JPH10140086A - Inorganic coating material composition and coated product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both an inorganic coating material composition, curable at normal temperatures and excellent even in weather resistance and toughness and a coated product using the inorganic coating material composition. SOLUTION: This composition is obtained by compounding (A) 100 pts.wt. of an organosiloxane, composed of a hydrolyzed condensate of 20-200 pts.wt. of a silicon compound represented by the formula Si(OR<1> )4 and/or a colloidal silica with 100 pts.wt. of a silicon compound represented by the formula R<2> Si(OR<1> )3 and 0-60 pts.wt. of a silicon compound represented by the formula R<2> 2 (OR<1> )2 (R<1> and R<2> are each a monovalent hydrocarbon) and having >=800 weight-average molecular weight expressed in terms of polystyrene with (B) 1-100 pts.wt. of an acrylic resin which is a copolymer of the first (meth)acrylic ester that is a monomer represented by the formula CH2 = CR<3> (COOR<4> ) (R<3> is H and/or methyl group; R<4> is a 1-9C monovalent hydrocarbon group), the second (meth)acrylic ester in which R<4> is at least one group selected from the group consisting of epoxy group, glycidyl group and a hydrocarbon group containing at least either one thereof and the third (meth)acrylic ester in which R<4> is a hydrocarbon group containing an alkoxysilyl group and/or a halogenated silyl group. The coated product has a coated and cured film of the composition on the surface of a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic coating material composition and a coated product using the same, and more particularly, to a plastic substrate; an inorganic material such as a glass substrate, an inorganic substrate for building materials, and a metal substrate. It is applied to the surface of a base material such as a base material, and can be cured by leaving it at room temperature using a heat treatment or a curing catalyst, and has appropriate hardness, heat resistance,
The present invention relates to an inorganic coating material composition capable of forming a coating film having excellent weather resistance, toughness, and the like, and a coated article provided with a cured coating film of the inorganic coating material composition on the surface of the substrate.

[0002]

2. Description of the Related Art Conventionally, plastic substrates; glass substrates,
Hydrolytic polycondensation or partial hydrolysis of hydrolyzable organosilane as a coating material to form a durable coating for the surface protection of inorganic base materials such as inorganic base materials for building materials and metal base materials A coating composition obtained by polycondensation or a coating composition obtained by mixing colloidal silica with the coating composition is known.

[0003] For example, Japanese Patent Application Laid-Open No.
JP-A-51-2737, JP-A-53-130732, JP-A-63-16
Japanese Patent No. 8470 discloses an organoalkoxysilane, a hydrolyzed polycondensate and / or a partially hydrolyzed polycondensate of the organoalkoxysilane, and colloidal silica, wherein the alkoxy group is converted to silanol with excess water. Coating materials have been proposed. The coating film obtained from this coating material has good weather resistance and is excellent for protecting a substrate, but has too high hardness (pencil hardness of 9H or more) and thus has poor toughness. Cracks easily occur during heat curing, when used outdoors, or when a sudden change in temperature occurs. In the coating process, it is often difficult to precisely control the thickness of the coating film to 10 μm or less. In particular, the coating thickness tends to exceed 10 μm on the painted surface, the peripheral portion of the painted product, and the concave portion of the painted surface, and manufacturing is difficult. Good products are likely to occur. In addition, these coating materials,
Since a high temperature of about 100 ° C. or more or a long heat treatment is required to obtain desired coating properties, a substrate having a shape that is difficult to apply heat uniformly, a substrate having a large size, or poor heat resistance It cannot be used when it is difficult to apply heat, such as when painting on a substrate or the like, or when performing painting work outdoors or the like, and there are limitations.

[0004] Coating materials having a composition obtained by removing colloidal silica from the above-mentioned coating materials have problems in that they lack film-forming properties at the time of coating and have low coating film strength. JP-A-4-175388 discloses a coating material containing a partially hydrolyzed oligomer of organosilane, a silanol group-containing polyorganosiloxane, and a curing catalyst. Although this coating material has the advantages of improved paintability and curability, curing at room temperature, and being unaffected by humidity, its hardness is relatively low (pencil hardness 5H or less) and its toughness is sufficiently high. Had not been improved. To solve this problem, Japanese Patent Application No. 8-27100 proposes to improve the toughness of a cured coating film by adding an acrylic resin to the coating material, but the hardness of the coating film is too low ( Pencil hardness 2H or less).

[0005]

An object of the present invention is not only to cure by heating, but also to cure at room temperature by using a curing catalyst, to form a coating film having high weather resistance and toughness ( An inorganic coating material composition capable of obtaining a cured film which does not crack even at a film thickness of 10 μm or more because of its excellent flexibility) and has neither too high nor too low hardness, and a coated product using the same. To provide.

[0006]

Means for Solving the Problems The inorganic coating material composition according to the present invention is based on 100 parts by weight of an organosiloxane of the following (A) and acrylic resins 1 to 1 of the following (B).
00 parts by weight. (A): (A ₁ ) 20 to 200 parts by weight of a silicon compound and / or colloidal silica represented by the general formula Si (OR ¹ ) ₄ ... (I ₁ ), and (A ₂ ) a general formula R ² Si ( OR ¹⁾ ₃ ... (the silicon compound to 100 parts by weight represented by the I _2), (A ₃₎ the general formula ^{_{R 2 2 Si (OR 1)}} 2 ... (0~60 weight silicon compound represented by I ₃₎ (Wherein R ¹ and R ^{2 each} represent a monovalent hydrocarbon group), and the weight average molecular weight of which is adjusted to be 800 or more in terms of polystyrene. . (B): a monomer represented by the general formula CH ₂ ＣＲCR ³ (COOR ⁴ ) (II) (where R ³ represents a hydrogen atom and / or a methyl group), wherein R ⁴ is substituted or unsubstituted A first (meth) acrylate which is a substituted monovalent hydrocarbon group having 1 to 9 carbon atoms, and a group in which R ⁴ is an epoxy group, a glycidyl group and a hydrocarbon group containing at least one of them. A second (meth) acrylate which is at least one group selected from the group consisting of: a third (meth) acrylic acid wherein R ⁴ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group; Acrylic resin which is a copolymer of ester and

[0007] In this specification, (meth) acrylic ester refers to either or both of acrylic ester and methacrylic ester. In the inorganic coating material composition according to the present invention, the relative organosiloxane (A) 100 parts by weight of, the R ⁵ is (here represented by the general formula _{^{HO (R 5 2 SiO) n}} H ... (III) 1 A divalent hydrocarbon group; n
≧ 3) linear polysiloxane diol 1-100
It is preferable that the weight part is further blended.

[0008] The coated article according to the present invention is an inorganic building material provided with a cured coating of the inorganic coating material composition according to the present invention on the surface of an inorganic substrate. Another coated product according to the present invention is a plastic product comprising a plastic substrate and a cured coating of the inorganic coating material composition according to the present invention on the surface thereof.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The silicon compound (A ₁ ) used as a raw material of the organosiloxane (A) in the present invention
(A ₃ ) can be generally represented by the following general formula: R ² _m Si (OR ¹ ) _4-m (I) (R ¹ and R ^{2 each} represent a monovalent hydrocarbon group; Integer of ~ 2).

R ² is not particularly limited, and includes, for example, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl,
Alkyl groups such as heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; An alkenyl group such as an allyl group; a chloromethyl group,
halogen-substituted hydrocarbon groups such as γ-chloropropyl group and 3,3,3-trifluoropropyl group; γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ -A substituted hydrocarbon group such as a mercaptopropyl group. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoints of ease of synthesis, availability, suppression of a decrease in hardness, and the like.

R ¹ is not particularly limited. For example, R ¹ is mainly composed of an alkyl group having 1 to 4 carbon atoms. In particular, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as the tetraalkoxysilane of m = 0, and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane can be exemplified as the organotrialkoxysilane of m = 1. Phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. Further, as the diorganodialkoxysilane of m = 2, dimethyldimethoxysilane,
Examples thereof include dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

These R ¹ and R ² are a silicon compound (A ₁ )
To (A ₃ ) may be the same or different. The organosiloxane (A) is prepared by, for example, diluting the raw materials (A ₁ ) to (A ₃ ) with a suitable solvent, adding water and a catalyst as required in a required amount to a hydrolysis and polycondensation reaction. To obtain a prepolymer, in which case the weight average molecular weight (Mw) of the obtained prepolymer becomes 800 or more, preferably 850 or more, more preferably 900 or more in terms of polystyrene. Adjust as follows. When the molecular weight distribution (weight average molecular weight (Mw)) of the prepolymer is less than 800, the hardness of the cured film formed from the inorganic coating material composition is too high, or the curing at the time of polycondensation of the inorganic coating material composition. The shrinkage is large and cracks are likely to occur in the coating film after baking.

The amount of the raw materials (A ₁ ) to (A ₃ ) used in preparing the organosiloxane (A) is _{20 to} 200 parts by weight of (A ₁ ) per 100 parts by weight of (A ₂ ) (preferably). Is 40 ~
160 parts by weight, more preferably 60 to 120 parts by weight),
(A ₃₎ 0 to 60 parts by weight (preferably 0 to 40 parts by weight, more preferably 0 to 30 parts by weight) is the percentage of. If the amount of (A ₁ ) is less than the above range, there is a problem that a desired hardness of the cured film cannot be obtained (the hardness is lowered). Conversely, if the amount is more than the above range, the crosslinked density of the cured film is high. There is a problem that the hardness is too high and the crack is easily generated. If the amount of (A ₃ ) is more than the above range, there is a problem that a desired hardness of the cured film cannot be obtained (hardness is lowered).

As the colloidal silica usable as the raw material (A ₁ ), water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content. When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used as a curing agent as described later. These are usually made from water glass, and such colloidal silica is readily available commercially. The organic solvent-dispersed colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product similarly to the water-dispersible colloidal silica. The type of the organic solvent in which the colloidal silica is dispersed is, for example, methanol, ethanol, isopropanol, n-
Lower aliphatic alcohols such as butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol And one or more selected from the group consisting of these can be used.
Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone oxime and the like can also be used in combination with these hydrophilic organic solvents.

The raw material (A₁) As colloidal silica
When using (A₁) Is the weight including the dispersion medium
Parts. The raw material (A₁)-(A_Three)
Water is used as a curing agent for the combination reaction.
However, as the amount, the silicon compound (A₁)-(A_Three)of
OR ¹From 0.01 to 3.0 moles of water is preferred per equivalent of group.
And more preferably 0.3 to 1.5 mol.

As the diluting solvent used in the hydrolysis polycondensation reaction of the raw materials (A ₁ ) to (A ₃ ), methanol, ethanol, and the like described above as the colloidal silica dispersion solvent are used.
Lower aliphatic alcohols such as isopropanol, n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol And the like, and one or more kinds selected from the group consisting of these can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone oxime and the like can also be mentioned.

Further, the p of the organosiloxane (A)
By adjusting H to 3.8 to 6, the organosiloxane (A) can be used stably within the above-mentioned range of molecular weight. If the pH is out of this range, the stability of the organosiloxane (A) is poor, so that the usable period from the preparation of the coating is limited. Here, the pH adjustment method is not particularly limited, but, for example,
When the raw materials of the organosiloxane (A) are mixed, the pH is 3.8
If less than, for example, it may be adjusted to a pH within the above range using a basic reagent such as ammonia,
Is greater than 6, for example, may be adjusted using an acidic reagent such as hydrochloric acid. In addition, depending on the pH, when the reaction does not proceed while the molecular weight is small and it takes time to reach the molecular weight range, the organosiloxane (A) may be heated to accelerate the reaction, After lowering the pH with a reagent and proceeding with the reaction,
May be returned.

The acrylic resin used as the component (B) of the inorganic coating composition of the present invention has an effect of improving the toughness of a cured film of the inorganic coating composition. The first (meth) acrylic acid ester, which is one of the constituent monomers of the acrylic resin (B), is represented by R in the formula (II)
⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-
Propyl group, n-butyl group, i-butyl group, sec-butyl group,
tert-butyl group, pentyl group, hexyl group, heptyl group, alkyl group such as octyl group; cyclopentyl group,
Cycloalkyl groups such as cyclohexyl groups; aralkyl groups such as 2-phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; chloromethyl group and γ-chloropropyl group ,
Halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl groups; hydroxy hydrocarbon groups such as 2-hydroxyethyl groups; and the like.

The second (meth) acrylic acid ester, which is another constituent monomer of the acrylic resin (B), is a compound in which R ⁴ in the formula (II) contains an epoxy group, a glycidyl group and at least one of these. At least one of at least one group selected from the group consisting of hydrogen groups (for example, γ-glycidoxypropyl group and the like).

A third (meth) acrylic acid ester, which is another constituent monomer of the acrylic resin (B), has the formula (I)
R ^{4 in} I) is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group, for example, a trimethoxysilylpropyl group, a dimethoxymethylsilylpropyl group, a monomethoxydimethylsilylpropyl group, a triethoxysilylpropyl group, Diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichlorosilylpropyl group, dichloromethylsilylpropyl group,
It is at least one of chlorodimethylsilylpropyl group, chlorodimethoxysilylpropyl group, dichloromethoxysilylpropyl group and the like.

The acrylic resin (B) comprises the first, second,
The third (meth) acrylic acid ester is a copolymer of (meth) acrylic acid esters containing at least one kind in total and at least three kinds in total, and the first, second and third (meth) acrylic acids are Another one selected from esters
Or two or more, or one or more selected from (meth) acrylates other than the above.
Copolymers containing more than one species may be used.

The first (meth) acrylic acid ester is an essential component for improving the toughness of the cured film of the inorganic coating material composition. For this purpose, a substituted or unsubstituted hydrocarbon of R ⁴ is used. It is desirable that the group has a certain volume or more, and it is preferable that the group has 2 or more carbon atoms. The second (meth) acrylic acid ester is an essential component for improving the adhesion to the substrate.

The third (meth) acrylic acid ester forms a chemical bond with the organosiloxane (A) during the formation of the coating film, whereby the acrylic resin (B) is fixed in the coating film. . The third (meth) acrylic acid ester is composed of an acrylic resin (B) and an organosiloxane (A).
Also has the effect of improving the compatibility with. Acrylic resin (B)
Has a great influence on the compatibility with the organosiloxane (A). If the weight average molecular weight in terms of polystyrene of the acrylic resin (B) exceeds 50,000, phase separation may occur and the coating film may be whitened. Therefore, it is desirable that the weight average molecular weight in terms of polystyrene of the acrylic resin (B) be 50,000 or less. The lower limit of the weight average molecular weight of the acrylic resin (B) in terms of polystyrene is preferably 1,000. If the molecular weight is less than 1,000, the toughness of the coating film tends to decrease, and cracks tend to occur, which is not preferable.

The second (meth) acrylic acid ester is desirably at least 2% by mole of the monomer in the copolymer. If it is less than 2%, the adhesion of the coating film will be insufficient. Third
The (meth) acrylic acid ester is desirably in the range of 2 to 50% by mole ratio of monomers in the copolymer. If it is less than 2%, the compatibility between the acrylic resin (B) and the organosiloxane (A) is poor, and the coating film may be whitened. On the other hand, if it exceeds 50%, the bond density between the acrylic resin (B) and the organosiloxane (A) becomes too high, and the improvement of toughness, which is the original purpose of the acrylic resin, cannot be seen.

As a method for synthesizing the acrylic resin (B), a known radical polymerization method by solution polymerization, emulsion polymerization or suspension polymerization in an organic solvent, or an anion polymerization method or a cationic polymerization method is used. Not something. In the inorganic coating material composition of the present invention, the content (blending ratio) of the acrylic resin (B) is 10% or less.
The amount is usually 1 to 100 parts by weight, preferably 5 to 30 parts by weight with respect to 0 parts by weight. When the amount is less than 1 part by weight, the toughness is weakly expressed, and when the amount is more than 100 parts by weight, the hardness is reduced or the curing of the coating film is inhibited.

As to the linear polysiloxane diol optionally contained in the inorganic coating material composition of the present invention, n is 3 or more in the above-mentioned general formula (III), and R ⁵ is As R ² in the formula (I), the same as those described above can be used. As described below, the linear polysiloxane diol has effects such as imparting water repellency or oil repellency to the surface of the cured film and, when n is small, further improving the toughness of the cured film. The linear polysiloxane diol is a molecule having relatively low reactivity because it has no reactive group other than the terminal OH group. Therefore, when blended in the inorganic coating material composition,
Lack of complete compatibility in the composition, dispersed as ultrafine particles, easily coordinate to the coating film surface to form a monolayer, but ultimately the terminal OH is It is fixed on the coating film surface by a condensation reaction. As a result, the R ⁵ groups are localized on the surface of the cured film, which has the effect of lowering the surface energy of the cured film. When the surface of the cured film has a low surface energy, the contact angle with a liquid such as water increases, and the surface of the cured film is given water repellency or oil repellency. When the cured coating surface becomes water or oil repellent, lacquer paint, oil,
There is an advantage in that even if contaminant components such as exhaust gas and tobacco tar adhere to the surface, a contaminant resistance effect of easily removing them is exhibited. Further, those having a relatively small n in the formula (III) have excellent compatibility, so that not only a layer is formed on the surface of the coating film, but also the effect of further improving the toughness of the coating film by being incorporated into the bulk is obtained. is there. From the viewpoint of further improving the toughness, n is preferably 3 to 100, more preferably 3 to 50, further preferably 3 to 30, and most preferably 10 to 20.

When the linear polysiloxane diol is contained in the inorganic coating material composition of the present invention, its content (blending ratio) is 100 parts by weight of the organosiloxane (A).
1 to 100 parts by weight, preferably 5 to 100 parts by weight,
-30 parts by weight. If the amount is less than 1 part by weight, lowering of surface energy or the development of toughness is weak, and if it is more than 100 parts by weight, curing of the coating film is inhibited.

The inorganic coating material composition of the present invention comprises:
In the case of curing by heating, it is not necessary to include a curing catalyst, but a curing catalyst can be further included as necessary for accelerating the curing of the coating film or curing at room temperature. Examples of the curing catalyst include, but are not particularly limited to, alkyl titanates; carboxylic acid metal salts such as tin octylate, dibutyltin dilaurate, and dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate, and ethanolamine acetate Amine salts such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-aminoethyl-γ Amine silane coupling agents such as aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate, sodium formate, potassium phosphate Alkali metal salts such beam; tetraisopropyl titanate, tetrabutyl titanate, titanium compounds such as titanium tetra acetyl acetonate; methyltrichlorosilane, dimethyldichlorosilane, halogenated silanes such as trimethyl monochloro silane, and the like. However, other than these, there is no particular limitation as long as it is effective for the condensation reaction of the organosiloxane (A).

The inorganic coating composition of the present invention comprises:
For ease of handling, it can be used after being diluted with various organic solvents, or may be diluted with the same organic solvent. The type of the organic solvent can be selected according to the type of the monovalent hydrocarbon group contained in the organosiloxane (A) or the molecular weight of the organosiloxane (A). Such organic solvents include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol,
Ethylene glycol derivatives such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether;
And toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol, etc., and one or more selected from the group consisting of these. Can be used.

The inorganic coating material composition of the present invention comprises:
Pigments may be included as needed. The pigments that can be used are not particularly limited, but include, for example, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; titanium oxide, barium sulfate, red iron oxide, composite metal oxides, and the like. Inorganic pigments are preferred, and one or two or more selected from these groups may be used in combination.
Dispersion of the pigment may be performed by an ordinary method. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used.

In addition, a leveling agent, a dye, a metal powder, a glass powder, an antibacterial agent, an antioxidant, an antistatic agent, an ultraviolet absorber and the like may be used within the range not adversely affecting the effect of the present invention. May be included. The inorganic coating material composition of the present invention can be applied to various substrates and cured. Thereby, it is possible to obtain various coated articles provided with the applied cured film of the inorganic coating material composition of the present invention on the surface of various substrates.

The method for applying the inorganic coating material composition of the present invention to a substrate is not particularly limited. For example, brushing, spraying, dipping, flow, roll,
Various ordinary coating methods such as a curtain and a knife coat can be selected. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be determined as needed.

As a method for curing the inorganic coating material composition applied to the substrate, a known method may be used.
There is no particular limitation. Further, the temperature at the time of curing is not particularly limited, and can be in a wide range from room temperature to heating temperature according to the desired cured film performance. The thickness of the coating film (cured coating) formed from the inorganic coating material composition of the present invention is not particularly limited, and is, for example, 0.1 to 50 μm.
However, in order to ensure that the coating film is stably adhered and held for a long period of time and cracks and peeling do not occur, it is 1 to 30.
μm is preferred.

The substrate used in the present invention is not particularly limited, and examples thereof include a plastic substrate; an inorganic substrate such as a glass substrate, an inorganic substrate for building materials, and a metal substrate. As the plastic substrate,
Although not particularly limited, for example, thermosetting plastics, thermoplastic plastics, fiber reinforced plastics and the like can be mentioned. Further, the plastic substrate may be a plate, a film, a molded product thereof, or a structure partially provided with at least one of these plastics. Since the inorganic coating material composition of the present invention has improved toughness of the cured film, it can be applied to a relatively soft substrate such as plastic, and an effect of preventing the surface from being damaged can be obtained.

The glass substrate is not particularly limited, and examples thereof include sodium soda glass, Pyrex glass, and quartz glass. Further, the glass substrate may be a plate of such a glass, a molded body thereof, or a structure partially provided with at least one of them. The inorganic base material for building material is not particularly limited, for example, fiber reinforced cement board, ceramic siding board, wood wool cement board, pulp cement board, slate / wood wool cement laminate board, gypsum board, clay tile, Thick slate, ceramic tile, water glass decorative board,
Alternatively, a structure or the like partially provided with at least one of them. Conventional silicone coatings are susceptible to alkali components solute from these inorganic base materials for building materials, and long-term durability cannot be obtained. The inorganic coating material composition has a feature that long-term durability can be obtained because the acrylic resin is introduced, so that it is not easily attacked by an alkali component.

The metal substrate is not particularly limited. For example, non-ferrous metals (eg, aluminum,
Aluminum alloy, etc.), iron, steel (eg, rolled steel, hot-dip galvanized steel, (rolled) stainless steel, etc.), tinplate,
Other metals in general are listed. Also, the metal substrate is
It may be a plate of these metals, a molded body thereof, or a structure partially provided with at least one of them.

In order to obtain high adhesion between the cured film of the inorganic coating material composition and the substrate, a primer layer is previously formed on the surface of the substrate before forming the applied cured film of the inorganic coating material composition. It is desirable to keep it. The primer layer is not particularly limited. For example, at least one selected from the group consisting of epoxy resin, acrylic resin, acrylic silicone resin, chlorinated rubber resin, urethane resin, phenol resin, polyester resin and melamine resin And a cured resin layer of a primer composition containing 10% by weight or more. The thickness of the primer layer is not particularly limited;
0 μm is preferable, and 0.5 to 10 μm is more preferable.
If the thickness is too small, adhesion cannot be obtained. If the thickness is too large, foaming or the like may occur during drying.

[0038]

The present invention will be described in detail below with reference to examples and comparative examples. In the examples and comparative examples, all “parts” represent “parts by weight” and all “%” represent “% by weight”. The molecular weight can be measured by GPC (gel permeation chromatography) using Tosoh Corporation's H
A calibration curve was prepared with standard polystyrene using LC8020 and measured. In addition, this invention is not limited to a following example. (Preparation Example of Organosiloxane (A)): (Preparation Example A-1): IPA organosilica sol, an acidic colloidal silica [trade name "OSCAL1432", manufactured by Catalyst Chemical Industry Co., Ltd.] in 100 parts of methyltrimethoxysilane. [Solid content 30%] was mixed with 60 parts of dimethyldimethoxysilane, and the mixture was diluted with 100 parts of isopropyl alcohol (hereinafter abbreviated as IPA), and 39 parts of water was added, followed by stirring. The obtained liquid was heated in a 60 ° C. constant temperature bath for 5 hours to obtain a weight average molecular weight Mw = 1.
Adjusted to 200 to obtain a 26% alcohol solution of organosiloxane. The organosiloxane obtained here is called A-1.

Preparation conditions of A-1: [Water] / [OR ¹ ] molar ratio 1.15 Weight average molecular weight 1200 Solid content 26% (Preparation Example A-2): 100 parts of methyltrimethoxysilane And 90 parts of an IPA organosilica sol (trade name “OSCAL1432”, manufactured by Catalyst Chemical Industry Co., Ltd., solid content 30%), which is an acidic colloidal silica,
The mixture was diluted with 100 parts of A, further added with 37.7 parts of water, and stirred. The obtained liquid was heated in a thermostat at 60 ° C. for 5 hours to adjust the weight average molecular weight Mw to 1500 to obtain a 23% alcohol solution of an organosiloxane. The organosiloxane obtained here is called A-2.

Preparation conditions of A-2: [Water] / [OR ¹ ] molar ratio 1.45 ・ Weight average molecular weight 1500 ・ Solids content 23% (Preparation example of acrylic resin): (Preparation example B-1) ): N-butyl methacrylate (BM) in a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, nitrogen gas inlet / outlet and thermometer
A) 5.69 parts, trimethoxysilylpropyl methacrylate (SMA) 1.24 parts, glycidyl methacrylate (GMA) 0.71
A solution obtained by dissolving 0.025 part of azobisisobutyronitrile in 3 parts of toluene was added dropwise to a reaction solution obtained by dissolving 0.784 part of γ-mercaptopropyltrimethoxysilane as a chain transfer agent in 8.49 parts of toluene under a nitrogen stream. At 70 ° C. for 2 hours. Thus, the weight average molecular weight Mw =
A 1,000% 40% toluene solution of acrylic resin was obtained. The acrylic resin obtained here is called B-1.

Preparation conditions of B-1: monomer molar ratio BMA / SMA / GMA = 8/1/1 weight average molecular weight 1,000 solid content 40% (Preparation Example B-2): Preparation Example B Perform the same operation as -1 and n-
A reaction solution prepared by dissolving 4.98 parts of butyl methacrylate (BMA), 2.48 parts of trimethoxysilylpropyl methacrylate (SMA), 0.71 parts of glycidyl methacrylate (GMA), and 0.784 parts of γ-mercaptopropyltrimethoxysilane in 9.26 parts of toluene was added to azobisisopropane. A solution obtained by dissolving 0.025 part of butyronitrile in 3 parts of toluene was dropped and reacted. The obtained acrylic resin is called B-2.

Preparation conditions of B-2: monomer molar ratio BMA / SMA / GMA = 7/2/1 weight average molecular weight 1,000 solid content 40% (Preparation Example B-3): Preparation Example B Perform the same operation as -1 and n-
Azobisisoisopropyl was added to a reaction solution obtained by dissolving 5.69 parts of butyl methacrylate (BMA), 1.24 parts of trimethoxysilylpropyl methacrylate (SMA), 0.71 part of glycidyl methacrylate (GMA), and 0.0392 parts of γ-mercaptopropyltrimethoxysilane in 8.49 parts of toluene. A solution obtained by dissolving 0.025 part of butyronitrile in 3 parts of toluene was dropped and reacted. The obtained acrylic resin is called B-3.

Preparation conditions of B-3:-Monomer molar ratio BMA / SMA / GMA = 8/1/1-Weight average molecular weight 12,000-Solid content 40% (Comparative Preparation Example B-4): Preparation Example The same operation as in B-1 was performed, and 3.56 parts of n-butyl methacrylate (BMA), 0 parts of trimethoxysilylpropyl methacrylate (SMA), 3.55 parts of glycidyl methacrylate (GMA), and 0.784 parts of γ-mercaptopropyltrimethoxysilane were added to toluene 7.7. A solution obtained by dissolving 0.025 part of azobisisobutyronitrile in 3 parts of toluene was added dropwise to the reaction solution dissolved in 3 parts, and reacted. The obtained acrylic resin is called B-4.

Preparation conditions of B-4: monomer molar ratio BMA / SMA / GMA = 5/0/5 weight average molecular weight 1,000 solid content 40% (linear polysiloxane diol): weight average A linear dimethylpolysiloxane diol having a molecular weight Mw = 800 (n ≒ 11).

Weight average molecular weight Mw = 3000 (n ≒ 4
0) is a linear dimethylpolysiloxane diol. (Curing acceleration catalyst): 10% aqueous solution of potassium formate. (Examples 1 to 6 and Comparative Examples 1 and 2): The components shown in Tables 1 and 2 were mixed in the proportions shown in the same table, and all were diluted with isopropyl alcohol so as to have a solid content of 20%.
An inorganic coating material composition was obtained. This composition was applied to an aluminum test piece (trade name: Ulster, manufactured by Nippon Test Panel Co., Ltd., dimensions 150 mm × 70 mm × 0.3 mm) by spray coating so that the cured coating thickness became 10 μm or 30 μm, and the curing temperature was 150 ° C. For 30 minutes to form a coating film, and a coating film property test was performed. The results are shown in Tables 1 and 2. (Evaluation of coating film properties): Adhesion: Adhesion to the substrate was evaluated by a cross-cut adhesive tape (using cellophane tape) peel test.

Coating film hardness: According to a pencil hardness test (according to JIS K5400). Solvent resistance: The coating film was gently pressed with a gauze impregnated with toluene and rubbed 100 times in a reciprocating manner. Boiling resistance: After the test was boiled in tap water for 5 hours, the test piece was left for 1 hour, and the state of the coating film was observed.

Weather resistance: Sunshine Super Long Life Weather Meter (WEL-SUN manufactured by Suga Test Instruments)
(HC type), and the coating was observed for 2500 hours, and the coating which did not change was evaluated as good.

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[Table 1]

[0049]

[Table 2]

As can be seen from Tables 1 and 2, the inorganic coating material compositions of the examples had better adhesion, coating film hardness, solvent resistance, boiling water resistance and weather resistance than the comparative examples. All were good. (Examples 7 to 14): The inorganic coating material composition of Example 4 was spray-coated on various substrates to have a cured film thickness of 30.
The coating was formed to a thickness of μm and cured at a curing temperature of 80 ° C. for 60 minutes to form a coating film. The coating film characteristics were evaluated in the same manner as in Example 4 (however, weather resistance was excluded). As a substrate,
The following were used.

Stainless steel plate: SUS304 plate (size 150 mm ×
70 mm x 0.5 mm). PMMA board: Polymethyl methacrylate board (Dimensions 150 mm x
70mm x 2mm). PC board: Polycarbonate board (Dimensions 150mm x 70mm x
5mm). Slate board: fiber reinforced cement board (size 150mm x 70
mm x 3 mm). If necessary, an epoxy-based sealer “Epolo E Sealer” (manufactured by Isamu Paint) was used as a primer. Even if no primer is used, there is no particular problem with the adhesion, but if sufficient adhesion is required even after treatment with boiling water for 5 hours, it is preferable to use a primer.

Table 3 shows the results.

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[Table 3]

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The inorganic coating material composition of the present invention can form a coating film having high hardness, high weather resistance, excellent adhesion, solvent resistance, boiling water resistance and the like. The cured film obtained from the inorganic coating material composition of the present invention does not have excessively high hardness and is excellent in toughness (flexibility). It has a wide range of properties and can widely cope with dimensional changes due to the temperature and humidity of the substrate. Also, the hardness of the cured film is not too low. Furthermore, the inorganic coating material composition of the present invention can be used not only by heat curing but also by ordinary temperature curing by using a curing catalyst, so that it can be used in a wide range of dry curing conditions or temperatures. Therefore, it is difficult to apply heat to a base material having a shape that is difficult to apply heat evenly, a base material having a large dimension or a base material having poor heat resistance, or a case where the coating work is performed outdoors or the like. Its industrial value is high because it can be painted even in cases.

Claims (4)

[Claims] An inorganic coating material composition comprising 100 parts by weight of an organosiloxane of the following (A) and 1 to 100 parts by weight of an acrylic resin of the following (B). (A): a silicon compound represented by the general formula Si (OR ¹ ) ₄ and / or 20 to 200 parts by weight of colloidal silica, and a silicon compound ¹ represented by the general formula R ² Si (OR ¹ ) ₃
And 00 parts by weight, the general formula R ² ₂ Si (OR ¹⁾ a silicon compound 0 to 60 parts by weight, represented by _2, consists of hydrolytic polycondensate (wherein R ^1, R ² are monovalent hydrocarbon A hydrogen group), and an organosiloxane whose weight average molecular weight is adjusted to be 800 or more in terms of polystyrene. (B): a monomer represented by the general formula CH ₂ ＣＲCR ³ (COOR ⁴ ) (where R ³ represents a hydrogen atom and / or a methyl group), wherein R ⁴ is a substituted or unsubstituted carbon number A first (meth) acrylate which is a monovalent hydrocarbon group of 1 to 9, and R ⁴ is selected from the group consisting of an epoxy group, a glycidyl group and a hydrocarbon group containing at least one of these groups; A second (meth) acrylate which is at least one group, and a third (meth) acrylate wherein R ⁴ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. Acrylic resin that is a copolymer. To wherein said organosiloxane (A) 100 parts by weight of the general formula _{^{HO (R 5 2 SiO) n}} H ( wherein R ⁵ represents a monovalent hydrocarbon radical, n
≧ 3) linear polysiloxane diol 1-100
The inorganic coating material composition according to claim 1, further comprising parts by weight. 3. An inorganic building material provided with a cured coating of the inorganic coating material composition according to claim 1 on the surface of an inorganic substrate. 4. A plastic product comprising a plastic substrate and a cured coating of the inorganic coating material composition according to claim 1 on the surface thereof.