JPH08209069A - Coating fluid and its production - Google Patents

Abstract

PURPOSE: To obtain the subject fluid including a specific acrylic polyol and a hydrolyzed condensate of a specific organic silicon compound, excellent in storage stabilities and capable of providing a thick film excellent in properties resistant to soil, abrasion, solvent and chemical, etc. CONSTITUTION: This coating fluid comprises (A) an acrylic polyol prepared by copolymerizing (i) 1-80wt.% monomer containing hydroxyl group (e.g. 2- hydroxyethylacrylate) with (ii) 20-99wt.% vinyl-based monomer copolymerizable therewith and (B) a hydrolyzed condensate formed by adding water in an amount of more than that of theoretically 100% capable of performing the hydrolyzing condensation, preferably 1-1.5 fold of 100% equivalent for the hydrolyzing condensation to an organic silicon compound of the formula (R is a 1-8C hydrocarbon) and/or a partially hydrolyzed condensate thereof. Furthermore, the component A is preferably obtained by a solution polymerization using an azo-based radical initiator. Also, as the previously mentioned organic silicon compound and/or partially hydrolyzed condensate thereof, a tetramethoxysilane oligomer containing <=3wt.% monomer content is preferred.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating solution and a method for producing the same, and more particularly to iron, stainless steel, aluminum and other metals, plastics, glass,
A coating liquid excellent in transparency, weather resistance, solvent resistance, adhesion, acid resistance, and hardness, which is suitable for application to the surface of products such as wood, cement and other substrates, powders, and linear materials, and The manufacturing method is related.

[0002]

2. Description of the Related Art The applicant of the present invention has previously proposed a novel coating using tetramethoxysilane, which has improved hardness, solvent resistance, chemical resistance, stain resistance, scratch resistance, etc. of conventional coating films. Proposed coating composition (Japanese Patent Application No. 5-204
229, Japanese Patent Application No. 5-80764, Japanese Patent Application No. 5-10111
6, Japanese Patent Application No. 5-296772, Japanese Patent Application No. 5-29677
3, Japanese Patent Application No. 6-96316, Japanese Patent Application No. 6-228349
etc).

[0003]

However, the coating film obtained by such a coating solution is excellent in stain resistance, scratch resistance, solvent resistance and chemical resistance, but the thickness of the obtained coating film is thin. Moreover, since flexibility is insufficient, if the film thickness is increased, cracks may occur during processing. In addition, the coating film obtained by the coating solution proposed in Japanese Patent Application No. 6-96316 is improved in these points, has a thick film thickness and is rich in flexibility, but is further improved in stain resistance and scratch resistance. Is desired.

[0004]

Therefore, as a result of intensive studies in view of the above problems, the present inventors have theoretically hydrolyzed a specific organosilicon compound and / or its partially hydrolyzed condensate to 100%. A coating film obtained by coating the coating liquid obtained by blending the specific acrylic polyol and the mixture after aging by adding water in an amount sufficient for condensation to allow the hydrolysis and condensation reaction to proceed sufficiently has a high hardness. , A few μ while maintaining stain resistance, solvent resistance and chemical resistance
The inventors have found that it is possible to have a film thickness of m to several tens of μm, and have excellent flexibility, and have reached the present invention.

That is, the present invention provides an acrylic polyol (A) obtained by copolymerizing (a) 1 to 80% by weight of a hydroxyl group-containing monomer, and (b) 20 to 99% by weight of a vinyl-type monomer copolymerizable therewith. ) And an organosilicon compound represented by the following general formula (I) and / or a partial hydrolyzed condensate thereof, and a hydrolyzed condensate obtained by adding at least a theoretically 100% hydrolytically condensable amount of water. A coating liquid containing (B), and

[0006]

Embedded image

The organosilicon compound represented by the general formula (I) and / or its hydrolytic condensate and theoretically 10
A method for producing a coating liquid, which comprises aging a liquid containing 0% or more of an amount of water capable of being hydrolyzed and condensed and then blending the liquid with an acrylic polyol (A).

The present invention will be described in detail below. First, as the hydroxyl group-containing monomer (a) in the acrylic polyol (A) in the present invention, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate. , 4-hydroxybutyl (meth)
Acrylate, 2-hydroxyethyl vinyl ether,
N-methylol (meth) acrylamide, Aronix 5700, 4-hydroxystyrene manufactured by Toagosei Chemical Industry Co., Ltd., HE-10, HE manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
-20, HP-10 and HP-20 (all of which are acrylic ester oligomers having a hydroxyl group at the terminal), NOF CORPORATION's BLEMMER PP series (polypropylene glycol methacrylate), BLEMMER PE series (polyethylene glycol mono). Methacrylate), Bremmer PEP series (polyethylene glycol polypropylene glycol methacrylate,
Bremmer AP-400 (polypropylene glycol monoacrylate), Bremmer AE-350 (polypropylene glycol polytriethylene monoacrylate), Bremmer NKH-5050 (polypropylene glycol polytriethylene monoacrylate) and Bremmer GLM (glycerol monomethacrylate),
An example is an ε-caprolactone-modified hydroxyalkylvinyl-based monomer obtained by the reaction of a hydroxyl group-containing vinyl compound and ε-caprolactone.

These hydroxyl group-containing vinyl monomers may be used alone or in combination of two or more as required. The amount of the hydroxyl group-containing vinyl monomer used is in the range of 1 to 80 parts by weight. If it is less than 1 part by weight, the thickness of the obtained coating film is thin, whitening or insufficient adhesion is observed. If it exceeds the amount by weight, storage stability decreases.

As the vinyl-based monomer (b) copolymerizable with (a), any radically polymerizable monomer can be used without particular limitation. Specifically, ethylene, propylene, chloroethylene, 1,1-dichloroethylene, 1-butene, isobutene, 1-pentene, 3-
Methyl-1-butene, 4-methyl-1-pentene, 1-
Hydrocarbon monomers such as hexene, vinylcyclohexane, cyclobutene, cyclopentene, cyclohexene, norporne, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, α-pinene, β-pinene, indene; butadiene, isoprene, Conjugated dienes such as chloroprene and phenylpropadiene; 1,5-hexadiene, 1,9-
Non-conjugated dienes such as decadienes; cyclic dienes such as cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate , I-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate. ) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2
-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, ethylcarbinol (meth) acrylate,
Allyl (meth) acrylate, (meth) acrylic acid and other (meth) acrylic acid and (meth) acrylic acid ester-based monomers; acrylamide, acrylonitrile, vinyl acetate, maleic anhydride, methyl vinyl ketone, N-vinylcarbazole Radical polymerizable monomers such as These monomers may be used alone or in combination of two or more. The amount of the vinyl-based monomer used is in the range of 20 to 99 parts by weight. When it is less than 20 parts by weight, storage stability and physical properties are difficult to balance, and when it is 99 parts by weight or more, the content of other components is small. It is not preferable.

In the present invention, the acrylic polyol (A) can be produced by a known method such as solution, bulk or suspension polymerization. However, from the viewpoint of ease of synthesis, an azo radical such as azobisisobutyronitrile is used. Most preferably, it is produced by a solution polymerization method using an initiator. Typical solvents used in solution polymerization are toluene,
Hydrocarbons such as xylene, n-hexane, cyclohexane and octane; alkyl alcohols such as methanol, ethanol, i-propanol, n-butanol, i-butanol, sec-butanol and octanol;
Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Glycols such as propylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate;
Acetic acid esters such as methyl acetate, ethyl acetate, butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, methyl acetoacetate, ethyl acetoacetate, cyclohexanone, ethyl ether, butyl ether, dioxane, furan, tetrahydrofuran. There are ethers. Further, if necessary, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl. The molecular weight can be adjusted by using a chain transfer agent such as methyldiethoxysilane. In the present invention, the organosilicon compound represented by the following general formula (I) and / or its partial hydrolysis-condensation product is an essential component.

[0012]

[Chemical 4]

R in the general formula (I) is a hydrocarbon group having 1 to 8 carbon atoms, and among them, when it is an alkyl group having 1 to 3 carbon atoms, that is, the organic silicon of the general formula (I). When tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane are specifically used as the compound, a coating film having a particularly high hardness can be obtained.
When tetramethoxysilane is used among these organic silicon compounds, a coating film having extremely high hardness can be obtained.

The tetramethoxysilane is obtained by a method such as a silicon tetrachloride method in which silicon tetrachloride is reacted with methanol, a direct method in which metal silicon is reacted with methanol, and / or partial hydrolysis thereof. Condensates can be used, but impurities can be easily removed by refining the raw materials, and hydrochloric acid does not form as a by-product, and the problem of equipment corrosion does not occur, so it is necessary to remove impurities. For the above, it is preferable to use tetramethoxysilane obtained by a direct method of reacting metallic silicon and methanol, and / or a partial hydrolysis-condensation product thereof. For example, a coating liquid having a chlorine content of 1 to 2 ppm or less can be easily obtained by using tetramethoxysilane and / or its partial hydrolysis-condensation product obtained by the direct method.

When obtaining an organosilicon compound other than tetramethoxysilane, the reaction using various alcohols or the esterification of tetramethoxysilane and / or its hydrolyzed condensate with various alcohols is carried out according to the above method. A manufacturing method in which an exchange reaction is performed can be adopted. When tetramethoxysilane is used as the organosilicon compound, the tetramethoxysilane monomer itself attacks the cornea of the eye,
It has been suggested that vapor is also highly toxic, causing injury. Further, since the activity is high, heat may be generated during work and bumping may occur. Furthermore, the performance of a coating liquid containing a large amount of monomer tends to gradually change due to the reaction of the monomer during storage.

Therefore, when tetramethoxysilane is used as the organosilicon compound, a partial hydrolysis-condensation product (hereinafter referred to as tetramethoxysilane oligomer) obtained by partially hydrolyzing and condensing the tetramethoxysilane is used.
It is possible to provide a coating liquid that can deal with these problems, exhibit excellent coating film characteristics for a long period of time, reduce toxicity, and have excellent workability.

The hydrolysis-condensation reaction itself for obtaining the partially hydrolyzed condensate of the organosilicon compound can be carried out by a known method. For example, when tetramethoxysilane is used as the organosilicon compound, tetramethoxysilane In the presence of an acid catalyst, a predetermined amount of water is added to the monomer, while the by-produced alcohol is distilled off, usually at about room temperature to 100
React at ℃. In this reaction, alcohol such as methanol may be used as a solvent. The methoxysilane is hydrolyzed by this reaction, and a liquid tetramethoxysilane oligomer having two or more hydroxyl groups by a condensation reaction (usually an average degree of polymerization of about 2 to 8, most of which is about 3 to
7) is obtained as a partially hydrolyzed condensate. The degree of hydrolysis can be appropriately adjusted depending on the amount of water used, and the amount of water required to hydrolyze and condense all the hydrolyzable groups, that is, alkoxy groups of the organosilicon compound, that is, the moles of these groups. It is represented by the actual amount added to water having a mole number of 1/2 of the number. The degree of hydrolysis of the tetramethoxysilane oligomer is usually selected from about 20 to 80%, preferably about 30 to 60%. When it is 20% or less, the residual monomer ratio is high and the productivity is low. If it is 80% or more, the obtained tetramethoxysilane oligomer tends to gel.

The water used in the present invention is not particularly limited and may be tap water, but depending on the purpose and application, it may be desirable to use dechlorinated water or ultrapure water, so it may be appropriately selected. For example, demineralized water when used for applications such as base materials such as mild steel, copper, aluminum, etc., which are particularly susceptible to corrosion by acids, electronic base materials such as heat resistant films, moisture resistant films, barrier resistant films such as chemical resistant films, and electrical insulation films. Alternatively, ultrapure water can be used when impurities are not desired to be mixed in, such as for semiconductors.

Tetramethoxysilane thus obtained
The oligomer usually contains about 2 to 10% of the monomer. When this monomer is contained, the storage stability of the coating liquid is poor, the viscosity may increase during storage, and it may be difficult to form a coating film. Therefore, the content of the monomer is 1% by weight or less, preferably 0.3%. It is advisable to remove the monomers so that the weight is not more than%. This monomer removal can be carried out by flash distillation, vacuum distillation, inert gas blowing, or the like. Even when an organosilicon compound other than tetramethoxysilane is used to form a partially hydrolyzed condensate, the hydrolysis reaction and the like can be carried out by an operation according to the above method.

In the present invention, the above-mentioned organosilicon compound and / or its partial hydrolyzed condensate can be theoretically hydrolyzed and condensed by 100% (hereinafter referred to as "hydrolyzed 10").
More water is added (referred to as 0% equivalent of water). That is, it is water in an amount equal to or more than the amount necessary for hydrolytically condensing all the hydrolyzable groups of the organosilicon compound, that is, the alkoxy groups. The same applies when a partially hydrolyzed condensate of an organosilicon compound is used, and water is added in an amount equal to or more than the amount necessary for hydrolytically condensing the remaining alkoxy groups.

As described above, any amount may be used as long as the hydrolysis is 100% equivalent or more.
The amount is 1 to 4 times, more preferably 1 to 2 times, and particularly preferably 1 to 1.5 times the% equivalent. The amount of water is 100% hydrolyzed
If it exceeds 4 times the equivalent weight, the storage stability of the coating solution may be lowered in some cases. Also, hydrolysis 1
If it is less than 00% equivalent, the physical properties of the coating film such as hardness are not sufficient.

In the present invention, a diluent can be further added. The addition of the diluent improves the storage stability of the obtained coating liquid. As the diluent, one of alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers, etc. may be used depending on the purpose.
One kind or a mixture of two or more kinds is used.

As the alcohol, methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, octanol, n-propyl alcohol, acetylacetone alcohol, etc., and as the glycol derivative, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether Examples thereof include ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like.

The hydrocarbons include benzene, kerosene,
Toluene, xylene, etc. can be used, and as esters,
Methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like can be used. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetylacetone, and ethers such as ethyl ether, butyl ether, dioxane, furan and tetrahydrofuran can be used.

Among these solvents, alcohols, especially C
₁ -C ₄ methanol, ethanol, preferably from the isopropanol or butanol good storage stability in is liquid is easy to handle, also the properties of the resulting coating film is excellent. Furthermore, by using methanol or ethanol among these, a coating film having extremely high hardness can be easily obtained.

When an organic solvent such as alcohol is used as the diluent, the amount of the solvent to be blended is 50 with respect to 100 parts by weight of the organosilicon compound and / or its partial hydrolysis-condensation product.
Up to 5000 parts by weight, preferably 100 to 1000 parts by weight. When the amount is 50 parts by weight or less, the storage stability of the coating solution is lowered, and gelation easily occurs. If it exceeds 5000 parts by weight, the thickness of the coating film becomes extremely thin.

In the present invention, a curing catalyst can be added if necessary. Examples of the catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid,
Organic acids such as phthalic acid and maleic acid, potassium hydroxide,
Sodium hydroxide, calcium hydroxide, an alkali catalyst such as ammonium, an organic metal, a metal alkoxide, for example, an organic tin compound such as dibutyltin dilaurylate, dibutyltin dioctiate, dibutyltin diacetate,
Aluminum tris (acetylacetonate), titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), zirconium Bis (butoxy) bis (acetylacetonate) and zirconium bis (isopropoxy)
There are metal chelate compounds such as bis (acetylacetonate), boron butoxide, boron compounds such as boric acid, etc., but the storage stability of the coating solution and the hardness and flexibility of the resulting coating film are excellent. Therefore, it is preferable to use one or more of organic acids such as acetic acid, maleic acid, oxalic acid, and fumaric acid, metal chelate compounds, boron compounds, and metal alkoxides.

It should be noted that the type of catalyst desired is the diluent used,
It can be appropriately selected depending on the type of the substrate to be coated and the application. For example, when a strong acid such as hydrochloric acid or nitric acid is used as a catalyst, the solution has good storage stability, the time required for aging described below can be shortened, and the hardness of the obtained coating film is excellent, but particularly corrosion It may be better to avoid this for substrates that are easy to do.
On the other hand, for example, maleic acid has little fear of corrosion,
The aging time is relatively short, and the resulting coating film has particularly excellent properties such as hardness and storage stability in liquid, which is desirable.

When methanol or ethanol is used as a diluent, in addition to the above-mentioned acid catalyst, for example, aluminum tris (acetylacetonate), titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetate). ), Titanium bis (isopropoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate) and zirconium bis (isopropoxy).
Even when a metal acetylacetonate compound such as bis (acetylacetonate) is used, a coating film having sufficient hardness can be obtained without impairing the storage stability in a liquid.

The amount of these catalyst components added is not particularly limited as long as it can exhibit the function as a catalyst, but usually 100 parts by weight of the organosilicon compound and / or its partial hydrolysis-condensation product is used. On the other hand, it is selected from the range of about 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight. The method of blending these components is not particularly limited, and a more uniform blend may be prepared by, for example, using a catalyst component dissolved in water in advance, or blending with stirring. When a catalyst that is easily decomposed by water or other solvent is used, it is preferable to mix this with the organosilicon compound and / or its partial hydrolysis-condensation product, and mix with water or other solvent before use. Further, the catalyst component may be added to other components when used.

In the present invention, the liquid mixture obtained by mixing these components is aged. By passing through the aging step, the partial crosslinking reaction due to hydrolysis and condensation of the organosilicon compound and / or its partial hydrolysis-condensation product sufficiently progresses, and the fine particles described later are formed. Would be excellent.

The maturing liquid may be aged by allowing the liquid to stand.
You may stir. The time for standing is sufficient for the above-mentioned partial cross-linking reaction to proceed sufficiently to obtain the desired film properties, and depends on the type of diluent and the type of catalyst used. For example, when methanol or ethanol is used as the diluent, hydrochloric acid is sufficient at room temperature for about 1 hour or more, and maleic acid is for several hours or more, preferably about 8 hours to 2 days.

The time required for aging is also influenced by the ambient temperature, and it may be better to take measures such as heating up to about 20 ° C. in an extremely cold region. Generally, aging proceeds rapidly at high temperatures, but gelation occurs when heated to 100 ° C. or higher, so heating to 50 to 60 ° C. is suitable at most.

By sufficiently aging, whitening and peeling of the obtained film can be prevented. In general, aging is sufficient if the reaction mixture is allowed to cool to room temperature after the exothermic heat of hydrolysis is completed and left to stand for a time to complete the partial crosslinking reaction. The compounded liquid of the present invention that has thus been aged (hereinafter,
In the "aged product"), it is possible to form fine particles having an inertial radius of 10 Å or less (hereinafter referred to as "reactive ultrafine silica"), which can be easily confirmed by means such as small-angle X-ray scattering. You can That is, due to the presence of fine particles, the diffraction intensity distribution of the incident X-ray shows diffuse scattering called central scattering in the incident ray direction, that is, small-angle X-ray scattering. The scattering intensity I is given by the following Guinier equation.

[0035] ^{I = Cexp (-H 2 Rg 2} /3) (I:
Scattering intensity, H: Scattering vector (= 2πsin2θ /
π), Rg: radius of gyration of fine particles, C: Const,
λ: incident X-ray wavelength, 2θ: divergence angle) Taking the common logarithm of both sides of the above Guinier equation,
^{logI = logC- (H 2 Rg 2} /3) next, therefore, if there is fine particles, the scattering intensity was measured by plotting the logarithmic scale for the scattering vector, by determining the slope, the inertia of the fine particle radius Can be asked.

When measuring the radius of gyration, some measurement errors may occur depending on the concentration of the liquid to be measured. The reactive ultrafine silica of the present invention has a radius of inertia of 10 Å or less when measured at a silica conversion concentration of 0.3% for the sake of accuracy. Especially when hydrolysis is carried out in the presence of an organic solvent such as ethanol when adding 100% equivalent or more of water for hydrolysis, the reactive ultrafine silica obtained has a radius of gyration of 6 Å even under the above measurement conditions. The following can be made extremely minute.

The reactive ultrafine silica of the present invention is G
The weight average molecular weight measured by PC is about 1000 to 3000 in terms of standard polystyrene. Further, most of these have a weight average molecular weight of about 1300 to 2000. The molecular weight of the reactive ultrafine silica particles obtained is slightly different depending on the conditions when the hydrolysis and condensation are carried out by adding 100% equivalent of water, and the molecular weight of the reactive ultrafine silica obtained is slightly different. When hydrolyzed in the presence, the weight average molecular weight is 1300 to 18
00, preferably in the range of about 1600 to 1800. (Note that the molecular weight described above is a weight average molecular weight determined by standard polystyrene conversion based on the value measured by GPC.)

As described above, the reactive ultrafine silica of the present invention has an extremely small radius of gyration relative to its molecular weight, and is therefore assumed to have an ultradense structure. , A unique form of silica. Moreover, the reactive ultrafine silica of the present invention has a large number of reactive functional groups such as a hydroxy group and an alkoxy group. For example, when the hydrolysis is carried out by adding 100% equivalent of water of hydrolysis in the presence of ethanol using an oligomer or monomer of tetramethoxysilane as a diluent, the reactive ultrafine silica obtained has a hydroxyl group as a reactive functional group. , A methoxy group, and an ethoxy group. For example, the number of moles of hydroxyl group is 0.6 times or 0.7 times, more than 0.8 times or more the total number of moles of methoxy group and ethoxy group, and the number of moles of ethoxy group is 1.5 times that of methoxy group. And even 2
It is also possible to easily form a reactive ultrafine silica having a double or more. As described above, the reactive ultrafine silica of the present invention having a large variety of reactive functional groups is highly reactive, and the aged product of the present invention containing the silica is a coating liquid prepared by blending the above-mentioned acrylic polyol (A). In this case, the cross-linking speed is high, the cross-linking density is increased, and a coating film exhibiting extremely excellent properties such as high hardness is formed.

In the coating liquid of the present invention, since the hydrolyzed condensate of the organosilicon compound forms such fine particles, the cross-linking reactivity between the components during film formation is excellent, for example, even at room temperature. It is curable and can be formed outdoors.

The above-mentioned acrylic polyol (A) is added to the aged product thus obtained. The addition amount of the acrylic polyol (A) is 5 to 1 with respect to 100 parts by weight of the organosilicon compound and / or its partial hydrolysis-condensation product.
900 parts by weight, preferably 25 to 400 parts by weight is suitable. In terms of SiO _{2 in the} film, it is preferable to adjust SiO _{2 to} 86 to 1% by weight, preferably 56 to 7.4% by weight. If it is 5 parts by weight or less, cracks are likely to occur in the obtained coating film. If it is 199 parts by weight or more, the hardness of the obtained coating film tends to be low.

Further, the above-mentioned acrylic polyol (A)
May be used alone or in combination of two or more depending on the purpose. When used in combination, two or more kinds may be preliminarily blended, or each may be added to an aged formulation liquid. When the acrylic polyol (A) is added to the aged product, a solvent, a curing catalyst, and other additives may be added together or afterward, if necessary.

For example, in the case of the film formation described below, particularly in the case of the spray method or the dip method, in order to prepare a coating liquid having a viscosity and a non-volatile component content depending on the physical properties of the target film such as coating conditions and film thickness, these solvents are used. Can be added. As the solvent, those having compatibility with both the aged product and the acrylic polyol (A) are suitable, and for example, one kind of alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers, or Two
More than one species can be used in combination.

Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, and octanol, and examples of glycol derivatives include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene. Glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate Etc. The.

The hydrocarbons include benzene, kerosene,
Toluene, xylene, etc. can be used, and as esters,
Methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like can be used. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetylacetone, and ethers such as ethyl ether, butyl ether, methyl cellosolve, ethyl cellosolve, dioxane, furan and tetrahydrofuran can be used.

Moreover, in general, it may be appropriately selected depending on the use conditions, desired film characteristics, and the like. Depending on the usage conditions, the type of acrylic polyol (A), the amount used, etc.,
Although there are many functional groups, it may be desirable to further add a catalyst to improve the curing rate after film formation, but in general, the catalyst added at the time of aging after compounding is sufficient.

The amount of the catalyst component added at this time is not particularly limited as long as it can exhibit the function as a catalyst, but it is usually an organosilicon compound and / or its partial hydrolysis-condensation product and acryl. -Mixture 1 of polyol (A)
It is selected from the range of about 0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight, relative to 00 parts by weight. still,
The order of addition when these solvents and catalysts are used is not particularly limited, and may be added to the aged product at the same time as the acrylic polyol (A), or may be added after mixing, mixing, leaving and the like. .

The coating liquid of the present invention thus obtained is used to form a film on a substrate such as a polymer, metal or ceramic or a wire material by an impregnation method, a spin coater method, a spray method or the like, or by mixing with a powder to form a film. . After being cured at room temperature or left as a solvent removal treatment at room temperature for 1 to 10 minutes, it is cured by heating at 20 ° C or higher. The heating furnace may be a general-purpose furnace such as a gas furnace or an electric furnace.

According to the coating liquid of the present invention,
Since the hydrolyzed condensate of the organosilicon compound forms fine particles with sufficient aging and has a large number of hydroxyl groups, it has good compatibility with acrylic polyols, and the progress rate and extent of the crosslinking reaction are high. Very good. Therefore, if a drying process is performed at room temperature and a desolvation process is performed without requiring a heating process, a crosslinking reaction of each component in the liquid also proceeds, and a coating film having a sufficiently high hardness can be obtained. It is also suitable for use in.

Further, since the coating liquid of the present invention has good recoatability, it may be dried and then recoated depending on the application, but according to the coating liquid of the present invention, it is applied once. It is possible to obtain a film thickness of 10 μm or more. The coating itself can be performed by a conventional method, and the film thickness can be appropriately selected.

The film thickness can be selected by a conventional method. For example, the concentration of the non-volatile components in the liquid, the viscosity of the liquid, the pulling rate in the dip method, the jetting time in the spray method, etc. can be adjusted, and re-coating can be performed. It can be selected by doing. Furthermore, the obtained film thickness can be appropriately changed by adjusting the type of acrylic polyol and the addition amount thereof.
The coating liquid of the present invention has a pot life of 2 weeks or more, can be formed into a film without thickening, has high coating hardness after film formation, is flexible, and is extremely excellent in stain resistance. It has the characteristic of being

[0051]

EXAMPLES The present invention will be described in more detail below with reference to examples. Parts and% are parts by weight and% by weight, unless otherwise specified. (1) Synthesis of oligomer 500 equipped with stirrer, reflux condenser and thermometer
In a ml four-neck round bottom flask, add tetramethoxysilane 2
After adding 34 g and 74 g of methanol and mixing, 0.0
22.2 g of 5% hydrochloric acid was added, and a hydrolysis reaction was carried out at an internal temperature of 65 ° C. for 2 hours.

Then, replace the condenser with a distilling pipe,
The temperature was raised until the internal temperature reached 130 ° C., and methanol was distilled off. Thus, a partially hydrolyzed condensate (hereinafter referred to as "tetramethoxysilane oligomer") was obtained (partial hydrolysis rate 40%). An oligomer having a degree of polymerization of 2 to 8 was confirmed, and the weight average molecular weight was 550. The amount of monomer in the tetramethoxysilane oligomer was 5%. Subsequently, the tetramethoxysilane oligomer was placed in a flask heated to 130 ° C., the vaporized monomer was discharged out of the system together with an inert gas, and the temperature was raised to 150 ° C. and maintained for 3 hours. The amount of monomers in the tetramethoxysilane oligomer obtained after removing the monomers was 0.2%.

(2) Synthesis of Acrylic Polyol Production Example 1 Synthesis of Acrylic Polyol (A-1) 510 parts of i-propyl alcohol was placed in a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet tube. , And after heating to 80 ° C., 278 parts of i-butyl methacrylate,
A mixed monomer solution prepared by dissolving 6 parts of azobismethylbutyronitrile in 126 parts of n-butyl metalylate and 196 parts of 2-hydroxyethyl methacrylate was dropped into a reaction vessel over 4 hours, and after completion, azobisisobutyro Polymerization was terminated by adding 1.2 parts of nitrile in 3 portions at intervals of 1 hour. The resulting copolymer has a hydroxyl value of 140 mgK
OH / g, GPC weight average molecular weight 17,30
It was 0. Finally, 90 parts of i-propyl alcohol was added and diluted to obtain a hydroxyl group-containing acrylic polyol solution (A-1) having a solid content of 49.6%.

Production Example 2 Acrylic polyol (A-
Synthesis of 2) i-Propyl alcohol (510 parts) was charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas introduction tube, and the temperature was raised to 80 ° C, and then 189 parts of i-butyl methacrylate,
A mixed monomer solution prepared by dissolving 6 parts of azobismethylbutyronitrile in 132 parts of n-butyl metalylate and 279 parts of 2-hydroxyethyl methacrylate was dropped into the reaction vessel over 4 hours, and after the completion, azobisisobutyro Polymerization was terminated by adding 1.2 parts of nitrile in 3 portions at intervals of 1 hour. The resulting copolymer has a hydroxyl value of 200 mgK
OH / g, weight average molecular weight by GPC is 15,000
It was 0. Finally, 90 parts of i-propyl alcohol was added and diluted to obtain a hydroxyl group-containing acrylic polyol solution (A-2) having a solid content of 50.2%.

Production Example 3 Acrylic polyol (A-
Synthesis of 3) i-Propyl alcohol (510 parts) was charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas introduction tube, and the temperature was raised to 80 ° C., and then 480 parts of i-butyl methacrylate,
A mixed monomer solution prepared by dissolving 6 parts of azobismethylbutyronitrile in 120 parts of n-butyl metalylate was dropped into a reaction vessel over 4 hours, and after the completion, 1.2 parts of azobisisobutyronitrile was added to 1 part. Add it in 3 portions at intervals of time,
The polymerization was terminated. The resulting copolymer has a hydroxyl value of 0 m
gKOH / g, the weight average molecular weight by GPC is 15,
It was 200. Finally, i-propyl alcohol 90
A portion was added and diluted to obtain a hydroxyl group-containing acrylic polyol solution (A-3) having a solid content of 49.3%.

Production Example 4 Acrylic polyol (A-
Synthesis of 4) i-Propyl alcohol (510 parts) was charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas introducing tube, and the temperature was raised to 80 ° C.
A mixed monomer solution prepared by dissolving 6 parts of azobismethylbutyronitrile in 138 parts of n-butyl metalylate and 348 parts of 2-hydroxyethyl methacrylate was dropped into a reaction vessel over 4 hours, and after completion, azobisisobutyro Polymerization was terminated by adding 1.2 parts of nitrile in 3 portions at intervals of 1 hour. The resulting copolymer has a hydroxyl value of 250 mgK
OH / g, GPC weight average molecular weight 17,30
It was 0. Finally, 90 parts of i-propyl alcohol was added and diluted to obtain a hydroxyl group-containing acrylic polyol solution (A-4) having a solid content of 50.7%.

Example 1 (Preparation of coating liquid and formation / evaluation of coating film) 62.4 g of ethanol was added to 30.8 g of the tetramethoxysilane oligomer obtained in the above (1) Synthesis of oligomer, and then aluminum tris was added. 0.3 g of (acetylacetonate) and 6.57 g of dechlorinated water were added. The amount of water added is 114% with respect to the amount which theoretically completely hydrolyzes the tetramethoxysilane oligomer. Aged at room temperature for 1 day for aging.

78 parts of the aged product thus obtained was mixed with 100 parts of the acrylic polyol (A-1) obtained in Production Example 1, thinner was added, and Ford Cup N was added.
o. After diluting to 4 seconds for 12 seconds, degreased aluminum plate (material A1050, plate thickness 0.8 mm), glass plate, SPCC plate are coated with a 150 μm applicator so that the dry film thickness is 1 to 200 μm, and 150 ° C. After drying for 2 hours, an evaluation test of coating film physical properties was performed.

(Confirmation of Fine Particles) (1) The test after removing the monomer obtained in the synthesis of the oligomer.
Ethanol added to 34.99 g of tramethoxysilane oligomer
And then maleic acid 0.38
g and 8.32 g of dechlorinated water were added. The amount of water added is
Theoretically complete hydrolysis of tramethoxysilane oligomer
It is 127% of the amount to be solved. Aging at room temperature for 2 days
The liquid obtained by (composition A, SiO₂ 16 weight equivalent
%, 8.1 vol%), and about 4 times this with ethanol
Liquid diluted to (composition B, SiO ₂ Converted concentration 4.3 weight
%, 2 vol%) under the following conditions
An analysis by disturbance was performed.

Measuring apparatus: Kratonki compact camera manufactured by Anton Paar Co., Ltd. X-ray source: 50 kV, 200 mA, Cu-Kα ray is mono-colored by Ni-filter. Optical system condition: Distance between sample and light receiving slit = 20c
m vacuum inside path = 19cm entrance slit = 80μm, light receiving slit = 200μm, beam
length = 16 mm Sample cell: Quartz capillary (diameter about 1 mm, wall thickness 10 μm) Other conditions: room temperature. Step scan method operation range 2θ = 0.086 to 8.1 deg 90 sec / po
Int data correction: Background correction was carried out by using scattering when the quartz capillary was filled with water. X-ray absorption correction was also performed. Analysis software: Analysis software ITP-81 (0.Glatter; J.App) for slit correction and inverse Fourier transform.
l. Cryst. ; 10 . 415-421 (1977)
by. )It was used.

FIGS. 1 and 2 show measured data (background correction and absorption correction) of the scattering intensity of the composition A and the composition B with respect to the moving distance of the scattered X-rays in the light receiving slit. FIG. 3 and FIG. 4 show point beam data after slit correction of the composition A and the composition B.

From these FIG. 3 and FIG. 4, Guinie
Formula of r I = C exp (-H² Rg ² / 3) (I: scattering
Intensity, H: Scattering vector (= 2πsin2θ / π), R
g: radius of gyration, C: const, λ: Cu-Kα ray wave
Length, 2θ: spread angle) to find the maximum value of the radius of gyration
As shown in FIG. 5 and FIG.
Then, assuming that it has a spherical shape, the real radius R = (5 /
3)^1/2 From composition Rg, radius 9.0Å) For composition B
It was 6.0Å (radius 7.7Å assuming a sphere).
In addition, the inverse Fourier transform of Fig. 3 and Fig. 4 is performed, and the radius (sphere
Figure 7 and Figure-8 show the results of the distribution of
You. The maximum radii were about 6Å and 7Å, respectively.

The tetramethoxysilane oligomer obtained by the synthesis of the oligomer (1) after the monomer was removed was analyzed by small-angle X-ray scattering under the same conditions. Fig. 9 shows the measurement data of the scattering intensity. As is clear from this, the structure of fine particles etc. was not recognized.

(Measurement of Molecular Weight) The molecular weight of the composition A was measured under the following conditions. Deaerator: Shodex DEGAS (Showa Denko) Pump: Shimadzu LC6A (Shimadzu) Incubator: Nishio Kogyo Column: Tosoh TSK-GEL for
GPC G-4000H, G-2000H, G-1000H (manufactured by Toyo Soda) Detector: Shodex RI SE-51 (refractive index detector) (manufactured by Showa Denko) Data collector: Shimadzu C-R3A (manufactured by Shimadzu Corporation) Data Treatment: PC (PC-9801 system) Column temperature: 40 ° C. Injection temperature: Room temperature Pump temperature: Room temperature Solvent: Tetrahydrofuran, 1.0 m
l / min Molecular weight calculation method: Standard polystyrene conversion results are shown below.

No. (Spiked molecular weight) Number average Weight average Mw / Mn Area% 1 22.62 min 816 1327 1704 1.28 -73.12 2 23.02 min 676 567 583 583 1.03 -24.01 3 26.02 min 236 269 271 1.01 -2.34 4 26.15 min 228 221 222 1.00 -0.18 5 26.6 2 minutes 204 194 194 1.00 -0.35 6 27.15 minutes 182 182 182 1.00 -0.00 7 27.18 minutes 181 181 181 1.00 0.00 ────────────────────────── ─────────── 919 1393 1.52 When the chlorine concentration of this composition A was measured, it was 1.5 pp.
It was m or less.

(Measurement of Amount of Reactive Functional Group) The aged product thus obtained was sealed and allowed to stand at room temperature for 13 days, and then methanol and ethanol in the liquid were subjected to gas chromatography and water in the liquid was curled. The amount of reactive functional groups contained in the reactive ultrafine silica particles in the aged product was calculated by measuring by Fisher analysis. The analysis conditions are as follows:

Gas chromatography analysis conditions: Injection temperature: 180 ° C. Column temperature: 180 ° C. TCD (detector): 200 ° C. Carrier gas: He 40 ml / min Current current: 100 mA Filler: Porapaq type Q

As a result, the amount of methanol in the liquid was 18.9.
% (0.591 mol), the amount of ethanol is 57.1%
(1.241 mol), the amount of water is 1.15% (0.06
39 mol), the amount of water consumed is 0.3
It became 041 mol. Therefore, when the amount of the reactive functional group possessed by the reactive ultrafine silica particles in the aged product is calculated,
Methoxy group 13.2 mol%, ethoxy group 40.3mo
1% and silanol groups were 46.0 mol%.

Examples 2 to 4 and Comparative Examples 1 to 2 In the same manner as in Example 1, the acrylic polyols (A-2 to 4) shown in Tables 1 and 2 and the aged product obtained in Example 1 were used. The composition, dilution and coating were applied and evaluated. * 1 A load of 500 g was applied to 1 cm ² of absorbent cotton impregnated with xylene to rub the coating film, and the appearance after 100 times was observed. * 2 A 5% sulfuric acid aqueous solution was spotted and the appearance of the coating film was observed after 15 hours. * 3 Performed according to the pencil scratch test according to JIS K5400, item 6-14. * 4 100 1 mm square Gobang eyes were made, and the number of unpeeled eyes after the tape was peeled off was recorded. * 5 Seal the formulation and immerse it in 40 warm water until gelation (days).

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

According to the present invention, a coating capable of obtaining a thick film having excellent storage stability in a liquid and excellent film properties such as stain resistance, scratch resistance, solvent resistance, and chemical resistance. A liquid can be obtained.

[Brief description of drawings]

FIG. 1 is measurement data of scattering intensity of composition A in Example 1.

FIG. 2 is the measurement data of the scattering intensity of composition B in Example 1.

FIG. 3 is point beam data after slit correction of composition A in Example 1.

FIG. 4 is point beam data after slit correction of composition B in Example 1.

5 is a distribution of radius of gyration of fine particles in composition A in Example 1. FIG.

6 is a distribution of radius of gyration of fine particles in composition B in Example 1. FIG.

7 is a distribution of assumed spherical spheres of fine particles in the composition A in Example 1. FIG.

8 is a distribution of assumed spherical spheres of fine particles of composition B in Example 1. FIG.

FIG. 9: Measurement data of scattering intensity of tetramethoxysilane oligomer obtained in Example 1 (1) oligomer synthesis.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsuji Kido 4-chome 1-60 Sunadabashi, Higashi-ku, Nagoya City Mitsubishi Rayon Co., Ltd. Product Development Laboratory (72) Inventor Takeshi Sawai 1-1, Kurosaki Shiroishi, Hachiman Nishi-ku, Kitakyushu Mitsubishi Chemical Co., Ltd. Kurosaki R & D Laboratory (72) Inventor Hozumi Endo 1-1, Kurosaki Shiroishi, Hachimannishi-ku, Kitakyushu Mitsubishi Chemical Co., Ltd. Kurosaki R & D Laboratory (72) Inventor Nobuyuki Matsuzoe 2-5-2 Marunouchi, Chiyoda-ku, Tokyo No. Sanryo Chemical Co., Ltd. New Business Development Room

Claims (13)

[Claims] 1. (a) Hydroxyl group-containing monomer 1 to 1
80% by weight, and (b) 20% to 99% by weight of a vinyl-based monomer copolymerizable therewith, an acrylic resin.
A hydrolyzate obtained by adding the polyol (A), an organosilicon compound represented by the following general formula (I) and / or a partial hydrolyzed condensate thereof to a theoretically 100% or more hydrolyzable and condensable amount of water. A coating liquid containing a decomposition condensate (B). Embedded image 2. The coating liquid according to claim 1, wherein the hydroxyl value of the acrylic polyol (A) is 5 to 220 mgKOH / g. 3. The Tg of the acrylic polyol (A) is-
The coating liquid according to claim 1 or 2, which has a temperature of 10 to 60 ° C. 4. The coating liquid according to claim 1, wherein the acrylic polyol (A) has a weight average molecular weight of 5,000 to 50,000. 5. The coating liquid according to any one of claims 1 to 4, wherein the acrylic polyol (A) contains 15 to 85% by weight of a methacrylic alkyl ester having an alkyl group having a carbon number of C _{1 to} C _4. . 6. The coating liquid according to claim 1, wherein the acrylic polyol (A) contains 0 to 60% by weight of an acrylic alkyl ester whose alkyl group has a carbon number of C _{1 to} C _4. . 7. The coating liquid according to claim 1, wherein the acrylic polyol (A) contains 1 to 80% by weight of a hydroxyalkyl methacrylate ester having an alkyl group having a carbon number of C ₄ or less. 8. The acrylic polyol (A) is obtained by solution polymerization in a solvent containing 5 to 100% by weight of an alkyl alcohol having an alkyl group of C ₄ or less.
~ The coating liquid according to any one of 7 to 7. 9. The coating liquid according to claim 1, wherein the organosilicon compound represented by the general formula (I) is tetramethoxysilane. 10. The organosilicon compound represented by the general formula (I) and / or its partial hydrolysis-condensation product is a tetramethoxysilane oligomer.
The coating liquid described. 11. The organosilicon compound represented by the general formula (I) and / or its partial hydrolysis-condensation product is a tetramethoxysilane oligomer, and the monomer content is 1% by weight or less. Item 10. The coating liquid according to item 10. 12. An organic silicon compound represented by the following general formula (I) and / or its partial hydrolysis-condensation product and a liquid containing water in an amount equal to or more than 100% of which can theoretically be hydrolyzed and condensed, a) Hydroxyl group-containing monomers 1-8
0% by weight, and (b) 20-99% by weight of a vinyl-based monomer copolymerizable therewith, and an acrylic polyol (A) formed by copolymerization, and a method for producing a coating liquid. Embedded image 13. A liquid containing fine particles having an inertia radius of 10 Å or less is added to (a) hydroxyl group-containing monomer 1 to 80.
%, And (b) a coating liquid obtained by blending the acrylic polyol (A) obtained by copolymerizing 20 to 99% by weight of a vinyl-based monomer copolymerizable therewith.