WO2006011260A1 - Coating composition - Google Patents

Abstract

A two-package type cold-setting organopolysiloxane coating composition which is excellent in bending resistance, crack resistance, and drying characteristics after application and which permits the application as a solventless or high-solids coating composition. The coating composition comprises (a) an alkoxy-containing organosilane compound having an Si content of 12 % by mass or above, (b) a compound having two or more glycidyl groups in one molecule, (c) a curing catalyst, and (d) an alkoxy-containing organosilane compound having a primary or secondary amino group as the essential components and, if necessary, contains (e) at least one additive selected from among color pigments, body pigments, matting agent, pigment dispersant, defoamer, leveling agent, ultraviolet absorber, plasticizer, antifungus agent, antialgal agent, and other additives for coating materials. It is preferable that the composition be used as a two-package type composition composed of the first fluid containing the glycidyl component reactive with the component (d) and the second fluid containing the component (d).

Description

 Specification

 Paint composition

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a coating composition, and more specifically, a two-pack type organopolysiloxane-based coating that is excellent in bending resistance and crack resistance, has excellent coating workability such as drying properties, and can be cured at room temperature. Relates to the composition.

 Background art

 [0002] Organopolysiloxane-based paints have been conventionally used as coating compositions having excellent weather resistance and stain resistance. These performances of organopolysiloxane-based paints are derived from the siloxane bond skeleton of silicone. Among silicone compounds that can be adjusted as a coating composition, typical ones that can be crosslinked at room temperature are mainly composed of organosiloxane compounds having a plurality of Si atoms having a plurality of alkoxy groups. After coating, siloxane bonds are three-dimensionally formed by dealcoholization condensation in the presence of moisture, and crosslinking proceeds. Since the siloxane bond obtained by this reaction is dense, a coating film having high coating hardness can be obtained. On the other hand, it leads to brittleness of the coating film and poor adhesion to the coated substrate. Siloxane bonds do not have sufficient performance with respect to alkali resistance. Therefore, as means for solving these performances, attempts have been made to introduce organic resin such as alkyd resin, polyester resin, acrylic resin, and epoxy resin into the paint.

 For example, Patent Document 1 (Japanese Patent Laid-Open No. 2000-63612) includes (A) an acrylic resin component having a functional group reactive with an epoxy group, a curing catalyst component composed of an organometallic compound, and a coloring pigment. There has been proposed a two-component coating composition comprising an organic composition containing, and (B) an inorganic composition containing a silane compound having an epoxy group or its oligomer component and a silicone resin component! The

 It is disclosed that a coating film excellent in weather resistance and adhesion to an old coating film can be obtained by using this two-component coating composition. It is also described that this coating composition has good storage stability.

[0004] However, with conventional organopolysiloxane paints, the resistance to crushing when a coating film is formed is reduced. It was a component that rackability and bending resistance were not sufficient. An attempt to improve this is described in Patent Document 2 (Japanese Patent Laid-Open No. 2003-238895). An alkoxy group-containing organic silane compound, a glycidyl group-containing organosilane, and a glycidyl group-containing non-silane system Proposals have been made on organic compounds, acrylic copolymers capable of reacting with glycidyl groups, and two-component coating compositions containing these as components. Further, it is disclosed that by using this two-component coating composition, it is possible to obtain a coating film having excellent weather resistance and stain resistance, as well as excellent bending resistance and crack resistance.

 Patent Document 1: Japanese Patent Laid-Open No. 2000-63612

 Patent Document 2: Japanese Patent Laid-Open No. 2003-238895

 Disclosure of the invention

 Problems to be solved by the invention

However, in the case of the one described in Patent Document 2, it has been found that the acrylic copolymer capable of reacting with the glycidyl group is less reactive than the other compositions. For this reason, it took a relatively long time for the surface tack to disappear immediately after painting, and during that time, foreign matter adhered to the painted surface could be contaminated with dust. In addition, when acryl-based copolymers that can react with glycidyl groups are used, many copolymers are more viscous than other components. It is necessary to adjust the viscosity of the paint by increasing the amount of organic solvent added. was there. Furthermore, since the acrylic copolymer that can react with the glycidyl group is poorly compatible with other components, it satisfies this requirement.

 The addition of an organic solvent was indispensable for the purpose of compensating for the poor compatibility. These were disadvantageous factors in the selection of raw materials when trying to obtain suitable physical properties.

 [0006] By the way, as a paint desired from the recent consideration for the influence on the environment, a paint having a small emission amount of an organic solvent or the like having a small influence is desired. The present invention has been made in response to a request for solving these problems. The object of the present invention is to have excellent bending resistance and crack resistance, excellent drying after coating, and nothing. It is an object of the present invention to provide a two-component room temperature curing organopolysiloxane coating composition that can be made into a solvent and high solid.

Means for solving the problem [0007] The present invention includes the following inventions.

 (1)

 (a) Organosilane-containing organosilane compound having a Si content of 12% by mass or more

 (b) Compound containing two or more glycidyl groups in one molecule

 (c) Curing catalyst

 (d) Alkoxy group-containing organosilane compound having l- or secondary amino group

 A coating composition containing as an essential component.

 [0008] (2) In addition to the component (a), the component (b), the component (c) and the component (d), (e) a color pigment, an extender pigment, a decoloring agent, a pigment dispersant, an antifoaming agent, (1) The coating composition according to (1), which contains at least one additive selected from a belling agent, an ultraviolet absorber, a plasticizer, an antifungal agent, an anti-algae agent and other coating additives.

 (3) The component (a) is a silane compound or a condensate thereof represented by the following general formula (1)

 The coating composition according to item (1) or (2).

 [Chemical 1]

R ³

 I

R ² — S i — OR ¹ (1)

(Wherein R ¹ is a hydrogen atom or an alkyl group, and R ² and R ⁴ are each independently a hydrogen atom, OR ¹ , an alkyl group or an aryl group)

[0010] (4) The component (b)

 (i) a compound obtained by glycidyl etherification of a hydroxyl group-containing compound,

(ii) Cyclooxylan type compound, glycidyl ester type compound, epoxidized type compound of aliphatic unsaturated compound, polyvalent carboxylic acid ester type compound, bisphenol A type compound, hydrogenated bisphenol A type compound and novolak type compound A compound selected from as well as

 (iii) Compound strength obtained by grafting a glycidyl group-containing component to an acrylic polymer.

 Group force as force The coating composition according to any one of items (1) to (3), wherein the composition is at least one compound selected.

[0011] (5) The mass average molecular weight of the component (b) is 200 or more and less than 100,000, and the content of the component (b), the component (c) and the component (d) is 100 masses of the component (a). (B) Component 30-200 parts by mass, (c) Component 0.1-30 parts by mass, and (d) Component 10-150 parts by mass, The coating composition according to item 1.

[0012] (6) The component (e) is contained in an amount of 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (a) (2

The coating composition according to item 1 of item 1 (5).

[0013] (7) The coating composition according to any one of items (1) to (6), further comprising an organic solvent.

 [0014] (8) The coating composition according to item (7), wherein the organic solvent is a petroleum hydrocarbon solvent.

 (9) Among the components (a) and (d), the component having a glycidyl group that reacts with the component (d) is blended in the first solution, and the component (d) is contained in the second solution. The coating composition according to paragraph 1 of paragraph (1)-(8), wherein the coating composition is a two-component composition.

(10) Among the components (a) and (d), the component having a glycidyl group that reacts with the component (d) is blended in the first liquid, and the component (d) is contained in the second liquid. The component (b), the component (c), and the component (e) force selected are mixed in one or both of the first liquid and the second liquid. The coating composition according to item (9).

 The invention's effect

 [0017] In the coating composition of the present invention, by combining the (a)-(d) component and the specific four components, the inherent weather resistance and stain resistance of the organopolysiloxane coating material are obtained. To obtain a coating composition that is superior in bending resistance and crack resistance, has excellent drying properties, and that can be made solvent-free and can prevent the occurrence of defects in the old coating film. Can

BEST MODE FOR CARRYING OUT THE INVENTION [0018] The two-component room temperature curable organosiloxane coating composition of the present invention has the above-described components (a) to (d) as essential components and, if necessary, a component containing component (e). In use, it is adjusted by mixing two liquids consisting of the first liquid and the second liquid. First, each component used in the coating composition of the present invention will be described below.

 [0019] <Component (a)>

 In the alkoxysilane-containing organosilane compound used as component (a), the lower limit of the Si content is 12% by mass or more, preferably 20% by mass, from the viewpoint of the weather resistance performance and stain resistance of the paint. On the other hand, the upper limit of the Si content is not particularly defined, but is preferably 35% by mass. In addition, an alkoxy group-containing organosilane compound containing a reactive group capable of reacting with an organic group, for example, glycidyl, acrylic group, or bur group, is also preferably used. These compounds can be used well even in one kind or a mixture of two or more kinds.

 [0020] Here, the Si content of the component (a) can be obtained by a pyrolysis method which is a public corporation standard. Specifically, weigh lg component (a) (solid content) in a Teflon pressure-resistant container and add 2-3 ml of concentrated sulfuric acid. Next, it is heated to 150-160 ° C and allowed to stand for 24 hours to decompose the alkoxy group-containing organosilane compound. The obtained sulfuric acid solution is transferred to a pre-weighed platinum dish and slowly raised to 700-800 ° C in the atmosphere to completely decompose the alkoxysilane-containing organosilane compound. Weigh after cooling, and first determine the amount of silica (SiO 2) from the residue using the following formula.

 2

 Silica (SiO) content = (residue after complete decomposition) / (mass of component (a) (solid content))

 2

 Then, from the calculated amount of silica (SiO 2) (mass%), the Si content (mass%) is calculated by the following formula:

 2

 Ask.

 Si content = [silica (SiO 2) amount X (Si / SiO 2)]

 twenty two

 In the present invention, the alkoxy group-containing organosilane compound is represented by the following general formula (1),

[Chemical 1] R ³

 I

R ² — S i — OR ¹ (1)

Wherein R ¹ is a hydrogen atom or an alkyl group, and R ² , R ³ and R ⁴ are each independently a hydrogen atom, OR ¹ , an alkyl group or an aryl group. Thing or its

 A condensate is preferred. In the present invention, the alkoxy group-containing organosilane compound as component (a) may be used alone or in combination of two or more.

In the present invention, as component (a), in the general formula (1), R ¹ is a methyl group or an ethyl group, and R ² , R ^3, and R ⁴ are each independently a methyl group It is more preferable to use a compound that is a phenyl group, a methoxy group, an ethoxy group, or an epoxy group.

 [0023] Preferable examples of the alkoxy group-containing organosilane compound include trade names, DC3074, DC3037, SR2402 (above, manufactured by Toray 'Dowcoing' Silicone), trade names, KR 9218, KR— 213, KR510, X40-9227, X40-9247, KR500, KR400, X40-9225, X40-9246, X40-9250 (above, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0024] As the glycidyl group-containing alkoxy group-containing organosilane compound, an epoxy equivalent (gZ eq.) Force of -2000 and a mass average molecular weight of 150-10000 are suitably used. Specifically, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, j8-glycidchichetiltrimethoxysilane, j8-glycidchichetiltriethoxysilane, γ-glycidoxypropyltrimethoxysilane Γ-Glycidoxyprobilt propyl (dimethyl) methoxysilane, γ-Glycidoxypropyl (ethyl) dimethoxysilane J8 (3,4-epoxycyclohexenole) ethynoletrimethoxysilane, γ-glycidoxypolysiloxane, and the like.

 [0025] In the present invention, trade names such as X41-1053 and X41-1056 (manufactured by Shin-Etsu Chemical Co., Ltd.), which are commercially available as glycidyl group-containing silicone alkoxy ligomers (a) It can also be used as a component.

 [0026] Furthermore, as component (a), glycidyl group-containing unsaturated monomers such as γ (meth) attaryloxypropylmethoxysilane and glycidyl (meth) acrylate, and hydrolyzable unsaturated silyl group-containing unsaturated monomers A copolymer with can also be used.

 [0027] <Component (b)>

 The compound containing two or more glycidyl groups in one molecule used as the component (b) has a mass average molecular weight of 200 or more and 100000 or less from the viewpoint of compatibility with other components! / The mass average molecular weight is preferably 200 or more and 5000 or less. The main skeleton of the compound is not particularly limited, but is preferably composed of a saturated hydrocarbon in order to obtain high weather resistance. Furthermore, the following (i) one (iii) is used in terms of improving flexibility and adhesion to an object to be coated.

 I prefer to do that!

 [0028] (i) A compound obtained by glycidyl ether-computing a hydroxyl group-containing compound:

Here, examples of the hydroxyl group compound include (i) methanol, ethanol, propyl alcohol, monovalent higher alcohols linked thereto, alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol, and the dehydration condensation described on the left. Polyols made of products, polyhydric alcohols such as glycerin and sorbitol; (mouth) succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexane One or more of polycarboxylic acids such as hydroisophthalic acid, hexahydroorthophthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic acid, pyromellitic acid, acid ester, or acid anhydride , Ethylene glycol, 1,2-propanediol, 1 , 3 Propanediol, 1,2 Butanediol, 1,3 Butanediol, 1,4 Butanediol, 1,5 Pentanediol, 1,6-Hexanediol, 1,8 Octanediol, Neopentyl glycol, Diethylene glycol, Dipropiol Polyester polyols obtained by dehydration condensation with one or more of low molecular polyols such as lenglycol, 1,4-cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, etc .; (c) low molecular polyols, low molecular polyamines, Latatone-based polyester polyols obtained by ring-opening polymerization of cyclic ester monomers such as ε-force prolatatone and _Ύ -valerolatataton using low molecular amino alcohol as an initiator; (2) low molecular polyol, diethylene carbonate, dimethyl carbonate, Examples thereof include polycarbonate polyols obtained by dealcoholization reaction, dephenol reaction and the like with jetyl carbonate, diphenol carbonate and the like.

 Specific examples include ether compounds having a glycidyl group at the terminal as represented by the following general formula.

[Chemical 2] CHO) n— CH ₂ — CH— CH ₂

CH ₂ — CH— CH ₂ _ 0 (CH ₂ CH ₂ 0) n— CH ₂ — CH— CH ₂

 〇 〇

_{CH 2 - 0 - (C 4} H 8 0) n- CH 2 - CH 2

(n is an integer, preferably 2 to 40)

(ii) Cyclic oxysilane type compounds, glycidyl ester type compounds, epoxidized compounds of aliphatic unsaturated compounds, polycarboxylic acid ester type compounds, bisphenol A type compounds, hydrogenated bisphenol A type compounds or novolac type compounds Compound. Examples of such compounds include those represented by the following general formula. [0031] [Chemical 3]

(R is a hydrocarbon group, an integer of 11 = 2 to 10)

[Iii] (iii) Compound obtained by grafting a glycidyl group-containing component to an acrylic polymer

Specific examples of such a powerful compound include a copolymer of a glycidyl group-containing unsaturated monomer and another ethylenically unsaturated monomer. Here, glycidyl-containing unsaturated monomers include glycidyl (meth) acrylate, j8-methyldaricidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3, 4 epoxycyclohexane. Xylpropyl (meth) acrylate. Of these, glycidyl (meth) acrylate is preferred because of its reactivity. In addition, the acrylic composition grafted with a glycidyl group-containing component has a Tg in the range of -50 to 10 ° C in terms of having an epoxy equivalent in terms of having a practically desirable flexibility after crosslinking and curing of the coating composition. The monomer composition is preferably 500 to 1500. For example, a copolymer composed of glycidyl (meth) acrylate, 2-ethylhexyl acrylate, n-butyl (meth) acrylate can be used. In the polymerization of (iii), the use of an organic solvent is not limited. The solvent used for the polymerization is not particularly limited as long as it can be solution-polymerized and can dissolve the monomer to be used and the polymer to be obtained. Specifically, toluene, xylene, ethylbenzene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl allyl, η-butyl alcohol, Examples include mineral spirits. These may be used alone or in combination of two or more. Furthermore, after the polymerization is complete, it is possible to remove the solvent according to the purpose and change the type of solvent.

 [0034] <(c) component>

 The curing catalyst used as component (c) is preferably an organometallic compound. Specifically, metal alkoxide compounds such as Ti, Al, Zr and Sn, metal chelate compounds, metal ester compounds and metal silicates are used. Toy compounds can be used.

The [0035] metal alkoxide compound, e.g., aluminum trimethoxide, aluminum preparative Rietokishido, aluminum tree _n - propoxide, aluminum triisopropoxide, Al Miniumutori _n - butoxide, aluminum triisobutoxide, aluminum tree sec- butoxy Kishido Aluminum alkoxide such as aluminum tree tert-butoxide; tetramethyl titanate, tetraethyl titanate, tetra n-propyl titanate, tetraisopropyl propitanate, tetra n-butyl titanate, tetra tert-butyl titanate, tetra n xyl titanate, tetraisooctyl titanate , titanium alkoxides such as 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, teller tert-pentinoresinoreconate, tetra-tert xinoresinoreco And zirconium alkoxides such as tetra-tert-butyl zirconate, tetra-tert-dioctyl zirconate and tetra-n-stearyl zirconate; and tin alkoxides such as dibutyltin dibutoxide.

As the metal chelate compound, for example, tris (ethyl acetate acetate) aluminum, Tris (isopropyl acetate) aluminum, tris (n-butylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (propolacetonato) aluminum, diisopropoxyp Pio-l-acetonatoaluminum, acetiacetonato'bis (propio-l-acetonato) aluminum, acetylacetonatoaluminum. Di-sec-butyrate, methylacetate-aluminum _sec -butyrate, di (methylacetate Acetate) 'mono-tert-butylate, diisopropoxy cetinoreacetoacetate anoreminium, monoacetinoreacetona' aluminum chelate compounds such as bis (ethylacetoacetate) aluminum; Titanium chelate compounds such as Roxy bis (ethinoreacetoacetate) titanium and diisopropoxy'bis (acetinoreacetonato) titanium; tetrakis (acetylacetonato) zircoyuum, tributoxy ) Zirconium chelate compounds such as zirconium; dibutyltin bis (acetylacetonate) and the like. Examples of metal ester compounds include titanium ester compounds such as polyhydroxytitanium stearate; tributoxyzirconium Zirconium ester compounds such as stearate; dibutyltin diacetate, dibutyltin di (2-ethylhexylate), dibenzyltin di (2-ethylhexylate), dibutyltin ditatoate, dibutyltin dilaurate, dibutyltin distearate , Dibutyltin diisooctyl malate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin distearate, and the like. Examples of metal silicate toy compounds include dibutyltin bistrimethoxysilicate. , Dibutyltin bistriethoxysilicate, dioctyltin bistrimethoxysilicate, and dioctyltin bistriethoxysilicate.

 These reaction catalysts can be used alone or in combination of two or more.

 [0037] When the curing catalyst causes problems in the pot life and storage stability of the paint, it is preferable to use a keto-enol-type tautomeric compound in combination. Examples of keto'enol-type tautomeric compounds include acetylacetone, acetoacetate ethyl ester, malonate diester, benzoylacetone, dibenzylmethane, diacetone alcohol, and methyl salicylate.

[0038] <(d) component> (d) Alkoxy group-containing organosilane compound having a primary or secondary amino group used as component having a mass average molecular weight of 150-10000, preferably a dish average molecular weight of 150-5000, It must have at least one amino group active hydrogen in the molecule. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane Γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, bis (trimethoxysilylpropyl) amine, _Ύ -ureidopropyltriethoxysilane, and the like. These can be used alone or in combination of two or more

[0039] Furthermore, a product obtained by subjecting an alkoxy group-containing organic silane compound having a primary or secondary amino group to dealcoholization condensation with a silicone alkoxy oligomer or the like within a range not impairing the performance can also be suitably used. These compounds can be used in combination with those listed in paragraph 0026 as an alkoxy group-containing organosilane compound having a primary or secondary amino group.

 [0040] The amount of component (d) to be added is preferably 0.1-2.0 equivalents relative to 1 equivalent of the glycidyl group of component (a) and Z or (b), more preferably, 5-1. Two equivalents. In addition, to the component (d), an alkoxy group-containing organosilane compound having a tertiary amino group can be added in combination as long as the object of the present invention is not impaired.

 [0041] <(e) component>

 In addition to the essential components (a) to (d) described above, the coating composition of the present invention can be used as a coating material in addition to the components (a) to (d) as long as the purpose of the present invention is not impaired. For the purpose of imparting performance, as component (e), coloring pigments, extender pigments, matting agents, pigment dispersants, antifoaming agents, leveling agents, rheology control agents, UV absorbers, plasticizers, antifungal agents Further, an anti-algae agent and other paint additives can be appropriately blended.

[0042] Further, an organic solvent can be added for the purpose of improving the coating workability within the range not impairing the object of the present invention. However, since the object of the present invention includes the reduction of the use of organic solvents, it is desirable to minimize the use. Usable organic solvents are aromatic solvents, ester solvents, ketone solvents, ether solvents, alicyclic hydrocarbons Any of solvent, alcohol solvent, and petroleum hydrocarbon solvent can be used. Among these, it is desirable to combine and use alicyclic hydrocarbon solvents, alcohol solvents, and petroleum hydrocarbon solvents, which are useful for improving the working environment.

 [0043] In the coating composition of the present invention, the coating component is composed of the first liquid and the second liquid, and the two liquids are mixed in use. In the coating composition of the present invention, it is desirable to adjust to the first liquid and the second liquid from the viewpoint of storage stability. That is, each component contained in the two-component coating composition of the present invention is preferably adjusted as follows. Further, the optional component (e) can be present in either the first liquid or the second liquid, or in both the first liquid and the second liquid.

 [0044] When the component (a) includes a glycidyl group-containing compound,

 Component (a) is present in the first liquid,

 Component (b) is present in the first liquid,

 (c) Component is present in the first liquid and Z or the second liquid,

 Component (d) is present in the second liquid,

 Component (e) is present in the first liquid and the Z or second liquid.

[0045] The component (a) does not contain a glycidyl group-containing compound! /,

 Component (a) is present in the first liquid and Z or the second liquid,

 Component (b) is present in the first liquid,

 (c) Component is present in the first liquid and Z or the second liquid,

 Component (d) is present in the second liquid,

 Component (e) is present in the first liquid and the Z or second liquid.

 [0046] The method for producing the coating composition of the present invention is not particularly limited, and the first liquid and the second liquid may be mixed and stirred when used. The mixing ratio of the first liquid and the second liquid is not particularly limited. The pot life as a paint is preferably 3-8 hours.

[0047] The coating composition of the present invention is suitably used in machinery, ships, vehicles, aircraft, civil engineering, construction, heavy anticorrosion, and other general industrial fields because it has room temperature curing and low contamination and high weather resistance. In particular, when the coating composition of the present invention is used, a coating film exhibiting excellent flexibility without impairing the performance of the organopolysiloxane-based coating can be obtained. It is suitable for an object to be coated. In addition, since the coating composition of the present invention can be expected to maintain the coating performance over a long period of 10 to 20 years, it has a long maintenance cycle such as ceramics-metal curtain walls used in high-rise buildings. It can be suitably used in the field.

 [0048] As described above, in the coating composition of the present invention, by combining the specific four components (a) to (d), the inherent weather resistance and stain resistance of the organopolysiloxane coating are obtained. It is possible to obtain an organopolysiloxane-based coating composition excellent in flexibility without impairing the properties. In addition, by setting the blending amount of the components (a) to (d) to a specific amount, the coating composition has excellent performance in all of weather resistance, stain resistance, flex resistance, crack resistance and alkali resistance. You will get things.

 [0049] Furthermore, the coating composition of the present invention has a coating workability without adding an organic solvent to the component (e) by making the blending amount of (a) one (d) component a specific amount. Can be designed with good paint. Since the coating composition of the present invention itself is composed of low odor components, it can be designed as an environmentally friendly coating. In addition, even when viscosity adjustment is required during painting operations, it is soluble in petroleum hydrocarbon solvents and alcohol solvents, which have low dissolving power, and can be diluted appropriately. It can be used for coating on places where there is a film or a substrate with poor solvent resistance.

 Example

 [0050] Hereinafter, the present invention will be described with specific examples, but the present invention is not limited to these examples. Moreover, the physical property evaluation method of the coating composition used in Examples and Comparative Examples will be described. In the following, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

 [0051] <Flexibility>

For evaluation of bending resistance, a mandrel with a diameter of 10 mm was used in accordance with JIS K 5600-5-1. In addition, as a test piece, a paint composition was applied to a 150 X 50 X 0.3 mm steel plate with a brush so that the dry coating thickness was O / zm, and the conditions were 23 ° C and 50% RH. After curing for 4 days, a product that was further forced to dry at 80 ° C for 3 days was used. In the evaluation, the bent part of the coating film is visually observed. “X”.

[0052] High crack resistance>

 Crack resistance 〖O In accordance with IS K 5600-7-4 (wet and cold-heat repeatability), soak in water at 23 ° C for 18 hours, then in a freezer at 20 ° C for 3 hours, then at 50 ° C for 3 hours Warmed up. This cycle was repeated for 50 cycles, and the state of the coating after the test was visually observed, and the degree of cracking, swelling and whitening in the coating was evaluated in the following three stages. The test piece is 70 X 70 X 6

 Paint the coating composition with a brush to a thickness of 50 μm on a flexible board of mm.

 It was prepared by curing for 4 days under conditions of 23 ° C and 50% RH, followed by forced drying at 80 ° C for 3 days.

 ◯: No change is seen in the coating film.

 Cracks and blisters are observed in a part of the coating film.

 X: Remarkable cracking and swelling are observed in the coating film.

 [0053] <Accelerated weather resistance>

The accelerated weathering test was performed using a super accelerated weathering tester [Isuper Japan UV Tester manufactured by Iwasaki Electric Co., Ltd.]. In addition, the test piece is painted on a 50 x 50 x 4 mm flexible board with a brush so that the dry coating is 50 m and dried for 7 days at 23 ° C and 50% RH. This was produced. The test conditions were as follows: wavelength 295-450nm, UV irradiation intensity 100mW'cm ² , black panel temperature 63 ° C, 50% RH, 1 cycle irradiation 4 hours, condensation 4 hours, 125 cycles (1000 hours) . After the test was completed, the gloss retention with respect to the initial 60 ° specular gloss value of the coating film was determined and evaluated in the following three stages.

 ○: Gloss retention 70% or more

 △: Gloss retention 50% or more, less than 70%

 X: Gloss retention less than 50%

 [0054] <Alkali resistance>

In the alkali resistance test, the test piece was immersed in a solution prepared by adjusting sodium hydroxide sodium hydroxide to 5 WZV% with deionized water in accordance with JIS K 5600-6-1 for 7 days at 23 ° C. After immersion, test The specimen was gently washed with running water, dried for 2 hours, and the swelling, cracking, peeling, and gloss change of the coating film were visually observed and evaluated in three stages. As a test piece, paint on a 150 x 70 x 4 mm flexible board with a brush so that the dry film thickness is 50 μm. C, dried for 14 days under the condition of 50% RH.

 〇: There is no significant change compared to the current test piece.

 (Triangle | delta): There exists a slight shrinkage compared with the present condition test piece.

 X: There are significant tearing, cracking, and peeling compared with the current test piece.

[0055] <Adhesiveness>

 The adhesion test was performed in accordance with JIS K 5600-5-6 cross-cut method, using a cutter guide with a gap interval of 2 mm to cut a grid (25 squares; 5 vertical x 5 horizontal).セ A cellophane adhesive tape was placed on the grid, and the tape was peeled off in a direction perpendicular to the coating surface with one end of the tape, and the area of the coating film peeled was measured. The test piece was a 150 x 70 x 4 mm flexible board painted with a brush to a dry film thickness of 50 μm and dried for 14 days under conditions of 23 ° C and 50% RH. Was used. The adhesion was evaluated as follows from the area of peeling of the coating film relative to the total area of the coating film.

 ○: When the area of the paint film is less than 5% of the total area

 Δ: When the peeled area of the coating is 5% or more and less than 35% of the total area

 X: When the peeling area of the coating is 35% or more of the total area

[0056] <Forced contamination>

Paint the paint composition with a brush on a 150 x 70 x 0.8 mm aluminum plate to a dry film thickness of 50 μm, and dry for 14 days at 23 ° C and 50% RH. Was made. The resulting specimen is air sprayed with carbon suspension (dispersed dispersion of paint shaker for 2 hours with 5 parts of carbon black Color Black FW200 manufactured by Dedasa Huls and 95 parts of deionized water. Then, it was applied until concealed and immediately dried at 60 ° C for 1 hour. After drying, it was allowed to cool to room temperature, and the surface of the test piece was washed under running water until the soiled material did not fall off. After washing, it was dried at room temperature for 3 hours, and the degree of soiling was measured with a color difference meter to determine the difference in lightness (AL *) of the coating film before and after the test, and evaluated in the following three stages. It should be noted that the smaller the difference in brightness, the more excellent the stain resistance. Yes.

 Lightness difference (AL *) = [Coat brightness after test (L * 1) Film brightness before test (L * 0)] ○: Lightness difference -5 or more

 △: Lightness difference 10 or more, less than 5

 X: Lightness difference less than -10

[0057] <Drying>

 Evaluation of drying property «JIS K 5600— 1 Can be performed according to one-touch drying. The test piece was painted on a 150 x 70 x 4 mm flexible board with a brush so that the dry film thickness was 50 μm, dried under conditions of 23 ° C and 50% RH. Lightly touch the center of the surface with your fingertips, measure the time until the fingertips are no longer soiled, and evaluate in the following three stages. 〇: Drying time within 4 hours · · · · Good drying

 Δ: Drying time 4 hours or more, less than 8 hours

 X: Drying time 8 hours or more · · · · Poor drying

[0058] <Overall evaluation>

 Based on the results of the performance measurement of the coating composition shown above, a comprehensive evaluation of the coating composition was performed according to the criteria shown below.

 ◯: All are rated as ◯, and can be used very favorably as a coating composition

△: There is an evaluation of △, and it is a level that can be used as a paint yarn and a composition. Its use may be limited.

 X: X is rated and is difficult to use as a paint composition.

[0059] Next, components to be blended in the coating composition will be described.

 <(a) component>

 (a-1) Methylphenol alkoxysilane oligomer (Product name: KR-510, Shin-Etsu Chemical Co., Ltd., S source approximately 25%)

 (a-2) Methyl-based alkoxysilane oligomer (trade name: KR-500, Shin-Etsu Chemical Co., Ltd. Si atom: about 31%)

(a-3) Glycidyl group-containing silicone oligomer (trade name: X-41-1053, Shin-Etsu Chemical Co., Ltd., epoxy equivalent 820, Si atom 23%) [0060] <(b) component>

 (b—1) Adeka Resin EP—4080S (Asahi Denka Co., Epoxy Equivalent 240 Molecular Weight 480) (b—2) Adeka Glycilol ED—506 (Asahi Denka Epoxy Equivalent 310 Molecular Weight 620) (b—3) Adekaoptomer KRM-240 (Asahi Denka Co., epoxy equivalent 250 molecular weight 500)

 [0061] <(c) component>

 (c 1) Alkyl acetate acetate aluminum diisopropylate

 (c 2) Dibutinoletin diacetate

[0062] <component (d)>

 (d-1) γ-Aminopropyltriethoxysilane (trade name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

)

 (d-2) γ- (2Aminoethyl) aminopropyltrimethoxysilane (trade name: A-1112, manufactured by Niunica Japan)

[0063] <(e) component>

 (e-1) Rutile-type acid-titanium (DuPont)

 (e-2) Polymer wetting and dispersing agent (Brand name: Disperbyk 110 BYK manufactured by Kemiichi Co., Ltd.

 )

 (e-3) Fumed silica (trade name: Aerosil 200, manufactured by Aerosil)

 (e-4) Surface conditioner (Brand name: BYK—300 BYK manufactured by Kemiichi Co., Ltd.)

[0064] The coating compositions of Examples 1 to 15 and Comparative Examples 1 to 13 in which the above components (a) and (e) were blended as shown in Table 1 were prepared.

s (¾、N-":ヽ- - [0065] [Table 1]

s (¾, N- ": ヽ--

[0066] Example 1 is a standard blend composition of the present invention, which is excellent in bending resistance, crack resistance, weather resistance and stain resistance intended by the present invention, and has a coating operation such as adhesion and drying properties. It can be seen that the paint composition has excellent properties.

 In Example 3, an epoxy group-containing methoxy group-containing silicone oligomer is added to the component (a) in the formulation of Example 1, and an amino group-containing silane compound is a compound having two primary and secondary amino groups. However, the coating film performance and coating suitability are also good. The degree of freedom in designing the coating composition is large. Appropriate raw materials can be selected according to the intended use.

[0067] Example 2 is an example of a coating composition in which a 1,2-secondary amino group-containing silane compound and a tertiary-amino group-containing silane compound are used in combination, and the same results as in Example 1 were obtained. . Examples In Comparative Example 3 in which the component (d) of 2 was replaced with a tertiary amino group-containing silane compound, due to its low reactivity, the coating film properties and coating suitability were insufficient. The ability to use a tertiary amino group-containing silane compound when used in combination with a 1,2-second amino group-containing silane compound is preferable because of the large degree of freedom in designing the paint composition.

 [0068] Example 4 shows the physical properties of the coating film and the coating suitability when the coating composition is performed based on the composition of Example 1. In any case, the performance obtained in Example 1 can be secured.

 Example 5 assumes that it is necessary to adjust the viscosity and viscosity of the coating composition of the present invention depending on the condition of the object to be coated. This is an example of blending high solids containing petroleum hydrocarbon organic solvent. Also in this case, the physical properties of the coating film and the coating suitability are suitably secured.

 [0069] Comparative Example 1 is (a) the limiting condition of the component, which is outside the limit of Si atom 12% or more. There are coating defects that appear to be insufficient bonding.

 In Comparative Example 2, when (d) component of (b) component has a large excess (2 equivalents or more of amine to 1 equivalent of epoxy), coating performance and coating suitability, which are thought to be due to unreacted free amine, are reduced. The

 [0070] As described above, the object of the present invention, which is excellent in bending resistance and crack resistance, and excellent in drying properties after coating, can be made solvent-free and high solids. It has become possible to provide a two-component room temperature curable organopolysiloxane coating composition.

Claims

The scope of the claims  [1] (a) Organosilane-containing organosilane compound having a Si content of 12% by mass or more  (b) Compound containing two or more glycidyl groups in one molecule  (c) Curing catalyst  (d) Alkoxy group-containing organosilane compound having l- or secondary amino group  A coating composition containing as an essential component.  [2] In addition to the component (a), the component (b), the component (c) and the component (d), (e) a color pigment, an extender pigment, a decoloring agent, a pigment dispersant, an antifoaming agent, and a leveling agent 2. The coating composition according to claim 1, further comprising at least one additive selected from a UV absorber, a plasticizer, a fungicide, an algae and other coating additives.  [3] The coating composition according to claim 1 or 2, wherein the component (a) is a silane compound represented by the following general formula (1) or a condensate thereof.  [Chemical 1] R ³  I R ² — S i — OR ¹ (1) Wherein R ¹ is a hydrogen atom or an alkyl group, and R ² , R ³ and R ⁴ are each independently a hydrogen atom, OR ¹ , an alkyl group or an aryl group.  The component (b) is  (i) a compound obtained by glycidyl etherification of a hydroxyl group-containing compound, (ii) Cyclooxylan type compound, glycidyl ester type compound, epoxidized type compound of aliphatic unsaturated compound, polyvalent carboxylic acid ester type compound, bisphenol A type compound, hydrogenated bisphenol A type compound and novolak type compound A compound selected from: and (iii) Compound strength obtained by grafting a glycidyl group-containing component to an acrylic polymer.  The coating composition according to any one of claims 1 to 3, which is at least one compound selected from the group force of force. [5] The component (b) has a mass average molecular weight of 200 or more and less than 100,000, and the content of the component (b), the component (c) and the component (d) is 100 parts by mass of the component (a). The component (b) is 30 to 200 parts by mass, the component (c) is 0.1 to 30 parts by mass, and the component (d) is 10 to 150 parts by mass. V, slip or paint composition according to item 1. [6] The coating composition according to any one of claims 2 to 5, wherein the component (e) is contained in an amount of 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (a). [7] The coating composition according to any one of claims 1 to 6, further comprising an organic solvent. 8. The coating composition according to claim 7, wherein the organic solvent is a petroleum hydrocarbon solvent. [9] Among the components (a) and (d), the component having a glycidyl group that reacts with the component (d) is the first component. The coating composition according to any one of claims 1 to 8, wherein the coating composition is a two-component composition that is blended in one liquid and the component (d) is blended in a second liquid. [10] Among the components (a) and (d), the component having a glycidyl group that reacts with the component (d) is the first component. The component (d) is blended in the second liquid, the component (b), the component (c), and the component (e) are selected from the first liquid and the second liquid. 10. The coating composition according to claim 9, which is blended in one or both of the above.