DE10106561A1 - Cold-curing coating composition, e.g. for metal, slate or mortar, contains an oxidatively-hardening resin obtained by combining epoxy-modified vinyl copolymer with unsaturated fatty acid and special silicone resin - Google Patents

Abstract

A cold-curing coating composition of oxidatively-hardening resin obtained by combining (a) an epoxy-vinyl copolymer with (b) unsaturated fatty acid and (c) silicone resin, in which (a) is a copolymer of an unsaturated monomer with epoxide groups and an unsaturated comonomer, and (c) has hydroxyl and/or alkoxy groups attached to silicon. A coating composition (I) which hardens at normal temperature, comprising an oxidatively-hardening silicone-modified vinyl-based resin (A) obtained by combining (a) an epoxide group-containing vinyl copolymer with (b) an unsaturated fatty acid-containing fatty acid component and (c) a silicone resin. Component (a) is a copolymer of (m1) an epoxide group-containing polymerisable unsaturated monomer and (m2) an unsaturated comonomer, and silicone (c) has hydroxyl and/or alkoxy groups attached to silicon.

Description

The present invention relates to an ordinary temperature curable one Coating composition in which an oxidatively curable silicone-modified Vinyl based resin is used. From the coating composition, a Coating film that, in terms of weatherability, is initial Drying property and, moreover, alkali resistance is superior will.

As a conventional coating resin which has the properties of to be curable at ordinary temperature and stable in solution over a long period of time an alkyd resin using an unsaturated fatty acid is well known. It will generally used for internal / external coatings of buildings, but that Alkyd resin easily causes deterioration due to ultraviolet rays Weathering and performance ("Performance") is for use in Insufficient outdoors. As a technique for solving this problem the Weather resistance is taught, for example, in British Patent No. 793,776 Fatty acid modified acrylic resin proposed. The one modified by fatty acids Acrylic resin is improved in terms of weather resistance. However, since the Fatty acid as a low polar soft component cannot be claimed that coating properties such as weather resistance, durability against water, acids and alkalis are sufficient.

The object of this invention is to provide an ordinary temperature curable coating composition having excellent properties in terms of Weather resistance, resistance to water, acids or alkalis.

The present invention relates to an ordinary temperature curable one Coating composition. The coating composition comprises in particular an oxidatively curable silicone-modified resin as a resin component vinyl-based (A) which is obtainable by combining an epoxy group containing vinyl copolymer (a), which is a copolymer of an epoxy group containing polymerizable unsaturated monomer and one having the epoxy groups containing polymerizable unsaturated monomers copolymerizable other polymerizable unsaturated monomer, with an unsaturated fatty acid containing fatty acid component (b) and a silicone resin (c) containing a Hydroxy group and / or an alkoxy group which is bonded directly to the silicon atom is. In the epoxy group-containing vinyl copolymer (a) Copolymerization ratio of epoxy group-containing unsaturated monomer to the other polymerizable unsaturated monomer, which with the upper Monomer is copolymerizable, be such that the epoxy group-containing polymerizable unsaturated monomer preferably in a range from 3 to 70% by weight and the other polymerizable unsaturated monomer is preferably in the range of 30 to 97% by weight is present. The epoxy group-containing vinyl copolymer (a) may be Be a copolymer, the number average molecular weight of which is preferably in the range of 1,000 to 100,000 and its glass transition temperature in the range from 0 ° C to 100 ° C. The fatty acid component (b) containing an unsaturated fatty acid can preferably have an iodine number of 50 to 200.

In the present invention, an oxidatively curable silicone modified resin is included Vinyl base (A) a resin which is obtainable by combining an epoxy group containing vinyl copolymers (a) with one containing an unsaturated fatty acid Fatty acid component (b) and a silicone resin (c), which is a directly to the Contains silicon atom-bonded hydroxyl group and / or an alkoxy group.

Examples of an epoxy group-containing polymerizable unsaturated monomer, which contains a copolymerization component of the epoxy group Vinyl copolymers (a) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate and Aryl glycidyl ether.

Examples of other polymerizable unsaturated monomers, which with the Polymerizable unsaturated monomer containing epoxy groups is copolymerized include: alkyl esters of 1 to 24 carbon atoms of acrylic acids or methacrylic acids such as. B. methyl (meth) acrylate, ethyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate and cyclohexyl (meth) acrylate, and containing hydroxyl groups Monomers such as hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylates, which 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, and α, β-ethylenically unsaturated Carboxylate esters which have alkylene oxide chains and hydroxyl groups which Polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate include. To the polymerizable unsaturated monomers, which with the Polymerizable unsaturated monomers containing epoxy groups are copolymerizable, isobornyl (meth) acrylate, 1,2,2,6,6- Pentamethyl piperidyl (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) is the copolymerization ratio from epoxy group-containing polymerizable unsaturated monomer to the other polymerizable unsaturated monomer usually such that the epoxy groups polymerizable unsaturated monomers containing preferably in the range of 3 to 70 % By weight, particularly preferably 5 to 40% by weight, and the other polymerizable unsaturated monomers preferably in the range from 30 to 97% by weight, especially preferably 60 to 95% by weight is present. This is reasonable in terms of Addition reaction property during the reaction with the unsaturated fatty acid (b), Solubility of the resulting epoxy group-containing vinyl copolymer (a) in one Solvents and the like.

In the epoxy group-containing vinyl copolymer (a), the use of a Hydroxy group-containing monomers are determined in such a way that a Gelation by reaction with a glycidyl group in vinyl copolymer (a) or Gel formation does not occur during reaction with a silicone resin. It is common appropriate and preferred that the monomer containing hydroxyl groups to 50 wt. Parts or less with respect to 100 parts by weight of the total monomer components, which constitute the vinyl copolymer (a) is used.

The copolymerization method for obtaining the epoxy group-containing Vinyl copolymers (a) is not particularly limited, but taking into account the Ease of reaction with the fatty acid component (b) and a silicone resin (c) is the method of polymerization in solution is preferred, which in an organic Solvent carried out in the presence of a radical polymerization initiator will.

Examples of the radical polymerization initiator for use in synthesis of the epoxy group-containing vinyl copolymer (a) by solution polymerization include: azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile and 2,2'- Azobis (2,4-dimethylvaleronitrile) and peroxide-based polymerization initiators such as Lauryl peroxide, t-butyl peroxy-2-ethylhexanoate and benzoyl peroxide. Furthermore include examples of the organic solvent for use in synthesis by solution polymerization: based on aliphatic hydrocarbons Solvents such as n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane, Cyclohexane and methylcyclohexane; Solvent based on aromatic Hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Solvent on Petroleum base such as mineral spirits, "SWASOL 1000" (product of Cosmo Oil Co., Ltd.), Petroleum ether, petrol and naphtha; Solvents based on ketones such as Methyl isobutyl ketone; Solvents based on esters such as isobutyl acetate; and Alcohol-based solvents such as isopropanol. These solvents can alone or as a mixture of two or more of them, if necessary Solvents can be used.

For the epoxy group-containing vinyl copolymer (a), that is number average Molecular weight preferably in the range from 1,000 to 100,000, particularly preferred 2,000 to 50,000, and a glass transition temperature (Tg) is preferably in the range from 0 ° C to 100 ° C. This is in terms of the physical properties of the Coating film and the quick drying properties when using a the resulting resin is preferable.

The fatty acid component (b) essentially contains an unsaturated fatty acid and if necessary a saturated fatty acid. The iodine number is preferably in the range of about 50 to 200. When the iodine value is less than 50, the hardenability tends to be Deterioration. On the other hand, an iodine number can be above about 200 not because of the possibility of gel formation during the manufacture of the resin be desirable.

Typical examples of the unsaturated fatty acid as an essential component of the Fatty acid component (b) include the fatty acids from fish oil, dehydrated castor oil, Safflower oil, linseed oil, soybean oil, sesame oil, poppy seed oil, perilla oil, hemp seed oil, Grape seed oil, corn oil, tall oil, sunflower oil, cottonseed oil, walnut oil and Rubber seed oil. The unsaturated fatty acid is a fatty acid with an oxidative curable, polymerizable unsaturated group, and gives silicon modified vinyl resin (A) has the property of oxidative curability.

In addition to the unsaturated fatty acids, the fatty acid component (b) if necessary contain a saturated fatty acid. Examples of the saturated fatty acid include: fatty acids from non-drying oils such as the fatty acids from coconut oil, hydrogen refined coconut oil and palm oil; Caproic acid; Capric acid; Lauric acid; Myristic acid; Palmitic acid and stearic acid.

The fatty acid component (b) is preferably used in an amount which is preferably in the Is in the range from 1 to 60 parts by weight, particularly preferably in the range from 5 to 30 parts by weight Parts based on 100 parts by weight of resin solids of the epoxy group-containing Vinyl copolymers (a) are used. This is preferable in terms of hardenability and Weather resistance of the resulting coating film.

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

R ¹ _a (R ² O) _b SiO _{(4-ab) / 2}

(In the formula, R ¹ denotes an identical or different alkyl or aryl group having 1 to 8 carbon atoms, R ² denotes H or an alkyl group having 1 to 8 carbon atoms, a is in the range 0 ≦ a ≦ 3.5, and b is in the range from 0.0005 ≦ b ≦ 4.0.)

In the above formula, examples of the alkyl group having 1 to 8 carbon atoms in R ¹ include methyl group, ethyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group and cyclohexyl group. Examples of the aryl group in R ¹ include phenyl group and tolyl group. Among them, as R ^1, methyl group, ethyl group and phenyl group are desirable from the viewpoint of easy availability and reactivity.

For R ² , examples of H and / or the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, pentyl group, hexyl group, heptyl group and octyl group. Among them, hydrogen, methyl group and ethyl group are preferred in view of reactivity.

In the formula, a is in the range of 0 ≦ a ≦ 3.5 and b is in the range of 0.0005 ≦ b ≦ 4.0. These ranges are preferred in terms of reactivity with the hydroxyl group in the epoxy group-containing vinyl copolymer (a), or the reaction product of Copolymer (a) with the fatty acid component (b), the physical properties of the resulting coating film, curability, weatherability, and the like.

In addition, it is in terms of physical properties and hardenability the one using the resulting silicone-modified vinyl-based resin (A) formed coating film is preferred when the silicone resin (c) is a number average Molecular weight ranging from 90 to 100,000 (by transferring polystyrene) having.

Examples of commercially available silicone resins (c) include: SH-6018, DC3074, DC3037 and SR2402 (products of Dow Corning Toray Silicone Co., Ltd.); KR9218 and X-40-9220 (products of Shin-Etsu Chemical Co., Ltd.); and TSR165 and XR-3181763 (Products by Toshiba Silicone Co., Ltd.).

The silicone resin (c) can be one or a mixture of at least two hydroxy or Alkoxy group-containing silicone resins such as those mentioned above are commercially available be a partial hydrolysis / condensation product of a or a mixture of at least two of the aforementioned products, and a partial Hydrolysis / condensation product of the hydroxyl or alkoxy group-containing Silicone resin with diorganodialkoxysilane or organotrialkoxysilane. examples for Diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, Diphenyldimethoxysilane and diphenyldiethoxysilane, methylphenyldimethoxysilane. Examples of organotrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, Methyltriisopropoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane.

The use of the silicone resin (c) preferably in a proportion in the range from 1 to 370 parts by weight, particularly preferably 1 to 200 parts by weight, very particularly preferably 1 to 100 parts by weight based on 100 parts by weight of the resin solids of the epoxy group containing vinyl copolymers (a) is preferred in terms of curability and Weather resistance of the resulting coating film.

In the present invention is used to produce the oxidatively curable silicone modified vinyl-based resins (A) show the sequence of reactions of epoxy groups containing vinyl copolymer (a), fatty acid component (b) and silicone resin (c) do not particularly limited. These three can be implemented simultaneously, but it's in In view of the easy controllability of the reaction, it is preferred that the Vinyl copolymer (a) containing epoxy groups reacted with the fatty acid component (b) and then the reaction product of the fatty acid-modified copolymer is reacted with the silicone resin (c).

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). This reaction usually creates a secondary hydroxy group.

During this reaction, if necessary, reaction catalysts such as tertiary Amines, e.g. B. N, N-dimethylaminoethanol, and quaternary ammonium salts such as Tetrabutylammonium bromide can be used. When using the reaction catalyst is, it is appropriately in an amount ranging from 0.01 to 100 wt. Parts based on 100 parts by weight of the total amount of copolymer (a) and Fatty acid component (b) is used.

The reaction conditions of copolymer (a) with fatty acid component (b) are not limited as long as the epoxy group in the copolymer (a) with the carboxyl group in the Fatty acid component (b) can be implemented without the reaction problems such as Gel formation are caused. Usually there are conditions for heating about 100 to 170 ° C for about 2 to 10 hours is adequate.

The reaction of the fatty acid-modified copolymer obtained as described with the silicone resin (c) can be heated and dehydrated or Dealcoholization condensation reaction, if necessary in the presence of a Reaction catalyst, are carried out. The dehydration or Dealcoholization condensation reaction is carried out through the reaction of the Hydroxy group in the fatty acid-modified copolymer having a hydroxy group or a Alkoxysilyl group in the silicone resin (c). Examples of the hydroxy group in fatty acid modified copolymer include a hydroxyl group, which in the copolymer (a) already is present, and a hydroxyl group obtained by reacting copolymer (a) with the Fatty acid component (b) is generated.

As a reaction catalyst in the dehydration or Dealcoholization condensation reaction becomes a metal alkoxide compound, a Metal chelate compound, metal ester compound or the like is used. Examples of the Metal alkoxide compounds include: aluminum alkoxides such as aluminum trimethoxide, Aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-isopropoxide, aluminum tri-n-butoxide, aluminum tri-isobutoxide, aluminum tri-sec-butoxide and aluminum tri tert-butoxide; Titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, Tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert.-butyl titanate, Tetra-n-hexyl titanate, tetraisoctyl titanate and tetra-n-lauryl titanate; Zirconium alkoxides such as 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 and Tetra-n-stearyl zirconate; and dibutyltin dibutoxide. Examples of metal chelate compounds include: aluminum chelate compounds such as tris (ethylacetoacetate) aluminum, tris (n propyl acetoacetate) aluminum, tris (isopropyl acetoacetate) aluminum, tris (n butylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, Tris (acetylacetonate) aluminum, Tris (proponylacetonate) aluminum, Diisopropoxypropionylacetone aluminum, Acetylacetonate bis (propionyl acetonate) aluminum, Monoethylacetoacetate bis (acetylacetonate) aluminum, acetylacetonate aluminum disc butylate, butyl acetoacetate aluminum di-tert-butylate, bis (acetylacetonatal aluminum monosec butoxide and di (methylacetoacetate) aluminum monotert-butoxide; Titanium chelate compounds such as di-isopropoxy bis (ethylacetoacetate) titanate, diisopropoxy bis (acetylacetonate) titanate and Di-n-butoxybis (acetylacetonate) titanate; Zirconium chelate compounds such as Tetrakis (acetylacetonate) zirconium, tetrakis (npropylacetoacetate) zirconium and Tetrakis (ethylacetoacetate) zirconium; and dibutyl tin bis (acetylacetonate). examples for Metal ester compounds include tin ester compounds such as dibutyl tin acetate, Dibutyltin di (2-ethylhexylate), dibenzyltin di (2-ethylhexylate), dibutyltin dilaurate and Dibutyltin diisooctyl malate. These reaction catalysts can be used alone or as Combination of at least two can be used.

For the reaction catalyst, the use is preferably from 0.001 to 5 Part by weight, particularly preferably 0.005 to 1 part by weight, based on 100 wt. Parts of total fatty acid-modified copolymer and silicone resin (c) appropriate, as far as the reaction-promoting effect is concerned.

The reaction conditions in the reaction between fatty acid-modified copolymer with silicone resin (c) are not particularly limited as long as the dehydration or Dealcoholization condensation reaction takes place. Usually the Reaction temperature preferably in the range from 60 to 250 ° C., particularly preferred 80 ° C to 200 ° C and very particularly preferably 100 ° C to 180 ° C. The response time is preferably in the range from 0.5 to 24 hours, particularly preferably 1 to 12 hours. In addition, the reaction can proceed smoothly if that generated by the reaction Water or alcohol is removed from the system.

Dehydration or dealcoholization condensation can be used for the reaction be carried out until the resin obtained has the performance of a Coating resin, and some or substantially all of the hydroxyl groups Hydroxy groups can be converted. The progress of the reaction can be controlled by the Method of measuring an infrared absorption spectrum (IR) can be determined by a A method of obtaining absorption intensity associated with the hydroxyl group Measure the amount of water or alcohol produced by the reaction, an increase in the viscosity of the system and the like.

The oxidatively curable silicone-modified vinyl-based resin (A), which is as above can be preferably used as the coating resin. The present invention provides an ordinary temperature curable one Coating composition ready, which is a resin component of the oxidative curable silicone-modified vinyl-based resin (A).

In the present invention, the oxidatively curable silicone-modified resin can have Vinyl base (A) can be used together with a polymer dispersion (B), which by Polymerization of the polymerizable unsaturated monomer in an organic Liquid, the organic liquid being a polymerizable unsaturated Monomer dissolved and the polymer formed from the monomer is not dissolved in Presence of a dispersion stabilizer (d) which is soluble in the organic liquid, was obtained.

Examples of the organic liquid include: based solvents Hydrocarbons such as n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane, Cyclohexane and methylcyclohexane; Solvent on the basis of aromatic Hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Solvent on the Based on petroleum like white spirit, "SWAZOL 1000" (product of Cosmo Oil Co., Ltd.), petroleum ether, petrol and naphtha; Solvents based on ketones such as Methyl isobutyl ketone; Ester based solvents such as isobutyl acetate; and Alcohol-based solvents such as isopropanol. These solvents can can be used singly or as a mixture of two or more, as desired.

A variety of well-known resins can be used as the dispersion stabilizer (d) which is soluble in the organic liquid. A resin having a number average molecular weight on the order of 1,000 to 100,000 is generally used. As the dispersion stabilizer (d), a resin having an oxidatively polymerizable double bond is preferred in view of the curability of the formed film. The resin, which has an oxidatively polymerizable double bond, is generally a copolymer which is obtained in that preferably 5 to 70% by weight, particularly preferably 15 to 50% by weight, of a first polymerizable unsaturated monomer which is an oxidatively polymerizable Has double bond, and preferably 30 to 95 wt .-%, particularly preferably 50 to 85 wt .-%, of a second polymerizable unsaturated monomer which is copolymerizable with the first monomer, subjected to radical polymerization in the organic liquid in the presence of a radical polymerization initiator will. The first polymerizable unsaturated monomer, which contains oxidatively polymerizable double bonds, has a position in the molecule which is represented by the following formula:

Examples include dihydrodicyclopentadiene derivatives such as Dihydrodicyclopentadiene mono (meth) acrylate, Dihydrodicyclopentadiene ethyl mono (meth) acrylate and Dihydrodicyclopentadiemnonoaryl ether.

Examples of the second polymerizable unsaturated monomer, which with the first monomer is copolymerizable include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2- Hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate and styrene, with one or two or more of them can be used together.

Examples of the radical polymerization initiator include azo-based initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) and initiators Peroxide base such as lauryl peroxide, t-butyl peroxy-2-ethylhexanoate and benzoyl peroxide.

Examples of polymerizable unsaturated monomers, which in the presence of a Dispersion stabilizer (d) obtained as described above is polymerized include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, 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, vinyl pyrrolidone, (meth) acrylate, maleic acid, 2- Hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, styrene, vinyl toluene and vinyl acetate, one or two or more of which can be used together.

The dispersion polymerization is carried out in the organic liquid in the presence of a Radical polymerization initiator carried out. The aforementioned Free radical polymerization initiators can also be used.

The polymer dispersion (B) obtained as described above is a stable, Particle-containing dispersion whose determined by dynamic light scattering light intensity mean particle diameter in the order of preferably 150 to 900 nm, particularly preferably 250 to 400 nm.

In the present invention, based on the total weight of the solids content on the two components (A) and (B), (A) in a range from preferably 5 to 95 % By weight, particularly preferably 50 to 90% by weight, and (B) in a range of preferably 5 to 95% by weight, particularly preferably 10 to 50% by weight, may be included. When deviating from this range (with less component (A) and more Component (B)), the weatherability tends to possibly deteriorate. On the other hand, with less component (B) and more component (A) the Alkali resistance of the coating film tends to be disadvantageously insufficient.

The coating composition of the present invention can further if necessary mixed with additives for the coating such as a Catalyst for the oxidative hardening reaction, pigments, organic solvents, Ultraviolet absorbers, light stabilizers, surface regulators, pigment dispersants, rheology-controlling agents, anti-skinning agents, Mold protectants, anti-algae agents, plasticizers and anti-foaming agents.

Examples of catalysts for the oxidative curing reaction include organic ones Metal compounds such as cobalt octylate, cobalt naphthenate, manganese octylate, Manganese naphthenate, zirconium octylate, zirconium naphthenate and lead octylate.

The coating film produced by the composition of the present invention has a very satisfactory appearance, such as surface gloss, is superior in terms of weather resistance, chemical resistance and beyond Alkali resistance. After coating, this film is in the presence of a Catalyst for the oxidative hardening reaction hardenable in just a few hours, whereby he has superior curability at ordinary temperature.

The coating composition of the present invention can be used on material surfaces of metal, slate and mortar, primer coatings of Surfaces or previous coating surfaces. In particular, the Coating composition of the present invention, which component (B) contains, useful in inorganic building materials such as slate and mortar.

Examples

The present invention will hereinafter be described in more detail by way of examples. The terms "parts" and "%" mean "parts by weight" and "percent by weight", respectively.

Preparation of a solution of the silicone modified vinyl based resin Production example 1

After adding 100 parts of mineral spirits to a flask, nitrogen was passed through and the mixture was stirred until the temperature had risen to 115.degree. Then, while maintaining a temperature of 115 ° C., a mixture of the following monomers was added dropwise over the course of four hours:

Styrene 25 parts n-butyl (meth) acrylate 15 parts i-butyl (meth) acrylate 20 parts 2-ethylhexyl acrylate 20 parts Glycidyl (meth) acrylate 20 parts 2,2'-azobisisobutyronitrile Part 1

After standing for two hours at 115 ° C, the temperature was increased to 140 ° C and 30 Parts of fatty acids from linseed oil and 0.4 parts of the reaction catalyst N, N- Dimethylaminoethanol added. It became a temperature of 160 ° C maintained in order to bring about the addition reaction of the fatty acid. The acid number of the Resin was followed by means of a KOH titration method and the time, also the The acid value of the resin reached 1.0 or less than the end determined. To Completion of the reaction was diluted by adding 45 parts of xylene, to obtain a solution of the fatty acid-modified copolymer (a) which has a non-volatile content of 50% and was brown, transparent and viscous.

It was then cooled to 100 ° C. and a water separator was mounted on the flask and 20 parts of silicone resin SH-6018 (manufactured by Dow Coming Toray Silicone Co., Ltd.), 14 parts of mineral spirits, 6 parts of xylene and 0.20 parts of the reaction catalyst Tetra-n butyl titanate added. The temperature was increased to 165 ° C, the water by means of Separated water separator under reflux and the reaction for five hours carried out. It became a silicone modified vinyl based resin solution obtained (A-1) which was brown, transparent and viscous, and a non-volatile content of had about 50%.

Production example 2

289.4 parts of a solution of the fatty acid-modified copolymer (a) with a non-volatile content of 50% obtained in the preliminary process of Preparation Example 1 was obtained, 10 parts of silicone resin SH-6018, 7 parts of mineral spirits, 3 parts of xylene and 0.10 Portions of the reaction catalyst tetra-n-butyl titanate were placed in a flask that a water separator was installed. Then the temperature was increased to 165 ° C, the Separated water under reflux with the water separator and the reaction for five Hours carried out a brown, transparent and viscous solution of the silicone modified vinyl-based resin (A-2), which is a non-volatile Content of 50%.

Production example 3

After adding 100 parts of mineral spirits to the flask, nitrogen gas was bubbled through and stirred until the temperature was raised to 115 ° C. Then, while keeping the temperature constant at 115 ° C., a mixture of the following monomers was added dropwise over a period of four hours.

Styrene 20 parts n-butyl (meth) acrylate 15 parts i-butyl (meth) acrylate 20 parts 2-ethylhexyl acrylate 20 parts Glycidyl (meth) acrylate 20 parts RUVA-093 (see Amn. 1 below) 5 parts 2,2'-azobisisobutyronitrile Part 1

After standing for two hours at 115 ° C, the temperature was increased to 140 ° C and 30 Parts of fatty acids from linseed oil and 0.4 parts of the reaction catalyst N, N- Dimethylaminoethanol added and kept at 160 ° C for five hours to achieve the To cause the addition reaction of the fatty acid. The acid number of the resin was determined using the Followed the KOH titration method and determined the point in time as the end point, as well as the The acid value of the resin reached 1.0 or less. After completing the reaction 45 parts of xylene were added for dilution to obtain a brown, transparent and viscous solution of the fatty acid-modified copolymer (b) to obtain the one non-volatile content of 50%.

It was then cooled to 100 ° C, a water separator was mounted on the flask, 5 parts of the silicone resin SH-6018, 3.5 parts of mineral spirits, 1.5 parts of xylene and 0.05 parts of the reaction catalyst tetra-n-butyl titanate were added, the temperature was increased to 165 ° C, The reflux water was separated by the water separator and the reaction was carried out for eight hours to obtain a brown, transparent and viscous solution of the silicone-modified vinyl-based resin (A-3) which had a non-volatile content of 50%.
(Note 1) RUVA-093: 2- (2'-Hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, manufactured by Otsuka Chemical Co., Ltd.

Preparation of the polymer dispersion Production example 4

After adding 100 parts of mineral spirits to a flask, nitrogen gas was bubbled through and stirred until the temperature reached 110 ° C. Then, while keeping the temperature constant at 110 ° C., a mixture of the following monomers was added dropwise over a period of four hours:

Styrene 25.0 parts n-butyl (meth) acrylate 12.0 parts i-butyl (meth) acrylate 43.0 parts 2-ethylhexyl acrylate 20.0 parts 2,2'-azobisisobutyronitrile 1.5 parts

Then, after increasing the temperature to 120 ° C and standing for two hours, a essentially colorless transparent solution of an acrylic resin with a non-volatile one Content of 55% obtained as a dispersion stabilizer.

After 185.4 parts of the dispersion stabilizer prepared as described above, 25.5 parts of isobutyl acetate and 101 parts of mineral spirits had been added to the flask, nitrogen gas was passed through and stirred until the temperature had increased to 100.degree. A mixture of the following monomers was then added dropwise while maintaining a temperature of 100 ° C. for three hours.

Methyl (meth) acrylate 25.0 parts Ethyl acrylate 15.0 parts Methyl acrylate 40.0 parts 2-hydroxyethyl acrylate 20.0 parts 2,2'-azobisisobutyronitrile 1.5 parts

After standing at 100 ° C for three hours, a milky white polymer dispersion (B-1) with a non-volatile content of 50%. The based dynamic light scattering determined light intensity mean particle diameter 370 nm.

Production example 5

The preparation was carried out similarly to Preparation Example 4, with the difference that the following mixture was used as the monomer mixture for the preparation of the dispersion stabilizer of the polymer dispersion. A milky white polymer dispersion (B-2) having a non-volatile content of 50% was obtained. The particle diameter was 350 nm.

FANCRYL FA-512MT (see note 2) 10 parts Styrene 25 parts n-butyl (meth) acrylate 12 parts i-butyl (meth) acrylate 33 parts 2-ethylhexyl acrylate 20 parts 2,2'-azobisisobutyronitrile Part 1

(Note 2) "FANCRYL FA-512MT": manufactured by Hitachi Chemical Co., Ltd., oxidative curable monomer represented by the following formula.

Preparation of the coating composition Examples 1 to 3

After adding 0.3 part of cobalt naphthenate and 1.0 part of lead naphthenate as Curing catalyst to 200 parts of the solution of the silicone-modified resin Vinyl based with a non-volatile content of 50% as found in each of the The aforementioned Preparation Examples were uniformly stirred to make each to obtain ordinary temperature curable coating composition. the Solutions of the silicone-modified vinyl-based resin of Preparation Examples 1, 2 and 3, each containing 50% non-volatile components, were used in Examples 1, 2 and 3 used.

Comparative example 1

After adding 0.3 part of cobalt naphthenate and 1.0 part of lead naphthenate as Curing catalyst to 200 parts of a solution of the fatty acid-modified copolymer (a) which had a non-volatile content of 50% and in the pre-process of Preparation Example 1 was obtained, was stirred uniformly to the ordinary temperature curable coating composition.

Performance test

For the respective curable at ordinary temperature Coating compositions used in Examples 1 to 3 and Comparative Example 1 were obtained, the storage stability was during storage at 20 ° C for a Week determined based on the presence / absence of deposits (○: none Deposits, good storage stability).

In addition, a plate with an ordinary temperature curable coating composition was coated based on various tests performed on the following test method. The test results are in Table 1 listed.

(1) Initial drying property

After the coating composition curable at ordinary temperature was coated on a glass plate by means of a 300 μm applicator, the coating film was stored for six hours in a room at 20 ° C. and 75% relative humidity and the dry tack was tested.

: No fingerprint.
○: Low fingerprint.
∆: fingerprint.
×: The coating film stuck to the finger.

(2) Feasibility of double coating

After the coating composition curable at ordinary temperature was coated on the glass plate by means of a 300 µm applicator, the coating film was kept at 20 ° C and 75% RH for six hours. Then, with a brush, the ordinary temperature curable coating film was kept at 20 ° C and 75% RH for six hours. Then, the ordinary temperature curable coating composition was applied to the coating film with a brush so as to have a dry film thickness of 80 to 100 µm. The coating feasibility and the condition of the coating film were determined.

○: No abnormality.
∆: Shrinkage was observed on the coating film.
×: The coating film after the first coating was dissolved; the brushstroke felt heavy.

(3) Gloss of the coating film

After applying the ordinary temperature curable coating composition to the surface of a slate plate coated with "ALES CELAMILD" (manufactured by Kansai Paint Co., Ltd., white matte coating) by means of the 300 µm applicator and drying for one week, the 60 ° - Mirror gloss measured.

: 90% or more.
○: 80% or more, less than 90%.
∆: 70% or more, less than 80%.
×: Less than 70%.

(4) Weather resistance

After applying the ordinary temperature curable coating composition to the surface of a slate plate coated with "ALES CELAMILD" (manufactured by Kansai Paint Co., Ltd., white matte coating) with the 300 µm applicator and drying for one week, with a sunshine -Weathering meter determines the gloss retention ratio after an exposure of 1500 hours.

: 90% or more.
○: 80% or more, less than 90%.
∆: 70% or more, less than 80%.
×: Less than 70%.

(5) water resistance

After the slate plate was coated with the ordinary temperature curable coating composition by means of the 300 µm applicator, and the coated plate was dried at 20 ° C and 75% relative humidity for one week and immersed in drinking water (20 ° C) for three days the state of the coating film was visually determined.

○: No abnormality.
∆: Little blistering.
×: Noticeable blistering was observed.

(6) Acid resistance

After 0.5 cm ^{3 of} a 0.1 N sulfuric acid aqueous solution was dropped onto a coated plate obtained similarly to the test of the original drying property, the plate was left to stand at 20 ° C. for 24 hours, rinsed, and the state of the coating film was determined.

○: No abnormality.
∆: Slight whiteness was found.
×: Noticeable whitening occurred; in addition, etching of the surface of the coating film was observed.

Table 1

Examples 4 to 12 and Comparative Example 2

The solutions of the silicone-modified resin based on vinyl containing non-volatile constituents of 50%, which are obtained according to the preparation example and have the mixture composition given in Table 2 (Solids content in parts by weight), along with 250 parts of glass beads with a diameter of 1.5 mm is used to create a Perform sand mill dispersion and obtain a pigment paste. Afterward the polymer dispersion was made with a non-volatile content of 50%, which was obtained in the preparation example, the curing catalyst "DICNATE 1000" (manufactured by Dainippon Ink & Chemicals Inc., active cobalt desiccant which contains a cobalt salt of an organic acid) and zirconium octylate in the table specified mixing ratios added (solids content in parts by weight). It was stirred uniformly to make the ordinary temperature curable To obtain coating composition. In addition, in Comparative Example 2 instead of a solution of the silicone-modified vinyl-based resin, a solution of the Fatty acid-modified copolymers (a) with a content of non-volatile Components of 50%, as it was obtained in the manufacturing process, used. How out Table 2 shows the total amount of solids content of silicone-modified Vinyl-based resin (A-1), (A-2) or (A-3) and the solid content of said Polymer dispersion (B-1) or (B-2) 100 parts.

Performance test

Those obtained in Examples 4 to 12 and Comparative Example 2, respectively, in Ordinary temperature curable coating compositions were the subjected to the following tests for weather resistance and alkali resistance. the Test results are given in Table 2.

(7) Resistance to alkali

The slate plate coated with "VP SEALER TOMEI" (manufactured by Kansai Paint Co., Ltd., transparent sealant based on vinyl chloride resin) was coated with the ordinary temperature curable coating composition by means of a brush in a coating amount of 160 g / m ² and in left in a room for six hours at 20 ° C and 75% relative humidity. Subsequently, 0.5 cm ^{3 of} a 0.1 N aqueous sodium hydroxide solution was dropped onto the surface of the coating film and the coated plate was left to stand for 24 hours in a room at a temperature of 20 ° C. and 75% relative humidity. The plate was then rinsed and the condition of the coating film was visually checked.

○: No abnormality
∆: Slight whitening was found.
×: Pronounced whitening and etching of the surface were found.

(8) Weatherability

A formation-treated steel plate coated with "ESCO" (manufactured by Kansai Paint Co., Ltd., an anti-corrosion coating based on an epoxy resin) was coated with the ordinary temperature curable coating composition by means of a brush until a coating amount of 160 g / m ^{2 was} reached, and then stored in a room at 20 ° C and 75% relative humidity for seven days. Then, after exposure for 1500 hours with a sunshine weatherometer, the gloss retention ratio was determined.

: 90% or more.
○: 80% or more, less than 90%.
∆: 70% or more, less than 80%.
×: less than 70%.

In the present invention an oxidatively curable silicone-modified In the vinyl-based resin, the main chain is a vinyl polymer and an unsaturated fatty acid is to give the polymer the property of drying at ordinary Temperature added. Another silicone resin is added to the To strengthen weather resistance of a coating film obtained.

Table 2

A coating composition of this invention contains as a resin component oxidatively curable silicone-modified vinyl-based resin. These Coating composition is curable at ordinary temperature and can have a Form a coating film that, in terms of weather resistance, Coating film gloss and the properties when carrying out the coating such as Storage property, initial drying property and brush stroke Double coats with a brush is superior.

In addition, in the coating composition of the present invention the oxidatively curable silicone-modified vinyl-based resin in combination with a Polymer dispersion is used, which ensures resistance to alkalis.

Although only a few exemplary embodiments of this invention have been detailed above those skilled in the art will readily recognize that in FIGS Many modifications are possible without changing the exemplary embodiments substantially remove the new teaching and advantages of this invention. Therefore All such modifications are intended to be included within the scope of this invention.

Claims (8)

1. An ordinary temperature curable coating composition, comprising an oxidatively curable silicone-modified vinyl-based resin (A) which is obtainable by combining a vinyl copolymer containing epoxy groups (a) with an unsaturated fatty acid-containing fatty acid component (b) and a The silicone resin (c), wherein the vinyl copolymer (a) is a copolymer of an epoxy group containing polymerizable unsaturated first monomer and a polymerizable unsaturated second monomers, which is copolymerizable with is the first monomer, and wherein the silicone resin (c) has a silicon atom and a Hydroxy group and / or an alkoxy group, which is attached to the silicon atom is bound. 2. Ordinary temperature curable coating composition according to claim 1, wherein the copolymerization ratio of the first and second monomer is such that the first monomer in the range of 3 to 70 wt .-% and the second monomer in the Ranges from 30 to 97 weight percent. 3. Ordinary temperature curable coating composition according to claim 1 or 2, wherein the epoxy group-containing vinyl copolymer (a) is a copolymer, whose number average molecular weight is 1,000 to 100,000 and whose Glass transition temperature is 0 ° C to 100 ° C. 4. Coating composition curable at ordinary temperature according to any one of Claims 1 to 3, wherein the unsaturated fatty acid-containing fatty acid component (b) has an iodine number of 50 to 200. 5. Ordinary temperature curable coating composition according to claim 1, wherein the oxidatively curable silicone-modified vinyl-based resin (A) is obtained by adding the fatty acid component (b) to the epoxy group-containing one Vinyl copolymer (a) followed by the addition of the silicone resin (c). 6. Ordinary temperature curable coating composition according to any one of Claims 1 to 5, this composition additionally comprising a polymer dispersion (B) which is obtained by adding a polymerizable unsaturated third monomer in an organic liquid in the presence of a dispersion stabilizer (d) in the organic liquid is soluble, is polymerized, and wherein the third monomer in the organic liquid is dissolved and that formed from the third monomer Polymer is not dissolved in the organic liquid, the solid content of the resin based on vinyl (A) in the range of 5 to 95 wt .-% and the solids content of the Polymer dispersion (B) is in the range from 5 to 95% by weight, based on the total Solid content of vinyl-based resin (A) and polymer dispersion (B). 7. Ordinary temperature curable coating composition according to claim 6, wherein the dispersion stabilizer (d) is a copolymer of a polymerizable unsaturated fourth monomer, which has an oxidatively polymerizable double bond, and a polymerizable unsaturated fifth monomer, which with the fourth Monomer is copolymerizable, is. The ordinary temperature curable coating composition of claim 7, wherein the fourth monomer contains the formula: