned, These can be used 1 type or in combination or 2 or more types.

As said radical polymerization initiator, For example, Azo initiators, such as 2,2'- azobisisobutyronitrile and 2,2'- azobis (2, 4- dimethylvaleronitrile); Peroxide-based initiators, such as lauryl peroxide, t-butyl peroxy-2-ethylhexanoate, and benzoyl peroxide, etc. are mentioned.

As a polymerizable unsaturated monomer superposed | polymerized in presence of the dispersion stabilizer (d) obtained as mentioned above, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, for example. T-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylonitrile, 2-methoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, vinylpyrrolidone, (meth) acrylic acid, maleic acid, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid Glycidyl, styrene, vinyl toluene, vinyl acetate, etc. are mentioned, These can be used 1 type or in combination or 2 or more types.

The dispersion polymerization is carried out in the presence of a radical polymerization initiator in the organic liquid. This radical polymerization initiator can use the same thing as mentioned above.

The polymer dispersion (B) obtained as described above is a dispersion of stable particles having a light intensity average particle diameter of 150 to 900 nm, preferably about 250 to 400 nm, by the dynamic light scattering method.

In the present invention, the component (A) and (B) is 5 to 95% by weight, preferably 50 to 90% by weight, (B) is 5 to 95% by weight, based on the total solids weight of both Preferably it may contain 10 to 50% by weight. Out of this range, when there are few (A) components (there are many (B) components), there exists a possibility that weather resistance may fall, while when there are few (B) components (there are many (A) components), the alkali resistance of a coating film It is not preferable because it becomes insufficient.

The coating composition of the present invention may further contain, if necessary, an oxidation curing reaction catalyst, pigments, organic solvents, ultraviolet absorbers, light stabilizers, surface conditioners, pigment dispersants, rheology modifiers, coating liquid film preventive agents, mold inhibitors, and seaweed antifoam agents. , Paint additives such as a plasticizer and an antifoaming agent can be blended.

Examples of the oxidative curing reaction catalyst include organic metal compounds such as cobalt octylate, cobalt naphthenate, manganese octylate, manganese naphthenate, zirconium octylate, zirconium naphthenate, and lead octylate.

The coating film obtained by the composition of the present invention has very good appearance such as surface gloss, excellent weather resistance, chemical resistance, and alkali resistance, and at the same time, in the presence of an oxidation curing reaction catalyst, it can be cured only after several hours after application, and thus has excellent room temperature. Curability is shown.

The coating composition of the present invention can be applied to material surfaces such as metals, slates, mortars, these undercoating surfaces, or coating film surfaces already applied, and in particular, when the coating composition of the present invention contains the component (B) It is useful for inorganic building materials, such as slate and mortar.

<Example>

Hereinafter, the present invention will be described in more detail with reference to Examples. "Parts" and "%" mean "parts by weight" and "% by weight", respectively.

Preparation of Silicone Modified Vinyl-Based Resin Solution

<Example 1>

100 parts of mineral spirits were put into the flask, and it heated up, stirring to 115 degreeC, ventilating nitrogen gas. Next, the mixture of the following monomers was dripped over 4 hours, maintaining temperature at 115 degreeC.

Styrene part 25

15 parts of n-butyl methacrylate

20 parts i-butyl methacrylic acid

20 parts 2-ethylhexyl acrylate

20 parts glycidyl methacrylate

2,2'-azobisisobutyronitrile 1 part

Subsequently, after aging at 115 ° C. for 2 hours, the temperature was raised to 140 ° C., and then 30 parts of linseed oil fatty acid and 0.4 part of N, N-dimethylaminoethanol were added as a reaction catalyst, and maintained at 160 ° C. for 5 hours to carry out the addition reaction of fatty acids. It was done. The resin acid value was traced by KOH titration method, and the end point was made when the resin acid value became 1.0 or less. 45 parts of xylenes were added and diluted after completion | finish of reaction, and the brown transparent fatty acid modified copolymer (a) solution which has the viscosity of 50% of non volatile matters was obtained.

Subsequently, it cooled to 100 degreeC, the flask was equipped with the water separator, 20 parts of silicone resin SH-6018 (made by Toray Dow Corning Silicone Co., Ltd.), 14 parts of mineral spirits, 6 parts of xylene, and tetra-n as a reaction catalyst -0.20 parts of -butyl titanate were added, and it heated up to 165 degreeC, and made it react for 5 hours, separating water with a water separator in a reflux system, and brown transparent silicone modified vinyl-type resin solution which has a viscosity of about 50% of non volatile matter (A-1) Got.

<Example 2>

Fatty acid-modified copolymer (a) solution of 50% non-volatile content (50%) obtained in all the steps of Example 1, 10 parts of silicone resin SH-6018, 7 parts of mineral spirits, 3 parts of xylene, and tetra-n-butyltita as a reaction catalyst 0.10 part of Nate was added to a flask equipped with a water separator, the temperature was raised to 165 ° C., and the reaction was carried out for 5 hours while the water was separated by a water separator in a reflux system to react with a brown transparent silicone-modified vinyl resin solution having a viscosity of 50% of nonvolatile content ( A-2) was obtained.

<Example 3>

100 parts of mineral spirits were put into the flask, and it heated up while stirring to 115 degreeC, ventilating nitrogen gas. Next, the mixture of the following monomers was dripped over 4 hours, maintaining temperature at 115 degreeC.

Styrene part 20

15 parts of n-butyl methacrylate

20 parts i-butyl methacrylic acid

20 parts 2-ethylhexyl acrylate

20 parts glycidyl methacrylate

RUVA-093 Part 5

2,2'-azobisisobutyronitrile 1 part

(RUVA-093: 2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, manufactured by Otsuka Chemical Co., Ltd.)

Subsequently, after aging at 115 ° C. for 2 hours, the temperature was raised to 140 ° C., and then 30 parts of linseed oil fatty acid and 0.4 part of N, N-dimethylaminoethanol were added as a reaction catalyst, and maintained at 160 ° C. for 5 hours to carry out the addition reaction of fatty acids. It was done. The resin acid value was traced by KOH titration method, and the end point was made when the resin acid value became 1.0 or less. After completion of the reaction, the mixture was diluted with 45 parts of xylene to obtain a brown transparent fatty acid modified copolymer (b) solution having a viscosity of 50% of nonvolatile content.

Subsequently, it cooled to 100 degreeC, the water separator was added to the flask, 5 parts of silicone resin SH-6018, 3.5 parts of mineral spirits, 1.5 parts of xylenes, and 0.05 parts of tetra-n-butyl titanate as a reaction catalyst were added, and it was until 165 degreeC. The mixture was heated and reacted for 8 hours while separating water using a water separator in a reflux system, thereby obtaining a brown transparent silicone-modified vinyl resin solution having a viscosity of 50% of a nonvolatile content.

Preparation of Polymer Dispersion

<Manufacture example 1>

100 parts of mineral spirits were put into the flask, and it heated up while stirring to 110 degreeC, ventilating nitrogen gas. Next, the mixture of the following monomers was dripped over 4 hours, maintaining temperature at 110 degreeC.

Styrene part 25

12 parts of n-butyl methacrylate

43 parts of i-butyl methacrylic acid

20 parts 2-ethylhexyl acrylate

1.5 parts of 2,2'-azobisisobutyronitrile

Then, after heating up at 120 degreeC, it aged for 2 hours and obtained the substantially colorless transparent acrylic resin solution of 55% of non volatile matters, and used it as a dispersion stabilizer.

Into the flask, 185.4 parts of the dispersion stabilizer prepared above, 25.5 parts of isobutyl acetate, and 101 parts of mineral spirits were put, and it heated up stirring at 10 degreeC, ventilating nitrogen gas. Next, the mixture of the following monomers was dripped over 3 hours, maintaining temperature at 100 degreeC.

25 parts of methyl methacrylate

15 parts ethyl acrylate

40 parts methyl acrylate

20 parts of 2-hydroxyethyl acrylate

1.5 parts of 2,2'-azobisisobutyronitrile

Thereafter, the mixture was aged at 100 ° C for 3 hours to obtain a milky white polymer dispersion (B-1) having a nonvolatile content of 50%. The light intensity average particle diameter by the dynamic light scattering method was 370 nm.

<Manufacture example 2>

In Production Example 1, a milky white polymer dispersion (B-2) having a nonvolatile content of 50% was obtained in the same manner as in Production Example 1, except that the following mixture was used as the monomer mixture used for preparing the dispersion stabilizer of the polymer dispersion. The particle diameter was 350 nm.

Pancrill FA-512MT, Part 10

Styrene part 25

12 parts of n-butyl methacrylate

33 parts of i-butyl methacrylic acid

20 parts 2-ethylhexyl acrylate

2,2'-azobisisobutyronitrile 1 part

("Panryl FA-512MT": Hitachi Kasei High School Co., Ltd., ceremony Oxidatively curable monomer represented by

Preparation of paint composition

<Examples 4 to 6>

0.3 parts by weight of cobalt naphthenate and 1.0 parts by weight of naphthenic acid as a curing catalyst were added to 200 parts of a silicone-modified vinyl-based resin solution having a nonvolatile content of 50% obtained in each example, followed by stirring until uniform, to obtain a room temperature-curable coating composition. Got. Example 4 used Example 1, Example 5, Example 2, and Example 6 the silicone modified vinyl resin solution of 50% of each non volatile matter of Example 3.

Comparative Example 1

0.3 parts by weight of cobalt naphthenate and 1.0 part by weight of naphthenic acid lead were added as a curing catalyst to 200 parts of a solution of the fatty acid-modified copolymer (a) having a nonvolatile content of 50% obtained in all the steps of Example 1, followed by stirring until uniform. The room temperature curable coating composition was obtained.

Performance test

The storage stability when stored at 20 ° C. for 1 hour for each of the room temperature curable coating compositions obtained in Examples 4 to 6 and Comparative Example 1 was evaluated according to the presence or absence of sediment (○: no sediment, good storage stability).

Moreover, the various tests were done about the coating plate which coat | covered each normal temperature curable coating composition based on the following test method. The test results are shown in Table 1 below.

(* 1) Initial drying property: After coating each room temperature curable coating composition with a 300 micrometer applicator on a glass plate, it was left to stand in the room of 20 degreeC and 75% RH for 6 hours, and the dryness of the coating film was investigated by finger.

◎: No fingerprint at all

(Circle): Slight fingerprints.

△: fingerprint

X: A coating film adheres to a finger.

(* 2) Double coating workability: After coating each room temperature curable coating composition with a 300 micrometer applicator on a glass plate, each room temperature curable coating composition on the coating film after leaving it indoors at 20 degreeC and 75% RH for 6 hours. The coating workability and the state of the coating film at the time of coating so as to have a dry film thickness of 80-100 micrometers with a chain hair were observed.

○: no abnormality

(Triangle | delta): Shrinkage was confirmed by a coating film.

X: The coating film at the time of 1st coating melt | dissolves and a hair-stroke movement becomes heavy.

(* 3) Coating film gloss: After coating each room temperature curable coating composition with an applicator of 300 micrometers on a slate plate which is coated with "Acer ceramide" (manufactured by Kansai Paint Co., Ltd., white matting dye), and dried for one week, 60 ° mirror reflectance was measured.

◎: 90% or more

○: 80% or more, less than 90%

△: 70% or more, less than 80%

×: less than 70%

(* 4) Weather resistance: Sunshine weathering is performed by coating each room temperature curable coating composition with an applicator of 300 µm on a slate plate coated with "Acer ceramide" (manufactured by Kansai Paint Co., Ltd., white matt coating) and drying for 1 week. It evaluated by gloss retention when it exposed for 1500 hours by -O-meter.

◎: 90% or more

○: 80% or more, less than 90%

△: 70% or more, less than 80%

×: less than 70%

(* 5) Water resistance: After coating the room temperature curable coating composition with an applicator of 300 µm on a slate plate, and immersing the coated plate dried at room temperature for 20 days at 20 ° C and 75% RH for 3 days in tap water (20 ° C). The state of the coating film was visually observed.

○: no abnormality

Δ: slightly expanded.

X: significantly expanded.

(* 6) Acid resistance: (* 1) 0.5 cc of 0.1 N sulfuric acid aqueous solution was added dropwise to the coating plate obtained in the same manner as the initial drying test, and left at 20 ° C for 24 hours, followed by washing with water to observe the state of the coating film. It was.

○: no abnormality

(Triangle | delta): Whitening is confirmed slightly.

X: It whitened remarkably and the etching of the coating film surface was also confirmed.

Example Comparative example 4 5 6 One Storage stability ○ ○ ○ ○ Early drying ○ ○ ○ ○ 2 coating workability ○ ○ ○ ○ Coating gloss ◎ ◎ ○ △ Weather resistance ◎ ◎ ◎ △ Water resistance ○ ○ ○ ○ Acid resistance ○ ○ ○ ○

<Examples 7 to 15 and Comparative Example 2>

Using a silicone-modified vinyl-based resin solution having a nonvolatile content of 50% obtained in the above Example, sand components were dispersed together with 250 parts of glass beads having a diameter of 1.5 mm using the composition (solid content indication) shown in Table 2 to give a pigment. After the paste was prepared, "DICNATE1000" (active cobalt dryer containing cobalt organic acid salt) and zirconium octylate as a polymer dispersion of 50% of the nonvolatile content obtained in the above production example and a curing catalyst. Was added by the compounding (solid content indication) shown in Table 2, and it stirred until it became uniform, and obtained each normal temperature curable coating composition. In addition, in the comparative example 2, the fatty acid modified copolymer (a) solution of the non volatile matter 50% obtained at the manufacturing process was used instead of the silicone modified vinyl resin solution.

Performance test

The following weather resistance and alkali resistance test was done about each normal temperature curable coating composition obtained by the said Examples 7-15 and Comparative Example 2. The test results are shown in Table 2 below.

(* 7) Alkali resistance: On a slate plate formed by coating "VP sealer transparent" (manufactured by Kansai Paint Co., Ltd., vinyl chloride resin-based transparent sealer), each room temperature curable coating composition is coated with chain hair so that the coating amount is 160 g / m 2, and 20 0.5 cc of 0.1 N sodium hydroxide solution was added dropwise to the coating film surface after 6 hours in a room at 75 ° C and 75% RH, and left at 20 ° C in a room at 75% RH for 24 hours, followed by washing with water to clean the film. Observed.

○: no abnormality

△: slightly whitening is confirmed

X: Remarkable whitening and the etching of the surface were confirmed.

(* 8) Weathering resistance: Each normal temperature curable coating composition is coated on a chemical conversion steel sheet formed by coating "ESCO" (manufactured by Kansai Paint Co., Ltd., an epoxy resin antirust coating) so as to have a coating amount of 160 g / m3 at a chain, and 20 ° C. , And left in a 75% RH room for 7 days, and evaluated by gloss retention when exposed to 1500 hours with a Sunshine Weather-O-meter.

◎: 90% or more

○: 80% or more, less than 90%

△: 70% or more, less than 80%

×: less than 70%

In the oxidation-curable silicone-modified vinyl resin of the present invention, the main chain is a vinyl polymer, unsaturated fatty acid is added to the polymer to provide room temperature dryness, and the weather resistance of the coating film obtained by adding a silicone resin is improved.

The coating composition of the present invention contains the oxidation-curable silicone-modified vinyl-based resin of the present invention as a resin component, and is excellent in weather resistance and gloss of a coating film, and is also in terms of storage property, initial dryness, and hair loss at the time of two coatings due to bristles. It is a normal temperature curable coating composition which can form the coating film excellent in coating workability, such as a good movement.

Moreover, the coating composition of this invention ensures alkali resistance by using a polymer dispersion liquid together with an oxidative hardening type silicone modified vinyl system resin.

Claims (6)

A hydroxyl group directly bonded to a fatty acid component (b) containing an unsaturated fatty acid and a silicon atom in an epoxy group-containing vinyl copolymer (a), which is a copolymer of an epoxy group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the monomer; (Or) Oxidation hardening type silicone modified vinyl type resin in which the silicone resin (c) containing an alkoxyl group is couple | bonded. The oxidation-hardening type silicone modified vinyl resin of Claim 1 obtained by adding a fatty acid component (b) to an epoxy group containing vinyl copolymer (a), and then adding a silicone resin (c). The room temperature curable coating composition containing the oxidation-hardening type silicone modified vinyl system resin (A) of Claim 1 or 2 as a resin component. The polymerizable unsaturated monomer is dissolved, and the polymer formed from the monomer is obtained by polymerizing the polymerizable unsaturated monomer in the presence of a dispersion stabilizer (d) soluble in the organic liquid in an insoluble organic liquid. The room temperature curable coating composition containing a polymer dispersion (B) so that (A) may be 5 to 95 weight% and (B) is 5 to 95 weight% based on the total solid weight of (A) and (B). The room temperature curable coating composition according to claim 4, wherein the dispersion stabilizer (d) is a copolymer of a polymerizable unsaturated monomer having an oxidative polymerizable double bond and another polymerizable unsaturated monomer copolymerizable with the monomer. 6. The polymerizable unsaturated monomer having an oxidative polymerizable double bond in the molecule according to claim 5 Room temperature curable coating composition having a portion represented by.