JP2003238895A - Coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-part, cold-setting organopolysiloxane coating composition showing an excellent elasticity and crack resistance. <P>SOLUTION: The organopolysiloxane coating composition contains (a) an alkoxy group-containing organosilane compound having a Si content of ≥15 wt.%, (b) an acrylic copolymer having a functional group which is reactive with a glycidyl group, (c) a curing catalyst, (d) a glycidyl group-containing organosiloxane and (e) an Si atom-free, glycidyl group-containing compound having an epoxy equivalent of 100-1,500 and a weight average molecular weight of ≥200 and ≤100,000. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition, and more particularly to a room temperature curable two-pack type organopolysiloxane coating composition having excellent flex resistance and crack resistance.

[0002]

2. Description of the Related Art Organopolysiloxane paints have hitherto been used as paint compositions having excellent weather resistance and stain resistance. These performances of the organopolysiloxane-based paint are due to siloxane bonds formed three-dimensionally, but on the other hand, they have problems of brittleness of the coating film and poor adhesion to the base material. Moreover, sufficient performance is not obtained with respect to alkali resistance of the coating film. Therefore, in order to improve these performances, it has been attempted to introduce an organic resin such as an alkyd resin, a polyester resin, an acrylic resin, or an epoxy resin into the paint.

For example, JP-A-2000-63612 discloses (A) an organic composition containing an acrylic resin component having a functional group reactive with an epoxy group, a curing catalyst component made of an organometallic compound, and a color pigment. And (B) an silane compound having an epoxy group or an oligomer composition thereof and an inorganic composition containing a silicone resin component,
A two-pack type coating composition has been proposed. And this 2
It is disclosed that a coating film excellent in weather resistance and adhesion to an old coating film can be obtained by using a liquid coating composition. It is also described that this coating composition has good storage stability.

[0004]

However, it has been found that the conventional organopolysiloxane paints are not sufficient in crack resistance and flex resistance when formed into a coating film. In particular, in the field of construction and civil engineering structures, there are many highly flexible members, and there is a strong demand for an inorganic low-pollution high-weathering coating material having excellent bending resistance and crack resistance. In recent years, even in detached houses,
Mainly for ceramic and metal siding materials, it is required to maintain coating film performance for a long period such as 10 or 20 years.

Therefore, in order to improve the bending resistance and crack resistance of the resulting coating film, studies have been made to increase the amount of the organic resin introduced into the organopolysiloxane coating composition. By increasing the amount of organic resin, it is possible to improve the bending resistance and crack resistance of the coating film, but on the other hand,
It was found that the weather resistance and stain resistance, which are the characteristics of the organopolysiloxane coating, deteriorate.

As described above, in the conventional organopolysiloxane-based paint, the weather resistance / contamination resistance and the flex resistance / crack resistance are not achieved at the same time. There is a demand for an organopolysiloxane-based coating composition which is excellent in flex resistance and crack resistance without impairing the resistance to cracking.

The present invention has been made based on such a demand, and an object of the present invention is to provide a two-part room temperature curing type organopolysiloxane coating composition having excellent flex resistance and crack resistance. To provide.

[0008]

That is, the present invention is
(A) an alkoxy group-containing organosilane compound having a Si content of 15% by weight or more, (b) an acrylic copolymer having a functional group capable of reacting with a glycidyl group, (c) a curing catalyst,
(D) a glycidyl group-containing organosiloxane, and (e) an epoxy equivalent of 100 to 1500 and a weight average molecular weight of 200 or more and 100,000 or less, S
An organopolysiloxane coating composition containing a glycidyl group-containing compound containing no i atom.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The two-part room temperature curing type organopolysiloxane-based coating composition of the present invention has the above-mentioned (a) to (a).
Although it contains the component (e) as an essential component, it is prepared by mixing two liquids consisting of a first liquid and a second liquid in use. First, each component used in the coating composition of the present invention will be described below.

<Component (a)> The alkoxy group-containing organosilane compound used as the component (a) has a lower limit of Si content of 15% by weight, preferably 20% by weight, from the viewpoint of weather resistance and stain resistance of the coating composition. %. On the other hand, the upper limit of the Si content is not particularly limited, but is generally 40% by weight, preferably 35% by weight.

Here, the Si content of the component (a) can be determined by a thermal decomposition method which is a standard of the Highway Public Corporation. Specifically, about 1 g of component (a) (solid content) is precisely weighed in a Teflon (registered trademark) pressure resistant container, and 2-3 ml of concentrated sulfuric acid is added. Then, it is heated to 150 to 160 ° C. and left for 24 hours to decompose the alkoxy group-containing organosilane compound.
The obtained sulfuric acid solution is transferred to a platinum dish previously weighed (weight) and slowly heated to 700 to 800 ° C. in the atmosphere to completely decompose the alkoxy group-containing organosilane compound. After cooling, the weight is measured, and the amount of silica (SiO ₂ ) (% by weight) is first determined from the residue by the following formula.

Then, the Si content (% by weight) is calculated from the calculated amount of silica (SiO ₂ ) (% by weight) by the following equation.

In the present invention, the alkoxy group-containing organosilane compound has the following general formula (1): (In the formula, 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 ,
It is preferably a silane compound having an alkyl group or an aryl group) or a condensate thereof. In the case of a condensate, the degree of condensation is generally in the range of 2 to 100, and from the viewpoint of compatibility, a liquid having a degree of condensation of 2 to 15 is preferable. In the present invention,
The alkoxy group-containing organosilane compound as the component (a) may be used alone or in combination of two or more.

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

Specific examples of preferable alkoxy group-containing organosilane compounds include DC3074, DC3037,
SR2402 (Toray Dow Corning Silicone Co., Ltd. product), KR9218, KR500, KR40
0, X40-9225, KR-510, X40-922
7, X40-9247 (above, Shin-Etsu Chemical Co., Ltd. product) etc. can be illustrated.

<Component (b)> The acrylic copolymer used as the component (b) is required to have a functional group capable of reacting with a glycidyl group. Examples of such a functional group include a carboxyl group, a primary amino group, a secondary amino group, a tertiary amino group, a mercapto group and a hydroxyl group. From the viewpoint of reactivity, an amino group is preferable,
Particularly, a tertiary amino group is preferable.

The acrylic copolymer has a weight average molecular weight (converted to standard polystyrene) of 3,000 to 100,
It is preferably 000, more preferably 5,000
It is 0 to 50,000.

The amount of the functional group capable of reacting with the glycidyl group in the component (b) is preferably 0.01 to 2 equivalents relative to 1 equivalent of the glycidyl group in the components (d) and (e). , And more preferably 0.1 to 1.2 equivalents. Specifically, an acrylic copolymer containing a tertiary amino group having an amine equivalent in the range of 300 to 10,000 can be mentioned.

The monomer composition constituting the component (b) is not particularly limited as long as it has a functional group capable of reacting with the glycidyl group, but the Tg of the component (b) is -10 to 30 ° C. It is preferable to use a different monomer composition. Tg is -1
The component (b) in the range of 0 to 30 ° C. includes, for example, an ethylenically unsaturated monomer (b1), and this monomer (b1).
Obtained by copolymerizing a functional group (preferably amino group) -containing ethylenically unsaturated monomer (b2) copolymerizable with 1) with a radical polymerization initiator in a solvent. You can

Here, the ethylenically unsaturated monomer (b
1) includes (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate. , C-C24 alkyl or cycloalkyl esters of (meth) acrylic acid such as, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate. C3 to C8 hydroxyalkyl ester of (meth) acrylic acid such as hydroxypropyl (meth) acrylate, styrene, vinyltoluene,
Basic aromatic unsaturated monomers such as α-methylstyrene, N-vinylpyrrolidone and vinylpyridine, alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, vinyl acetate, maleic acid, itaconic acid, crotonic acid And so on. In addition,
The above-mentioned monomers (b1) may be used in combination of two or more kinds.

The ethylenically unsaturated monomer (b1)
As the above, it is also possible to use a hydroxyl group-containing ethylenically unsaturated monomer. Specifically, polyoxyalkylene glycol (meth) acrylates (wherein the alkylene group has 2 carbon atoms, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, and diethylene glycol (meth) acrylate). 4 to 4, and the number of moles of alkylene oxide added is 1 to 50), and caprolactone-modified hydroxy (meth) acrylate (Daicel Chemical Co., Ltd.).
Manufactured, trade name: Praxel FM, FA), N-methylol acrylamide and the like.

An ethylenically unsaturated monomer (b) containing a functional group (preferably an amino group) capable of reacting with a glycidyl group.
2) is a monomer copolymerizable with the above-mentioned monomer (b1), and specifically, amino group-containing (meth) acrylic acid ester such as dimethylaminoethyl (meth) acrylate, acrylamide, diacetone acrylamide,
N, N-dimethylaminopropyl acrylamide, N,
Examples thereof include amino group-containing (meth) acrylamides such as N-dimethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N, N-diethylacrylamide and diethylaminopropylacrylamide. Among these, dimethylaminoethyl methacrylate is preferable from the viewpoint of reactivity. In addition, these monomers can also be used in combination of 2 or more types.

The solvent used for the polymerization is not particularly limited as long as it can be solution polymerized and can dissolve the monomer used and the polymer obtained. Specific examples include toluene, xylene, methyl ethyl ketone, ethyl acetate, acetone, isopropyl alcohol, and mineral spirits. Also, it is acceptable to use two or more of these in combination.

When a petroleum hydrocarbon solvent such as mineral spirit is used as the solvent, the monomer is a vinyl monomer having a side chain alkyl having 4 to 8 carbon atoms, especially n-butyl methacrylate, i-butyl. Those containing methacrylate, t-butyl methacrylate or cyclohexyl (meth) acrylate are preferred.

The polymerization initiator is not particularly limited as long as it is radically decomposed by heat or a reducing substance to cause addition polymerization to the monomer. For example,
Azobisisobutyronitrile, benzoyl peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide and the like can be used alone or in combination of several kinds. . It is also possible to add a chain transfer agent such as octyl mercaptan or dodecyl mercaptan in order to control the molecular weight of the resin.

The specific method for polymerizing the component (b) is as follows. A functional group (preferably an amino group) capable of reacting with the ethylenically unsaturated monomer (b1) and a glycidyl group in the presence of a radical polymerization initiator in a solvent. ) A monomer dropping method in which a mixture of the contained ethylenically unsaturated monomer (b2) is dropped; a one-bath polymerization method (monomer etc.) in which radical polymerization of a mixture of a solvent, a radical polymerization initiator, and the monomers (b1) and (b2) is performed. And a method of polymerizing the same. From the viewpoint of safety and control of molecular weight, the monomer dropping method is preferable.

As the component (b) of the present invention, specifically,
A copolymer composed of methyl methacrylate, n-butyl acrylate, n-butyl methacrylate and dimethylaminoethyl methacrylate, or cyclohexyl methacrylate, n-butyl acrylate, n-butyl methacrylate and dimethylamino methacrylate. Examples thereof include a copolymer composed of ethyl.

<Component (c)> The curing catalyst used as the component (c) is preferably an organometallic compound, specifically, a metal alkoxide compound such as Ti, Al, Zr or Sn, a metal chelate compound, Metal ester compounds can be 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 alkoxides such as aluminum 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,
Titanium alkoxides such as tetra-n-hexyl titanate, tetraisooctyl titanate, 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- Zirconium alkoxides such as octyl zirconate and tetra-n-stearyl zirconate;
Examples thereof include dibutyltin dibutoxide, and examples of the metal chelate compound include tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, and tris (n-butylacetoacetate). Aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (proponylacetonato) aluminum, diisopropoxypropionylacetonato aluminum, acetylacetonato bis (propionylacetonato) aluminum, mono Ethyl acetoacetate bis (acetylacetonato) aluminum, acetylacetonato aluminum di-sec-butyrate, methylacetoacetate Te 10-sec- butyrate,
Di (methylacetoacetate) aluminum mono-te
Aluminum chelate compounds such as rt-butyrate, diisopropoxyethylacetoacetate aluminum, monoacetylacetona bis (ethylacetoacetate) aluminum; diisopropoxy bis (ethylacetoacetate) titanate, diisopropoxy bis (acetylacetoacetate Titanium chelate compounds such as nato) titanate and di-n-butoxy bis (acetylacetonato) titanate; tetrakis (acetylacetonato) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium Zirconium chelate compound; dibutyltin bis (acetylacetonate) and the like,
Examples of the metal ester compound include dibutyltin diacetate, dibutyltin di (2-ethylhexylate),
Examples thereof include tin ester compounds such as dibenzyltin di (2-ethylhexylate), dibutyltin dilaurate and dibutyltin diisooctyl maleate. These reaction catalysts can be used alone or in combination of two or more.

When the curing catalyst causes problems in the pot life and storage stability of the coating material, it is preferable to use a keto / enol type tautomeric compound in combination. Keto
Examples of enol-type tautomeric compounds include acetylacetone, acetoacetic acid ethyl ester, malonic acid diester,
Examples thereof include benzoylacetone, dibendiylmethane, diacetone alcohol, methyl salicylate and the like.

<Component (d)> The glycidyl group-containing organosiloxane used as component (d) is not particularly limited, and specifically, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β
-Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl (methyl) dimethoxysilane , Γ-glycidoxypropyl (dimethyl) methoxysilane, γ-glycidoxypropyl (ethyl) dimethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypolysiloxane and the like can be mentioned. Among these, from the viewpoint of compatibility and reactivity,
γ-glycidoxypropyltrimethoxysilane is preferred.

Further, in the present invention, as the component (d), γ- (meth) acryloxypropylmethoxysilane, a glycidyl group-containing unsaturated monomer such as glycidyl (meth) acrylate, and a hydrolyzable silyl group-containing unsaturated monomer. It is also possible to use a copolymer with a saturated monomer.

<Component (e)> The glycidyl group-containing compound used as component (e) has an epoxy equivalent of 100 to 15.
00, preferably 150-1000,
It is more preferably 200 to 500. If the epoxy equivalent is out of the above range, the resulting coating composition may not have sufficient flex resistance and adhesion.

Here, the epoxy equivalent can be determined by the following method. First, the epoxy compound is 0.2
About 1g is precisely weighed and 90ml of methyl ethyl ketone at room temperature
Dissolve into a sample solution. About 10 m of glacial acetic acid
1, CTAB (cetyltrimethylammonium bromide) 1.0 g, CV (crystal violet) solution (indicator) 10 to 15 drops, and titrated with 0.1N perchloric acid standard solution until a blue-green color appears. To do. The end point is the point where blue-green color lasts for 1 minute. A blank test is conducted in the same manner, and the epoxy equivalent (WPE) of the glycidyl group-containing compound is calculated by the following formula. W: Weight of sample (g) Vs: Amount of 0.1N perchloric acid standard solution used (dripping amount) ml Vb: Amount of used perchloric acid standard solution in blank test (dripping amount) N number N: excess Normality of chloric acid solution

Further, the glycidyl group-containing compound as the component (e) is 200 or more and 10 or more from the viewpoint of compatibility with other components (particularly the components (a) and (b)) in the coating composition.
It preferably has a weight average molecular weight of 50,000 or less. Further, from the viewpoint of giving flexibility to the obtained coating film and improving bending resistance and adhesion, it is preferable to use the ones shown in the following (i) to (iii).

(I) Compound obtained by converting a hydroxyl group-containing compound into a glycidyl ether Here, as the hydroxy group-containing compound, (a) monohydric alcohols such as methanol, ethanol, propyl alcohol and higher alcohols, ethylene glycol, propylene Glycol, alkylene glycol such as neopentyl glycol, polyethylene glycol, polypropylene glycol, polyalkylene glycol such as polytetramethylene ether glycol, polyhydric alcohol such as glycerin and sorbitol; (b) succinic acid, adipic acid, sebacic acid, azelaic acid , Terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, 1,4-sic Hexane dicarboxylic acid, polycarboxylic acids such as trimellitic acid,
One or more acid esters or acid anhydrides, and 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, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, pentaerythritol, etc. 1 of low molecular weight polyols
Polyester polyol obtained by dehydration condensation with more than one kind; (c) ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and γ-valerolactone using low molecular weight polyol, low molecular weight polyamine and low molecular weight amino alcohol as an initiator. The obtained lactone polyester polyol;
(D) Low molecular weight polyol, diethylene carbonate,
Examples thereof include polycarbonate polyols obtained by dealcoholation reaction with dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like, dephenolation reaction and the like.

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

(Ii) Cyclic oxirane type, glycidyl ester type, epoxidized type of aliphatic unsaturated compound, polycarboxylic acid ester type, bisphenol A type or novolak type compound Examples of such compounds include the following general formulas. As shown in.

[0038]

(Iii) A compound obtained by grafting a glycidyl group-containing component onto an acrylic polymer. Specific examples of such a compound include copolymers of a glycidyl group-containing unsaturated monomer and another ethylenically unsaturated monomer. Here, as the glycidyl group-containing unsaturated monomer, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4
-Epoxy cyclohexyl propyl (meth) acrylate etc. are mentioned. Among these, glycidyl methacrylate is preferable from the viewpoint of reactivity. Further, from the viewpoint of flex resistance and crack resistance, a monomer composition in which the Tg of the acrylic polymer grafted with the glycidyl group-containing component is in the range of -50 to 10 ° C and the epoxy equivalent is 500 to 1500. Is preferred. For example, glycidyl methacrylate, 2-ethylhexyl acrylate,
A copolymer composed of n-butyl methacrylate and n-butyl acrylate can be used.

<Component (f)> The coating composition of the present invention comprises, in addition to the above-mentioned essential components (a) to (e),
As the component (f), a color pigment, an extender pigment and an organic solvent may be appropriately contained.

The color pigments include inorganic pigments such as titanium oxide, zinc oxide, carbon black, ferric oxide (red iron oxide), yellow lead, yellow iron oxide, ocher, ultramarine blue, cobalt green, azo pigments, naphthol pigments, Pyrazolone,
Anthraquinone type, perylene type, quinacridone type, disazo type, isoindolinone type, benzimidazole type,
Examples include organic pigments such as phthalocyanine type and quinophthalone type.

Extending pigments include heavy calcium carbonate,
Examples thereof include clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon and diatomaceous earth.

Examples of the organic solvent include aromatic solvents such as toluene, xylene and ethylbenzene, ester solvents such as ethyl acetate, butyl acetate, propylene glycol methyl ether acetate and propylene glycol methyl ether propionate, acetone and methyl ethyl ketone. , Methyl isobutyl ketone, ketone solvents such as cyclohexanone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, methyl alcohol, ethyl Alcohol-based solvents such as alcohol, propyl alcohol and butyl alcohol, petroleum hydrocarbon-based solvents such as mineral spirits Etc. can be used. Among these, petroleum hydrocarbon solvents such as mineral spirit are particularly preferable because they do not easily attack the old coating film and the base material and have a low odor, which greatly contributes to the improvement of the working environment.

Further, the coating composition of the present invention contains a plasticizer, an antiseptic agent, an antifungal agent, within a range not impairing the object of the present invention.
Additives for paints such as an anti-algae agent, an antifoaming agent, a leveling agent, a pigment dispersant, an anti-settling agent, an anti-sagging agent, a matting agent, an ultraviolet absorber and a titanium oxide photocatalyst can be appropriately added.

Subsequently, in the coating composition of the present invention,
The blending amount of each component will be described.

First, the essential components (b) and (c)
The component and the component (d) are 30 to 130 parts by weight (solid content) and 0.1 to 100 parts by weight of the component (a), respectively.
-30 parts by weight, preferably 1-50 parts by weight.
Here, if the amount of the component (b) is small, the alkali resistance of the coating film is insufficient, and if it is too large, the weather resistance of the coating film is deteriorated. Further, if the amount of the component (d) is small, the adhesion of the coating film is deteriorated, while if used in a large amount, the flexibility of the coating film is reduced and the flex resistance is adversely affected. When the amount of the component (c) is less than 0.1 parts by weight, it cannot function sufficiently as a curing catalyst, and even when it is used in an amount of more than 30 parts by weight, the coating film performance is not improved. It is not preferable from an economic point of view. From the viewpoint of the balance of weather resistance, stain resistance, flex resistance, crack resistance and alkali resistance,
The blending amounts of the component (b), the component (c) and the component (d) are
50 to 10 parts by weight per 100 parts by weight of component (a).
It is particularly preferable that the amount is 0 parts by weight (solid content), 5 to 15 parts by weight, and 5 to 30 parts by weight.

Similarly, regarding the component (e) which is an essential component, the preferable blending amount varies depending on the molecular weight.
That is, the weight average molecular weight of the component (e) is 200 or more,
When it is less than 5,000, it is preferably 5 to 30 parts by weight (solid content) with respect to 100 parts by weight of the component (a).
On the other hand, the weight average molecular weight of the component (e) is 5,000 or more, 1
When it is at most 0,000, it is preferably 10 to 60 parts by weight (solid content), and more preferably 25 to 45 parts by weight (solid content) with respect to 100 parts by weight of the component (a). If the amount of component (e) is small, the flexibility of the coating film tends to decrease, and if it is large, the stain resistance of the coating film may deteriorate.

Next, regarding the optional component (f), these components may be blended in a range that does not impair the object of the present invention depending on various applications. The amount of the organic solvent is 20 to 2 with respect to 100 parts by weight of the coating solid content.
It is preferably set to 00 parts by weight.

As described above, the coating composition of the present invention comprises the first liquid and the second liquid, and the two liquids are mixed at the time of use. In the coating composition of the present invention, the first liquid and the second liquid are prepared from the viewpoint of storage stability so that the component (b) and the components (d) and (e) are mixed immediately before use. Is desirable. That is, each component contained in the two-pack type coating composition of the present invention is preferably prepared as follows. The component (f), which is an optional component, is
It can be present in either the liquid or the second liquid, or in both the first and second liquids.

[0050] (A) component: present in the first liquid and / or the second liquid, (B) component: present in the first liquid, (C) component: present in the first liquid and / or the second liquid, (D) component: present in the second liquid, Component (e): Present in the second liquid.

In the two-pack type coating composition of the present invention, from the viewpoint of improving the storage stability of the coating and flexibly responding to the use environment and use of the coating,
It is particularly preferable to prepare the component (e) as follows.

(A) component: present in the first and second liquids, (b) component: present in the first liquid, (c) component: present in the first liquid, (d) component: present in the second liquid , (E) component: present in the second liquid. As the component (f), it is more preferable that the first liquid contains a color pigment and an organic solvent, and the second liquid contains an organic solvent.

(A) component: present in second liquid, (b) component: present in first liquid, (c) component: present in first liquid, (d) component: present in second liquid, (e) Ingredient: Present in the second liquid. As the component (f), (1) a color pigment and an organic solvent are present in the first liquid, and an organic solvent is present in the second liquid, or
(2) It is more preferable that the first liquid contains an organic solvent, and the second liquid contains a color pigment and an organic solvent.

(A) component: present in first liquid, (b) component: present in first liquid, (c) component: present in first liquid, (d) component: present in second liquid, (e) Ingredient: Present in the second liquid. As the component (f), it is more preferable that the first liquid contains a color pigment and an organic solvent, and the second liquid contains an organic solvent.

(A) component: present in first liquid, (b) component: present in second liquid, (c) component: present in first liquid, (d) component: present in first liquid, (e) Ingredient: Present in the first liquid. As the component (f), it is more preferable that the first liquid contains a color pigment and an organic solvent, and the second liquid contains an organic solvent.

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 at the time of use. The mixing ratio of the first liquid and the second liquid is not particularly limited. The pot life of the paint is preferably 3 to 8 hours.

Since the coating composition of the present invention is cured at room temperature and has low pollution and weather resistance, it can be used in machines, ships, vehicles, aircraft,
It is preferably used in civil engineering, construction, heavy corrosion protection, ink, and other general industrial fields. In particular, when the coating composition of the present invention is used, it is possible to obtain a coating film having excellent flex resistance and crack resistance, and therefore for many construction and civil engineering structures that have many flexible members. Suitable for the above materials. Further, the coating composition of the present invention can be suitably used for a ceramic siding material and a metal siding material of a detached house, which is required to maintain the coating performance for a long period of 10 to 20 years.

[0058]

As described above, in the coating composition of the present invention, by combining the five specific components (a) to (e), the weather resistance and stain resistance of the original organopolysiloxane coating are improved. It is possible to obtain an organopolysiloxane-based coating composition excellent in bending resistance and crack resistance without impairing the properties. In addition, the component (a)
By adjusting the compounding amount of the component (e) to a specific amount, it is possible to obtain a coating composition having excellent performance in all of weather resistance, stain resistance, flex resistance, crack resistance and alkali resistance. Become.

Furthermore, when a petroleum hydrocarbon solvent is added as the component (f) to the coating composition of the present invention, the coating composition does not easily attack the old coating film or the base material. It can be easily performed. In addition, since the paint containing a petroleum hydrocarbon solvent has a low odor, it is possible to greatly improve the working environment.

[0060]

The present invention will be described in more detail below, but the present invention is not limited to these examples. First, the methods for evaluating the physical properties of coating compositions used in Examples and Comparative Examples will be described. In the following, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

<Bending Resistance> The bending resistance is evaluated according to JIS.
According to the method of K5400 8.1, the diameter of the mandrel is 10
The thing of mm was used. Also, as a test piece, 150
The coating composition was spray coated onto a steel plate of × 50 × 0.3 mm so that the dry coating film thickness would be 50 μm, and the temperature was maintained at 23 ° C. for 5 minutes.
After being aged for 4 days under the condition of 0% RH, it was subjected to forced drying at 80 ° C. for 3 days. In the evaluation, the bent portion of the coating film was visually observed, and the test piece without cracking or peeling was rated as "O", and the others were rated as "X".

<Crack resistance> The crack resistance is JIS
According to K5400 9.4 (wet cold / heat repeatability test), water was immersed in water at 20 ° C for 18 hours, and then heated in a freezer at -20 ° C for 3 hours and further at 50 ° C for 3 hours. This cycle was repeated 10 times, the state of the coating film after the test was visually observed, and the degree of cracking, swelling and whitening in the coating film was evaluated according to the following 3 grades. The test piece is 70 × 7.
Dry coating thickness is 50μ on 0x6mm flexible board
spray paint composition to reach m.
After curing for 4 days at ℃ and 50% RH, 80 ℃
It was prepared by carrying out forced drying for 3 days. ◯: No change is seen in the coating film. Δ: Cracks and swelling are observed in part of the coating film. X: Significant cracks and swelling are observed in the coating film.

<Accelerated weather resistance> The accelerated weather resistance test was carried out using a super accelerated weather resistance tester (Isuper UV tester manufactured by Iwasaki Electric Co., Ltd.). Moreover, the test piece is 50 × 50 × 4.
mm of flexible board is spray coated with the coating composition so that the dry coating thickness is 50 μm, and the temperature is 50 ° C. at 23 ° C.
It was prepared by performing drying for 7 days under the condition of% RH. The test conditions include a wavelength of 295 to 450 nm, an ultraviolet irradiation degree of 100 mW / cm ² , and a black panel temperature of 63.
C., 50% RH, 1 cycle was 4 hours for irradiation and 4 hours for condensation, and 125 cycles (1000 hours) were tested. After the test was completed, the gloss retention rate with respect to the initial 60-degree specular gloss value of the coating film was obtained and evaluated in the following three grades. ◯: Gloss retention rate 70% or more B: Gloss retention rate 50% or more and less than 70% ×: Gloss retention rate less than 50%

<Alkali resistance> For the alkali resistance test, see J.
According to IS K5400 8.21, sodium hydroxide was adjusted to 5 W / V% with deionized water, and two test pieces were used.
It was dipped for 7 days under the condition of 3 ° C. After the immersion, the test piece was gently washed with running water and dried for 2 hours to swell the coating film.
Cracking, peeling, and change in gloss were visually observed and evaluated in three levels. In addition, as a test piece, 150 × 70 ×
A 4 mm flexible board was spray-coated so that the dry coating film thickness was 50 μm, and dried for 14 days at 23 ° C. and 50% RH. ◯: No significant change compared with the current test piece. Δ: There is a slight luster compared to the current test piece. X: Significant luster, cracking, and peeling are present as compared with the current test piece.

<Adhesion> The adhesion test is conducted according to JIS K54.
00 8.5.2 According to the cross-cut tape method, the gap distance is 2m
Using a cutter guide of m, make a cut in a grid pattern (25 squares; vertical 5 divisions × horizontal 5 divisions), stick cellophane adhesive tape on this grid and hold one end of the tape at a right angle to the coated surface. The film was peeled off instantaneously in the direction, and the peeled area of the coating film was measured. In addition, as a test piece, 15
A paint composition is sprayed onto a 0 × 70 × 4 mm flexible board so that the dry coating film thickness is 50 μm.
The one dried for 14 days under the conditions of 23 ° C. and 50% RH was used. From the peeled area of the coating film to the total area of the coating film, the adhesion was evaluated as follows. ◯: When the peeled area of the coating film is less than 5% of the total area Δ: When the peeled area of the coating film is 5% or more and less than 35% of the total area ×: When the peeled area of the coating film is of the total area If more than 35%

<Forced Contamination> The coating composition was sprayed onto a 150 × 70 × 0.8 mm aluminum plate so that the dry coating film thickness was 50 μm, and dried under conditions of 23 ° C. and 50% RH for 14 days. Then, a test piece was prepared. Hidden carbon suspension water (dispersion liquid in which 5 parts of carbon black Color Black FW200 manufactured by Degussa Hurus and 95 parts of deionized water and glass beads were added and dispersed for 2 hours with a paint shaker) was air-sprayed on the obtained test piece. And was immediately dried at 60 ° C. for 1 hour.
After drying, the sample was allowed to cool to room temperature, and the surface of the test piece was washed under running water using gauze until the dirt substance could not be removed. After washing, it was dried at room temperature for 3 hours, and the degree of stain was measured with a color difference meter, and the difference in lightness of the coating film before and after the test (ΔL
*) Was obtained and evaluated in the following three stages. The smaller the difference in brightness, the better the stain resistance. Brightness difference (ΔL *) = [Coating film brightness after test (L * 1) -Coating film brightness before test (L * 0)] ○: Brightness difference −5 or more Δ: Brightness difference −10 or more and less than −5 × : Brightness difference less than -10

<Comprehensive Evaluation> Based on the results of the performance measurement of the coating composition shown above, the comprehensive evaluation of the coating composition was performed according to the following criteria. ◯: All are evaluated as ◯, which is a level that can be used very suitably as a coating composition. Δ: There is an evaluation of Δ, which is a level that can be used as a coating composition, but its use may be limited. X: There is an evaluation of x, which is a level that is difficult to use as a coating composition.

Next, the components to be added to the coating composition will be described. <Component (a)> (a-1) Methylphenyl-based alkoxysilane oligomer (trade name: DC3074, Toray Dow Corning
Made by Silicone, active ingredient 100%, Si atom about 25%
(A-2) Methyl-based alkoxysilane oligomer (S
R2402, manufactured by Toray Dow Corning Silicone,
(100% active ingredient, about 30% Si atom)

<Component (b)> (b-1) 400 parts of toluene was charged into a reactor equipped with a stirrer, a thermometer, a cooling pipe, a nitrogen gas introducing pipe, and a dropping device, and the temperature was raised to 110 ° C. with stirring. Warmed. 200 parts of methyl methacrylate, 130 parts of n-butyl acrylate, 120 parts of n-butyl methacrylate,
A mixture of 50 parts of dimethylaminoethyl methacrylate, 5 parts of azobisisobutyronitrile and 10 parts of toluene was added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Furthermore, a mixture of 2.5 parts of azobisisobutyronitrile and 90 parts of toluene was added dropwise over 1 hour. After completion of the dropping, react at the same temperature for 3 hours,
Nonvolatile content (solid content) 50%, viscosity 1000 mPa · s
(25 ° C), weight average molecular weight 20000, amine equivalent 3
100 transparent acrylic resin solutions containing a tertiary amine (b-1) were obtained.

(B-2) 300 parts of petroleum hydrocarbon solvent (trade name: LAWS, manufactured by Shell Japan Co., Ltd.) in a reactor equipped with a stirrer, a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a dropping device. , And petroleum hydrocarbon solvent (trade name: HAWS, manufactured by Shell Japan Co., Ltd.) were charged, and the temperature was raised to 110 ° C. with stirring. there,
50 parts of n-butyl acrylate, 200 parts of n-butyl methacrylate, 200 parts of cyclohexyl methacrylate
Part, 50 parts of dimethylaminoethyl methacrylate, 5 parts of azobisisobutyronitrile, and 10 parts of LAWS were added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Furthermore, a mixture of 2.5 parts of azobisisobutyronitrile and 90 parts of LAWS was added dropwise over 1 hour. After completion of the dropping, the mixture is reacted at the same temperature for 3 hours to give a nonvolatile content (solid content) of 50% and a viscosity of 1000 mPa.
A transparent tertiary amino group-containing acrylic resin solution (b-2) having s (25 ° C.), a weight average molecular weight of 15,000 and an amine value equivalent of 3100 was obtained.

<Component (c)> (c-1) Alkyl acetoacetate aluminum diisopropylate (trade name: aluminum chelate M, manufactured by Kawaken Fine Chemical Co., Ltd.)

<Component (d)> (d-1) γ-glycidoxypropyltrimethoxysilane (trade name: SH6040, Toray Dow Corning
(Made by Silicone)

<Component (e)> (e-1) Polypropylene glycol diglycidyl ether (trade name: Epolite 400P, manufactured by Kyoeisha Chemical Co., Ltd.,
Epoxy equivalent 315) (e-2) Polyethylene glycol diglycidyl ether (trade name: Epolite 400E, manufactured by Kyoeisha Chemical Co., Ltd., epoxy equivalent 290) (e-3) Stirrer, thermometer, cooling pipe and nitrogen gas introduction pipe, dropping device 400 parts of toluene was charged into a reactor equipped with and heated to 110 ° C. with stirring. 70 parts of methyl methacrylate, 130 parts of n-butyl acrylate, 150 parts of n-butyl methacrylate, 70 parts of glycidyl methacrylate, 80 parts of 2-ethyl 2-hexyl acrylate, and azobisisobutyronitrile 5
And 10 parts of toluene were added dropwise over 3 hours. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Furthermore, 2.5 parts of azobisisobutyronitrile and 9 parts of toluene
A mixture of 0 parts was added dropwise over 1 hour. After the completion of the dropping, the reaction is carried out at the same temperature for 3 hours, and the nonvolatile content (solid content)
%, A viscosity of 1000 mPa · s (25 ° C.), a weight average molecular weight of 20,000, and an epoxy equivalent of 1000, to obtain a transparent glycidyl-containing acrylic resin solution (e-3).

<Component (f)> (f-1) Butyl acetate (f-2) Petroleum hydrocarbon solvent (trade name: LAWS,
Shell Japan Co., Ltd. (f-3) Titanium oxide (trade name: TIPAQUE C
R-90, made by Ishihara Sangyo)

<Blending of coating composition>

[Example 1] Coating composition example 1 <First liquid> (a-1) 18 parts, (b-1) 30 parts, (f-1) 24
Parts, (f-3) 25 parts, and glass beads 100 parts were placed in a mixing container and dispersed for 1 hour with a paint shaker. After the dispersion is completed, the glass beads are removed, and (c-
1) 3 parts were added and mixed with a stirrer for 3 minutes. The obtained first liquid has a solid content of 60% and a viscosity of 300 mPa · s (2
5 ° C.).

<Second liquid> (e-1) 10 parts, (a-2) 30 parts, (d-1) 15
Parts and (f-1) 45 parts were charged into a mixing vessel and stirred with a stirrer for 3 minutes. The obtained second liquid has a solid content of 55%,
The viscosity was 10 mPa · s (25 ° C).

The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 5/1 to obtain a coating composition.
Physical properties of the obtained coating composition were evaluated by the methods described above. The results are shown in Table 1.

[0078]

Examples 2 to 17 A coating composition was prepared in the same manner as in Example 1 except that the composition of each component and the weight ratio of the first liquid and the second liquid were changed according to Table 1. For, the physical properties were evaluated by the methods described above. The results are shown in Table 1.

[0079]

[Table 1]

Coating Composition Example 2 <First Liquid> 30 parts of (a-1), 10 parts of (a-2), (f-3) 4
1.7 parts, (d-1) 5 parts, (e-1) 3.3 parts, (f
-1) 10 parts and 100 parts of glass beads were placed in a mixing container and dispersed for 1 hour with a paint shaker. After the dispersion was completed, the glass beads were removed. First obtained
The liquid has a solid content of 90% and a viscosity of 500 mPa · s (25 ° C)
Met.

<Second Liquid> (b-1) 50 parts, (c-1) 5 parts, and (f-1) 4
5 parts were placed in a mixing vessel and stirred with a stirrer for 3 minutes. The obtained second liquid has a solid content of 30% and a viscosity of 100 mPas.
-It was s (25 degreeC).

The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 1/1 to obtain a coating composition.
When the physical properties of the obtained coating composition were evaluated by the methods described above, the same physical properties as those of the coating composition of Example 1 were confirmed.

Coating composition example 3 <First liquid> (b-1) 37.5 parts, (f-3) 31.2 parts, (f-
1) 27.5 parts and 100 parts of glass beads were placed in a mixing container and dispersed for 1 hour with a paint shaker.
After the dispersion is completed, the glass beads are removed, and (c-1)
3.8 parts were added and mixed with a stirrer for 3 minutes. The obtained first liquid has a solid content of 54% and a viscosity of 500 mPa · s (2
5 ° C.).

<Second liquid> (a-1) 45 parts, (a-2) 15 parts, (d-1) 7.
5 parts, 5 parts of (e-1), and 27.5 parts of (f-1) were charged into a mixing vessel, and stirred for 3 minutes with a stirrer. The obtained second liquid has a solid content of 72.5% and a viscosity of 50 mPa · s.
(25 ° C).

The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 2/1 to obtain a coating composition.
When the physical properties of the obtained coating composition were evaluated by the methods described above, the same physical properties as those of the coating composition of Example 1 were confirmed.

Coating Composition Example 4 <First Liquid> 18 parts of (a-1), 6 parts of (a-2), 30 of (b-1)
Parts, 18 parts of (f-1), 25 parts of (f-3), and 100 parts of glass beads were charged in a mixing container, and dispersed for 1 hour with a paint shaker. After the dispersion was completed, the glass beads were removed, 3 parts of (c-1) was added, and mixed for 3 minutes with a stirrer. The obtained first liquid has a solid content of 67% and a viscosity of 3
It was 00 mPa · s (25 ° C.).

<Second liquid> (e-1) 10 parts, (d-1) 15 parts, and (f-1)
75 parts were charged into a mixing vessel and stirred with a stirrer for 3 minutes. The obtained second liquid has a solid content of 25% and a viscosity of 10 mPas.
-It was s (25 degreeC).

The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 5/1 to obtain a coating composition.
When the physical properties of the obtained coating composition were evaluated by the methods described above, the same physical properties as those of the coating composition of Example 1 were confirmed.

Coating Composition Example 5 <First Liquid> (a-1) 22.5 parts, (a-2) 7.5 parts, (f-
3) 31.2 parts, (d-1) 3.8 parts, (e-1) 2.
5 parts, (f-1) 28.7 parts, and glass beads 100
Parts were placed in a mixing container and dispersed for 1 hour with a paint shaker. After dispersion, remove the glass beads,
(C-1) 3.8 parts was added and mixed with a stirrer for 3 minutes. The obtained first liquid has a solid content of 71% and a viscosity of 500 mP.
It was a * s (25 degreeC).

<Second Liquid> 75 parts of (b-1) and 25 parts of (f-1) were placed in a mixing vessel and stirred for 3 minutes with a stirrer. The obtained second liquid had a solid content of 38% and a viscosity of 100 mPa · s (25 ° C.).

The above-mentioned first liquid and second liquid were mixed and stirred at a weight ratio of first liquid / second liquid = 2/1 to obtain a coating composition.
When the physical properties of the obtained coating composition were evaluated by the methods described above, the same physical properties as those of the coating composition of Example 1 were confirmed.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroshi Momori             Saitama Prefecture Kita-Katsushika-gun Washimiya-cho Ookami 478 I             Miya housing complex 1-1-102 (72) Inventor Kazuyoshi Nomura             1-11-12 Mutsumicho, Kazo City, Saitama Prefecture (72) Inventor Kentaro Imai             901-8 Kokuki, Kuki-shi, Saitama Etoile             Kuki 305 (72) Nobuyuki Hirama, Inventor             3-2-6 Hanasakikita, Kazo City, Saitama Prefecture (72) Inventor Atsushi Miki             1505-1-B201 Shimoteguna, Takahagi City, Ibaraki Prefecture (72) Inventor Kuniaki Inui             2-24-202 Kasuga Town, Takahagi City, Ibaraki Prefecture (72) Inventor Kyoki Takaichi             8-4--4-404 Kagawa, Chigasaki City, Kanagawa Prefecture F-term (reference) 4J038 BA202 CG141 CG142 CH201                       CH202 DB002 DB032 DB262                       DL031 DL032 DL052 GA03                       GA06 GA09 GA13 JA23 JA69                       JC32 JC34 JC38 JC39 KA04                       KA06 MA14 NA11 PA18

Claims (7)

[Claims] 1. An (a) alkoxy group-containing organosilane compound having a Si content of 15% by weight or more, (b) an acrylic copolymer having a functional group capable of reacting with a glycidyl group,
(C) Curing catalyst, (d) Glycidyl group-containing organosiloxane, and (e) Epoxy equivalent of 100 to 1500, weight average molecular weight of 200 or more and 100,000 or less, Si atom-free glycidyl group-containing An organopolysiloxane-based coating composition containing a compound. 2. The weight average molecular weight of the component (e) is 200 or more and less than 5,000, and the component (b), the component (c),
The amounts of the component (d) and the component (e) are 30 to 130 parts by weight (solid content), 0.1 to 30 parts by weight, 1 to 50 parts by weight, and 100 parts by weight of the component (a), respectively. 5-3
The coating composition according to claim 1, which is 0 part by weight (solid content). 3. The weight average molecular weight of component (e) is 5,000.
0 or more and 100,000 or less, the component (b),
The amounts of the components (c), (d) and (e) are (a)
The amount is 30 to 130 parts by weight (solid content), 0.1 to 30 parts by weight, 1 to 50 parts by weight, and 10 to 60 parts by weight (solid content) with respect to 100 parts by weight of the component, respectively. Coating composition. 4. The coating composition according to claim 1, further comprising an organic solvent. 5. The organic solvent is a petroleum hydrocarbon solvent,
The coating composition according to claim 4. 6. The coating composition is a two-pack type coating composition comprising a first liquid and a second liquid, wherein the component (a) is present in the first liquid and / or the second liquid, and (b). The component is present in the first liquid, the component (c) is present in the first liquid and / or the second liquid,
The coating composition according to claim 1, wherein the components (d) and (e) are present in the second liquid. 7. The coating composition is a two-pack type coating composition comprising a first liquid and a second liquid, wherein the component (a) is present in the first liquid and / or the second liquid, and (b). The component is present in the first liquid, the component (c) is present in the first liquid and / or the second liquid,
The coating composition according to claim 4, wherein the components (d) and (e) are present in the second liquid and the organic solvent is present in the first liquid and / or the second liquid.