KR910009831B1 - Low-temperature curable composition - Google Patents

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Description

Low temperature curable composition

The present invention relates to novel curable compositions.

The compositions are already known to be prepared by mixing acids, bases, organometallic catalysts and the like with alkoxysilane-containing vinyl polymers and can be cured crosslinking at relatively low temperatures, ie from room temperature to 100 ° C. For example, Japanese Patent Laid-Open No. 60-67553 describes a composition containing a vinyl polymer containing an alkoxysilane such as methacryloxypropyltrimethoxysilane and an aluminum chelate compound mixed with a polymer.

However, conventional compositions have drawbacks. Since the silanol groups produced by hydrolysis of alkoxysilanes are the only crosslinking functional groups, the compositions require large amounts of water to cure. As a result, large amounts of by-products, such as alcohols, due to hydrolysis give impaired properties to the cured product. In addition, when the composition is cured in the condition that only water in the air is present, the composition is cured only on the contact surface with air and hardly cures the rest of the interior thereof. The product tends to shrink.

It is an object of the present invention to provide a novel low temperature curable composition which overcomes the above drawbacks.

Another object of the present invention is to provide a novel composition which can be completely cured at low temperatures with a small amount of water.

It is another object of the present invention to provide novel compositions which can be cured at low temperatures in order to obtain cured products of excellent properties.

It is another object of the present invention to provide a novel composition which can be cured at low temperatures with only moisture in the air without shrinkage, as the difference in the degree of curing between the surface and the interior is reduced, and can be easily applied to prepare a coating having an excellent appearance. To provide.

These objects and features of the present invention will become apparent from the following description.

The present invention provides a low temperature curable composition comprising the following (a) and (b).

(a) a copolymer containing an oxirane-containing vinyl monomer as the monomer component and an alkoxysilane-containing vinyl monomer of the following general formula (I) (hereinafter abbreviated as “copolymer X”) and as a monomer component iii) the following general At least two compounds prepared by reacting about 70 to about 99.999 mol% of compound (A) of formula (II) with about 30 to 0.001 mol% of compound (B) of formula (III) At least one of a polysiloxane high molecular weight monomer having a functional group of about 400 to about 100,000 and a vinyl copolymer containing (ii) an oxirane-containing vinyl monomer (hereinafter abbreviated as “copolymer Y”). A non-aqueous dispersion of particulate polymer insoluble in an organic liquid, prepared by polymerizing radical-polymerizable unsaturated monomers in an organic liquid in the presence of a dispersion stabilizer resin, and (b) a chelate compound.

(Where A is or R ₁ is a hydrogen atom or methyl, R ₂ is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ₃ and R ₄ are the same or different and each is phenyl, alkyl having 1 to 6 carbon atoms or 1 Alkoxyl having 10 to 10 carbon atoms, R ₅ is alkyl having 1 to 10 carbon atoms, R ₆ is an aliphatic hydrocarbon group or phenyl having 1 to 8 carbon atoms, and R ₇ , R ₈ and R ₉ are each 1 to 4 Alkoxyl or hydroxyl having carbon atoms, R ₁₀ is hydrogen or methyl, R ₁₁ , R ₁₂ and R ₁₃ are hydroxyl, alkoxyl having 1 to 4 carbon atoms or aliphatic hydrocarbon group having 1 to 8 carbon atoms, respectively At least one of R ₁₁ , R _12, and R ₁₃ is hydroxyl or alkoxyl, m is an integer from 1 to 6, and n is an integer from 1 to 10.

Research by the inventors has led to the above drawbacks of the prior art to prepare non-aqueous dispersions of the above-mentioned specific particulate polymers using at least one copolymer X and copolymer Y as dispersion stabilizer resins, and the chelate compounds are combined with the non-aqueous dispersions. It has been found that it can be overcome by mixing. This study also revealed the following facts.

(1) The alkoxysilane-containing vinyl polymer contains an oxirane group to provide not only the silanol group but also the oxirane as a crosslinking functional group so that the composition can be completely cured in the presence of a small amount of water.

(2) Thus, the composition forms a very reduced amount of alcohol and similar byproducts upon curing to produce a cured product having excellent properties.

(3) When only cured with moisture in the air, the composition is crosslinked due to the presence of silanol groups on the coated surface exposed to air and crosslinked in chain-like form throughout the interior due to the presence of oxirane groups. This reduces the difference in degree of cure between the surface and the interior and prevents shrinkage.

(4) The composition together with the particulate polymer present in the composition having good stability exhibits high storage stability and can be effectively applied.

(5) The particulate polymer present in the cured product gives the product an aesthetic appearance and enhances the product to impart improved properties.

The present invention has been completed based on this new finding.

The dispersion stabilizer resin used in the present invention will first be described.

In general formula (I) which shows one monomer component of copolymer X, n is an integer of 1-10.

In the general formula (I), the divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms and represented by R ₂ is methylene, ethylene, propylene, 1,2-butylene, 1,3-butylene, 2,3-butyl Linear or branched alkylene groups such as ethylene, tetramethylene, pentamethylene, hexamethylene and the like. Alkyl groups represented by R ₃ and R ₄ and having 1 to 6 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary-butyl, tert-butyl, n-pentyl, iso Linear or branched alkyl groups such as pentyl, neopentyl, n-hexyl, isohexyl and the like. Examples of the alkyl group having 1 to 10 carbon atoms and represented by R ₅ include the aforementioned alkyl group and n-heptyl, 1-methylpentyl, 2-methylhexyl, n-octyl, n-nonyl, n-decyl and the like. . The alkoxyl groups represented by R ₃ and R ₄ and having 1 to 10 carbon atoms are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secondary-butoxy, tertiary- Linear or branched alkoxyl groups such as butoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, n-octyloxy and the like. When n in formula (I) is at least 2, the groups R ₃ as well as the groups R ₄ may be the same or different.

Among the compounds of the general formula (I) used in the present invention, A is For example, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxyripropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, and γ- (meth) Acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (Meth) acryloxybutylphenyl diethoxysilane, (gamma)-(meth) acryloxybutylphenyl dipropoxysilane, (gamma)-(meth) acryloxypropyl dimethyl methoxysilane, (gamma)-(meth) acryloxypropyl dimethyl ethoxysilane , γ- (meth) acryloxypropylphenylmethylmethoxysilane, γ- (meth) acryloxypropylphenylmethylethoxysilane,

And so on.

In another compound of Formula (I), A is To be, for example,

And

to be.

The oxirane-containing vinyl monomer used is one of a variety of vinyl monomers having an oxirane group in the molecule.

In particular, it is preferable to use, for example, a vinyl monomer containing an alicyclic oxirane group in view of curability. Since the cycloaliphatic oxirane groups have high reactivity in the ring-cut polymerization reaction, the use of this monomer has the advantage that the curing can be accelerated and the coating can be given improved properties upon curing.

Preference is given to using acrylic or methacrylic acid esters containing alicyclic oxirane groups such as the following general formulas (IV) to (XV).

Wherein R ₁₄ is a hydrogen atom or methyl, R ₁₄ groups are the same or different, R ₁₅ is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ₁₅ groups are the same or different, and R ₁₆ groups are the same or Where k is an integer from 0 to 10.)

Examples of the divalent aliphatic saturated hydrocarbon group R ₁₅ having 1 to 6 carbon atoms include linear or branched alkylene groups such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene and hexamethylene. Examples of the divalent hydrocarbon group R ₁₆ having 1 to 10 carbon atoms include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene, Etc. can be mentioned.

As a typical vinyl monomer containing an oxirane group other than an alicyclic oxirane group, the compound of the following general formula (XVI) is mentioned.

Wherein R ₁₄ and R ₁₅ are the same as defined above.

Specific examples of the compound (XVI) include glycidyl methacrylate, glycidyl acrylate, methylglycidyl methacrylate, methylglycidyl acrylate and the like.

Incorporating a mixture with at least two alicyclic oxirane groups in the molecule as described below can result in improved curability of the composition, while using monomer (XVI) as the oxirane-containing monomer, the composition is characterized by monomers (IV) to ( It should be fired at slightly higher temperatures than when using XV).

Copolymer X used as its resin component in the curable composition of the present invention is an alkoxysilane-containing vinyl monomer (I) (hereinafter abbreviated as “monomer A”) and its oxirane-containing monomer (hereinafter “monomer B”). (Abbreviated as ”). Therefore, Copolymer X consists essentially of Monomer A and Monomer B. The ratio of monomer A to monomer B, ie A: B, is generally in a ratio of from 1: about 0.02 to about 10,000 weight. If monomer B is present in a larger fraction than this range, the curability is reduced, while monomer B is present in a fraction smaller than this range, which is undesirable since shrinkage is increased to give a cured product of impaired properties. The A: B ratio is preferably 1: about 0.1 to about 1,000 weight ratio, more preferably about 1: about 0.25 to about 100 weight ratio.

Copolymer X may be prepared by a general production method under conventional conditions.

α, β-ethylenically unsaturated monomers may be used as the optional monomer component of one of copolymers X. Such monomers can be selected from various compounds depending on the desired properties. Typical examples of such unsaturated monomers are as follows.

(1) esters of acrylic acid or methacrylic acid

Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, iso C ₁ to C ₁₈ alkyl esters of acrylic acid or methacrylic acid such as propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate and lauryl methacrylate; C ₂ to C of acrylic or methacrylic acid such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate and ethoxybutyl methacrylate ₁₈ alkoxy alkyl esters; C ₂ to C ₈ alkenyl esters of acrylic acid or methacrylic acid such as allyl acrylate and allyl methacrylate; C ₂ to C ₈ hydroxy alkylesters of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; Addition products of the aforementioned hydroxyalkyl esters of acrylic or methacrylic acid with polycaprolactone; And C ₃ to C ₁₈ alkenyloxyalkyl esters of acrylic acid or methacrylic acid such as allyloxyethyl acrylate and allyloxyethyl methacrylate.

(2) vinyl aromatic compounds

Styrene, α-methylstyrene, vinyltoluene and p-chlorostyrene

(3) polyolefin compounds

Butadiene, isoprene and chloroprene

(4) other

Acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, beova monomer (manufactured by Shell Chemical), vinyl propionate, vinyl pivalate and the like.

As well as these monomers (1)-(4), for example, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-methylol acrylamide butyl ether, dimethylamino Ethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid allyl alcohol, maleic acid and fumaric acid can be used. This monomer can be used in an amount which does not gel the dispersion stabilizer.

In order to give copolymer X an improved ability to be used as a dispersion stabilizer, its monomer component is at least about based on the total amount of all monomers of monomers in the form of methacrylic acid or esters of acrylic acid with C ₄ to C ₁₈ monoalcohols. It is preferred to contain 20 to about 95% by weight, preferably at least about 40 to about 90% by weight.

Another copolymer Y contains polysiloxane high molecular weight monomer as its monomer component. This high molecular weight monomer has a main skeleton of a siloxane bond having an aliphatic hydrocarbon group, phenyl, hydroxyl, alkoxyl, polymerizable unsaturated bond, or the like, directly or bonded to Si of the siloxane bond. A high molecular weight monomer is obtained by reacting compound (A) represented by formula (II) with compound (B) represented by formula (III).

In the general formula (II) representing the compound (A), R ₆ is an aliphatic hydrocarbon group or phenyl having 1 to 8 carbon atoms, and R ₇ , R ₈ and R ₉ are each alkoxyl or hydroxyl having 1 to 4 carbon atoms. to be. R ₇ , R ₈ and R ₉ may all be the same or different, or at least one of them may be different from the others.

In the compound (A), examples of the alkoxyl group having 1 to 4 carbon atoms include straight or branched chain groups such as methoxy, ethoxy, propoxy, butoxy and the like. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and the like which are linear or branched groups.

As R ₆ of compound (A), methyl and phenyl are particularly preferable. Preferred as R ₇ , R ₈ and R ₉ are methoxy, ethoxy, propoxy, butoxy and hydroxyl. Examples of the preferred compound (A) include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, methyltrobutoxysilane, phenyltrisilol, methyltrisilol and the like. Among them, methyltrimethoxysilane, phenyltrimethoxysilane and phenyltrisilol are particularly preferred. These compounds can be used individually or in combination.

In the compound (B), R ₁₀ is hydrogen atom or methyl, and R ₁₁ , R ₁₂ and R ₁₃ are hydroxyl, alkoxyl having 1 to 4 carbon atoms or aliphatic hydrocarbon group having 1 to 8 carbon atoms, respectively. m is an integer of 1-6. R ₁₁ , R ₁₂ and R ₁₃ may all be the same or different, or at least one of them may be different from the others. But at least one of these is hydroxyl or alkoxyl.

In compound (B), examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms and the alkoxyl group having 1 to 4 carbon atoms may be those exemplified in compound (A). As R ₁₁ , R ₁₂ and R ₁₃ , methoxy, ethoxy and hydroxyl groups are particularly preferred, and m is preferably in the range of 2 to 4. Examples of preferred compounds (B) include β-acryloxyethyltriethoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane , (gamma) -acryloxypropyl trimethoxysilane, (gamma)-methacryloxy butyl triethoxysilane, (gamma) -acryloxypropyl trisilanol, etc. are mentioned. More preferred among these examples are β-acryloxyethyltriethoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ -Acryloxypropyltrisilol. These compounds can be used individually or in combination.

According to the present invention, the polysiloxane high molecular weight monomer can be prepared by reacting compound (A) with compound (B). The fraction of the two compounds is about 70 to about 99.999 mol%, preferably about 90 to about 99.9 mol%, more preferably about 95 to about 99 mol%, based on the total amount thereof. In the compound (B), about 30 to about 0.001 mol%, preferably about 10 to about 0.1 mol%, more preferably about 5 to about 1 mol%. If the amount of the compound (A) is about 70 mol% or less, the mixture is likely to gel during the copolymerization reaction, whereas when the amount of the compound (A) is about 99.999 mol% or more, the amount of the uncopolymerized polysiloxane increases and the resin solution becomes cloudy. not.

The reaction between the compound (A) and the compound (B) is carried out by dehydration condensation of the hydroxyl group generated by the hydrolysis of the hydroxyl group and / or the alkoxyl group of the compound contained in these compounds. Depending on the reaction conditions, the reaction includes dealcohol condensation in addition to the dehydration reaction.

Although the reaction can be carried out in the absence of a solvent, it is preferable to carry out the reaction in an organic solvent in which both water and / or compounds (A) and (B) are dissolved. Examples of preferred organic solvents include hydrocarbon solvents such as heptane, toluene, xylene, octane and mineral spirits, ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, methylcellosolve acetate and butylcarbitol acetate, methyl ethyl Ketone solvents such as ketones, methyl isobutyl ketone and diisobutyl ketone, alcohol solvents such as ethanol, isopropanol, n-butanol, secondary-butanol and isobutanol, n-butyl ether, dioxane, ethylene glycol monomethyl ether and Ether solvents such as ethylene glycol monoethyl ether, and the like. These solvents can be used alone or in combination.

When using compounds (A) and (B) in the form of a solution, it is appropriate that the total concentration of these compounds in the solution is at least 5% by weight.

According to the present invention, compounds (A) and (B) are suitably reacted at a temperature of about 20 to about 180 ° C, preferably about 50 to about 120 ° C. The reaction time is suitably usually about 1 to about 40 hours.

If necessary, the reaction can be carried out in the presence of a polymerization inhibitor effective for preventing the polymerization reaction by the unsaturated bond of compound (B). Examples of useful inhibitors are hydroquinone, hydroquinone monomethylether and similar quinone compounds.

The reaction system of the compound (A) and (B) for producing the polysiloxane high molecular weight monomer may contain tetraalkoxysilane, dialkyldialcoholsilane, and the like incorporated therein, and these are the total amount of the compound (A) and (B) It can be used in an amount of about 20 mol% or less based on.

When R ₇ , R ₈ , R ₉ , R ₁₁ , R ₁₂ and R ₁₃ of compounds (A) and (B) are all hydroxyl, it is preferable to carry out the reaction under heating and stirring in an organic solvent to dehydrate and condense. .

In addition, when at least one of compound (A) and (B) has an alkoxyl bonded to Si, it is preferable to perform hydrolysis before condensation. Hydrolysis reaction and condensation reaction can be performed continuously, heating and stirring in presence of water and a catalyst. The amount of water used for these reactions is not particularly limited, but is preferably at least about 0.1 mole per mole of alkoxyl. If less than about 0.1 mole of water is present, the reactivity of the two compounds may be lowered. It is most preferred to use excess water. If the condensation reaction produces alcohols that are poorly soluble in water, the combined use of water and water soluble organic solvents makes the reaction system homogeneous. Preferred for use as the water soluble organic solvent are the alcohols, esters, ethers and ketone solvents described above. Acid or alkali catalysts can be used as catalysts for the hydrolysis reaction. Examples of useful acid catalysts include hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid and the like. Examples of useful alkali catalysts are sodium hydroxide, triethylamine, ammonia and the like. It is appropriate to use the catalyst in an amount of about 0.0001 to about 5% by weight, preferably about 0.01 to about 0.1% by weight, based on the total amount of compounds (A) and (B).

The polysiloxane high molecular weight monomers used in the present invention have a number average molecular weight of about 400 to about 100,000, preferably about 1,000 to about 20,000. If this value is about 400 or less, the copolymerization reaction system tends to gel, whereas a value above about 100,000 may result in impaired suitability, which is undesirable.

In the present invention, the main skeleton of the polysiloxane high molecular weight monomer provided by the reaction of Compounds (A) and (B) includes siloxane bonds. The main skeleton mainly has a structure of a straight chain structure, ladder structure, or a combination of these structures. It is preferable to use a high molecular weight monomer of a ladder structure or a high molecular weight monomer of a combination structure having a large portion of a ladder structure in view of resistance to water, heat and light. The structure of the high molecular weight monomer can be selectively determined as necessary according to the ratio between the compound (A) and the compound (B), the amount of water and acid catalyst, and the like. Polysiloxane high molecular weight monomer is a siloxane bond of Si is R _6, R ₇ and R ₉ of the general formula (II) _, And a structure bonded to a group such as R ₁₁ to R ₁₃ of the general formula (III). High molecular weight monomers have at least two free functional groups per molecule, such as hydroxyl and alkoxyl (ie silanol groups and / or alkoxy silane groups) having 1 to 4 carbon atoms bonded to Si.

Furthermore, it is preferred that the polysiloxane high molecular weight monomers have on average about 0.2 to about 1.9, preferably about 0.6 to about 1.4, more preferably about 0.9 to about 1.2 polymerizable unsaturated bonds per molecule. The presence of a very small amount of polymerizable unsaturated bonds makes the copolymerization product easily turbid, whereas having an excess of these bonds is undesirable because the high molecular weight monomers are likely to gel during the reaction.

The number of unsaturated bonds in a high molecular weight monomer can be determined according to the following method.

(1) Compound (A) and compound (B) are reacted at the ratio which changed suitably, and various polysiloxane high molecular weight monomers are manufactured.

(2) A non-functional vinyl monomer and a high molecular weight monomer are reacted in various ratios to obtain various vinyl copolymers. The nonfunctional vinyl monomers used are vinyl monomers which have a polymerizable unsaturated bond moiety as a site which reacts with the unsaturated bond in the high molecular weight monomer and no functional group which reacts with the alkoxysilane group and / or silanol group in the high molecular weight monomer. Examples of nonfunctional vinyl monomers that can be used include styrene, vinyltoluene, acrylic acid or methacrylic acid and esters of monohydric alcohols and the like.

(3) The molecular weight distribution of the resulting vinyl copolymer is determined by gel permeation chromatography (G.P.C.).

(4) copolymers obtained using various proportions of high molecular weight monomers and non-functional vinyl monomers are approximately equal in peak molecular weight (highest molecular weight), and low molecular weight components (high molecular weight monomers without unsaturated bonds) or In the case of a single peak distribution curve without high molecular weight components (copolymers of high molecular weight monomers having at least two unsaturated bonds), the high molecular weight monomers used are interpreted as having an average of one polymerizable unsaturated bond per molecule. Can be.

(5) The average number of polymerizable unsaturated bonds in other high molecular weight monomers can be given by the following formula.

Wherein [A] is the number of moles of compound (A) used, [B] is the number of moles of compound (B) used, and [A ₁ ] and [B ₁ ] are each on average one polymerizable unsaturated bond Moles of compound (A) and compound (B) used to obtain a high molecular weight monomer having

For example, the molar ratio of Compound (B) / Compound (A) = 1/20 is estimated to provide a high molecular weight monomer having one polymerizable unsaturated bond. The molar ratio of Compound (B) / Compound (A) = 0.9 / 20 yields a high molecular weight monomer having 0.9 polymerizable unsaturated bonds on average.

Another monomer of copolymer Y used in the present invention is an oxirane-containing vinyl monomer. Examples of such monomers include glycidyl methacrylate, glycidyl acrylate and analogs of general formula (XVI), vinyl glycidyl ethers and similar glycidyl-containing monomers, the following general formulas (XVII) to (XIX) And alicyclic oxirane-containing monomers of the formula (III), monomers of the general formulas (IV) to (XV), and the like.

Wherein R ₁₄ and R ₁₅ are the same as defined above.

Among these oxirane-containing vinyl monomers, it is preferable to use alicyclic oxirane-containing vinyl monomers of general formulas (IV) to (XV) to (XVII) to (XIX) in terms of curability.

However, even when using a monomer (XVI), an alicyclic oxirane-containing compound can be further used to improve the curability. Glycidyl methacrylate, a typical compound (XVI), has the advantage of being cheap and readily available.

Polysiloxane high molecular weight monomers and oxirane-containing vinyl monomers are used as monomer components to provide vinyl copolymers used as copolymer Y of the present invention. If necessary, polymerizable vinyl monomers other than this monomer can be used as the monomer component of copolymer Y. Such polymerizable vinyl monomers may be selected from various monomers depending on the desired properties. These typical unsaturated monomers are the said monomers (1)-(4).

Among these monomers, the presence of large amounts of acrylic, methacrylic and similar acid monomers, and dimethylaminoethyl methacrylate, acrylamide and similar basic monomers in the copolymer is likely to gel during the reaction, so these monomers should be used in minimal amounts. do.

In order to give copolymer Y an improved ability to be used as a dispersion stabilizer, the monomer whose monomer component is in the form of an ester of methacrylic acid or acrylic acid with C ₄ to C ₁₈ monoalcohol is based on at least the total amount of all monomers. It is preferred to contain about 20 to about 95 weight percent, preferably at least about 40 to about 90 weight percent.

The monomers for preparing copolymer Y used in the composition of the present invention are used in the following amounts. If the copolymer consists of two components: the polysiloxane high molecular weight monomer and the oxirane-containing vinyl monomer, the former is about 0.01 to 98% by weight and the latter is about 99.99 to about 2% by weight, preferably the former is about 0.1 to About 80% by weight and the latter are used at about 99.9 to about 20% by weight. If the amount of the polysiloxane high molecular weight monomer used is less than this range, the curability is reduced, while exceeding this range is undesirable because the cured product exhibits impaired properties and tends to shrink.

Also, when other polymerizable vinyl monomers are used together with the two types of monomers, from about 0.01 to about 80 weight percent polysiloxane high molecular weight monomer, from about 1 to about 90 weight percent oxirane-containing vinyl monomer and up to about 98.99 weight percent Other polymerizable vinyl monomers are used. Particularly preferably, about 0.1 to about 60 weight percent polysiloxane high molecular weight monomer, about 3 to about 60 weight percent oxirane-containing vinyl monomer and about 10 to about 96.9 weight percent other polymerizable vinyl monomers are used. For the reasons mentioned above, it is not desirable to use high molecular weight monomers and oxirane-containing vinyl monomers in amounts outside the above ranges.

Copolymer Y may be prepared by the same preparation method under the same conditions as are conventionally used for producing acrylic resin or vinyl resin. For example, the copolymer may be prepared by dissolving or dispersing the monomer component in an organic solvent and stirring and heating the solution or dispersion to a temperature of about 60 to about 180 ° C. in the presence of a radical polymerization initiator. The reaction is typically carried out for about 1 to about 10 hours. Organic solvents used include, for example, alcohol solvents, ether solvents, ester solvents, hydrocarbon solvents and the like. The hydrocarbon solvent to be used is preferably used in combination with other solvents from the viewpoint of solubility. The radical polymerization initiator may be any one generally used. Examples of such initiators include benzoyl peroxide, tert-butylperoxy-2-ethyl hexanoate and like peroxides, azoisobutyronitrile, azobisdimethylvaleronitrile and similar azo compounds.

In general, it is appropriate for the copolymers X or Y used as dispersion stabilizer resins in the present invention to have a number average molecular weight of about 2000 to about 200000, preferably about 5000 to about 200000. If the molecular weight is 2000 or less, the dispersed particles are not completely stabilized and are likely to aggregate or settle, whereas if the molecular weight is about 200000 or more, the dispersion is very viscous and difficult to handle, which is not preferable.

When the dispersion stabilizer resin is used, it may be used singly or in combination of at least two resins having different copolymerization compositions or molecular weights. If desired, the resin may be used together with a small amount of other dispersion stabilizers such as butylether melamine-formaldehyde resins, alkyd resins or other common acrylic resins containing no compound (I) as copolymer components.

According to the present invention, a radical polymerizable unsaturated monomer is polymerized in an organic liquid in the presence of a dispersion stabilizer resin to prepare a non-aqueous dispersion of particulate polymer insoluble in an organic liquid.

Organic liquids used for the polymerization include those in which the dispersed particulate polymer obtained by polymerization is substantially insoluble and is an excellent solvent for stabilizer resins and radical-polymerizable unsaturated monomers. Examples of such organic liquids include aliphatic hydrocarbons including hexane, heptane, octane, mineral spirits and naphtha; Aromatic hydrocarbons including benzene, toluene and xylene; Alcohols including isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and octyl alcohol; Ethers including cellosolves, butylcellosolves, diethylene glycol monobutyl ethers; Ketones including methyl isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, ethyl acyl ketone, methyl hexyl ketone and ethyl butyl ketone; Ester including ethyl acetate, isobutyl acetate, amyl acetate, and 2-ethylhexyl acetate, etc. are mentioned. These organic liquids may be used alone or in combination of at least two of them. In general, it is appropriate to use aliphatic hydrocarbons in combination mainly with aromatic hydrocarbons, alcohols, ethers, ketones or esters. If necessary, trichlorotrifluoroethane, m-xylenehexafluoride, tetrachlorohexafluorobutane and the like can be used.

The particulate polymer component of the non-aqueous dispersion can be any of the monomers described above that can be used to prepare the dispersion stabilizer. Since the particulate polymer should be insoluble in the organic liquid in which it is used, the polymer is methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylonitrile, 2-hydroxy (meth) acrylate, hydroxypropyl (meth ) Containing a large amount of monomers having high polarity, such as acrylate, (meth) acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene, α-methylstyrene or N-methylol (meth) acrylamide Copolymers are preferred. The particles in the non-aqueous dispersion may already be crosslinked. Internal crosslinked particles can be obtained by copolymerizing functional monomers such as divinylbenzene and ethylene glycol diacrylate or by reacting these monomers with each other. On the other hand, after polymerizing at least one monomer having functional groups which react with itself to obtain particles, a non-aqueous dispersion is prepared and the particles are crosslinked. Various intraparticle crosslinking reactions can be used, including the reaction described in Japanese Patent Laid-Open No. 53-133236.

The monomer can generally be polymerized using a radical polymerization initiator. Examples of radical polymerization initiators that can be used include azo initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile); And peroxide initiators such as benzoyl peroxide, lauryl peroxide, tert-butyl peroctoate and tert-butylperoxy-2-ethyl hexanoate. This initiator may be used in an amount of about 0.2 to about 10 parts by weight, preferably about 0.5 to about 5 parts by weight, per 100 parts by weight of the monomer to be polymerized.

The fraction of the dispersion stabilizer resin present in the polymerization system varies greatly depending on, for example, the type of resin used. Generally, it is appropriate to use about 3 to about 240 parts by weight, preferably about 5 to about 82 parts by weight of radical-polymerizable unsaturated monomer, per about 100 parts by weight of the stabilizer resin. The total concentration of the stabilizer resin and the radically polymerizable unsaturated monomer in the organic liquid is generally about 30 to about 70% by weight, preferably about 30 to about 60% by weight.

The polymerization is carried out by known methods. The polymerization reaction temperature is generally about 60 to about 160 ° C. The reaction generally takes about 1 to about 15 hours.

In this way, a stable non-aqueous dispersion is obtained in which the liquid phase is an organic liquid with a stabilizer resin dissolved therein and the solid phase is a polymer particle formed by polymerization of a radical-polymerizable unsaturated monomer. Particulate polymers generally have a particle size in the range of about 0.1 to about 1.0 μm. If the particle size is smaller than this range, it is undesirable because the composition has a higher viscosity, and if the particle size is larger than this range, it is also undesirable because the particles swell or aggregate during storage.

In accordance with the present invention, dispersion stabilizer resins are bonded to particulate polymers to impart improved storage stability to the resulting composition and upon curing, the composition forms a coating with excellent transparency, smoothness and mechanical properties. The stabilizer resin can be bonded to the particulate polymer by introducing a polymerizable double bond into the stabilizer and polymerizing the radical polymerizable unsaturated monomer in the presence of the stabilizer.

Most preferably, polymerizable double bonds can be introduced into the stabilizer resin by adding α, β-ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid or itaconic acid to some oxirane groups in the copolymer. On the other hand, isocyanate-containing monomers such as isocyanoethyl methacrylate are added to the hydroxyl groups present in the copolymer.

The composition of the present invention contains an aqueous dispersion and a chelate compound which is a crosslinking curing agent mixed with each other.

The chelate compound used in the present invention is preferably an aluminum chelate compound, a titanium chelate compound and a zirconium chelate compound. Among these chelate compounds, it is preferable to contain a compound capable of forming a keto-enol tautomer as a ligand which forms a stable chelate ring.

Examples of useful compounds that can form keto-enol tautomers include β-diketones (such as acetylacetone), acetoacetic acid esters (such as methylacetoacetate), and malon esters (such as ethylmalonate) , ketones having hydroxyl at the β-position (such as diacetone alcohol), aldehydes having hydroxyl at the β-position (such as salicylate), esters having hydroxyl at the β-position (methylsalicyl) Rate), and the like. In particular, the most desirable results can be obtained when using acetoacetate and β-diketone.

The aluminum chelate compound is, for example, a mixture of a compound capable of forming a keto-enol tautomer with an aluminum alcoholate of general formula (XX), generally at a rate of about 3 moles of electrons per mole of the latter, if necessary The mixture can be preferably prepared by heating:

(Wherein R ₁₇ is alkyl or alkenyl having 1 to 20 carbon atoms and the R ₁₇ groups are the same or different).

Examples of the alkyl group having 1 to 20 carbon atoms are the aforementioned alkyl group having 1 to 10 carbon atoms, undecyl, dodecyl, tridecyl, tetradecyl, octadecyl and the like. Examples of alkenyl groups are vinyl, allyl and the like.

Examples of the aluminum alcoholate represented by the general formula (XX) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum Triisobutoxide, aluminum tri-secondary-butoxide, aluminum tri-tert-butoxide and the like. Particular preference is given to using aluminum triisopropoxide, aluminum tri-secondary butoxide and aluminum tri-n-butoxide.

The titanium chelate compound is, for example, a compound capable of forming a keto-enol tautomer and a titanate of the general formula (XXI) below, typically having a ratio of about 1 to about 4 moles of electrons relative to 1 mole of Ti in the titanate. After mixing, it can manufacture advantageously by heating as needed.

(Wherein ι is an integer from 1 to 10, R ₁₈ represents alkyl having 1 to 20 carbon atoms, or alkenyl and the R ₁₈ groups are the same or different.)

Examples of the alkyl group and alkenyl group having 1 to 20 carbon atoms are the same as those given above.

Examples of the titanate represented by general formula (XXI) in which ι is 0 include tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate tetraisopropyl titanate, tetra-n-butyl titanate, tetra Isobutyl titanate, tetra-tert-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate and the like. Preferred results can be obtained by using tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate and tetra-tert-butyl titanate. In the formula, in the titanate having? Of 1 or more, dimers to 11-mers of tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate and tetra-tert-butyl titanate (formula (XXI) Ι = 1 to 10) achieves good results.

Zirconium chelate compounds are, for example, compounds that can form keto-enol tautomers and zirconates of the general formula (XXII) below typically at a ratio of about 1 to about 4 moles of electrons per mole of Zr in zirconate. After mixing, it can manufacture advantageously by heating as needed.

(Wherein ι is an integer from 0 to 10, R ₁₉ represents alkyl having 1 to 20 carbon atoms, or alkenyl and the R ₁₉ groups are the same or different.) Examples of alkyl and alkenyl groups having 1 to 20 carbon atoms Are the same as those exemplified above.

Examples of zirconates represented by the general formula (XXII) in which ι is 0 include tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, Tetra-tert-butylzirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-tert-pentyl zirconate, tetra-tert-hexyl zirconate, tetra -n-heptyl zirconate, tetra-n-octyl zirconate, tetra-n-stearyl zirconate and the like. Tetraisopropyl zirconate, tetra-n-propyl zirconate, tetraisobutyl zirconate, tetra-n-butyl zirconate, tetra-tert-butyl zirconate and tetra-tert-butyl zirco Particularly good results can be obtained using the nates. Among the zirconates in which ι is one or more, tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate, tetraisobutyl zirconate, tetra-secondary-butyl zirco Dimers to 11-mers of nitrate and tetra-tert-butylzirconate (ι = 1 to 10 in formula (XXII)) produce excellent results. Chelating compounds may contain structural units in which these zirconates are linked to each other.

Examples of particularly preferred chelate compounds for use in the present invention include diisopropoxy ethylacetate acetate aluminum, tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, Tris (n-butylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (propionylacetoacetate) aluminum, tris (acetylacetonate) aluminum, tris (propylacetoacetate) Aluminum, tris (propionylacetonato) aluminum, acetylacetonatobis (ethylacetoacetate) aluminum, ethylacetoacetatebis (acetylacetonato) aluminum, tris (isopropionylacetonate) aluminum, tris (secondary) -Butyryl acetonate) aluminum, [bis ( Bovine propionyl acetonitrile Nei Sat) secondary-butyryl acetonitrile Nei Sat] aluminum and tris (butyl acetoacetate), aluminum chelate compounds such as aluminum; Titanium chelate compounds such as diisopropoxy bis (ethylacetoacetate) titanate, diisopropoxy bis (acetylacetonato) titanate and isopropoxy tris (propionylacetonato) titanate; And zirconium chelate compounds such as tetrakis (acetylacetonato) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (propionylacetonato) zirconium and tetrakis (ethylacetoacetate) zirconium.

According to the present invention, one of an aluminum chelate compound, a zirconium chelate compound and a titanium chelate compound may be used, or at least two of these compounds may be appropriately combined. Among these chelate compounds, preference is given to using aluminum chelate compounds and / or zirconium chelate compounds which reliably impart high curability and reduce the coloring of the cured product. It is appropriate to use the chelate compound in an amount of about 0.01 to about 30 parts by weight per 100 parts by weight of the resin solid in the composition.

Use in amounts outside this range results in lower crosslink curability, while use in amounts outside this range is undesirable, because higher amounts result in chelating compounds remaining in the cured product and lower water resistance. Preferred amounts are from about 0.1 to about 10 parts by weight.

According to the invention, a compound having at least two alicyclic oxirane groups in the solution-form vinyl copolymer and in the molecule can be incorporated into the composition together with the non-aqueous dispersion and the chelate compound.

The solution-type vinyl copolymer used may be the same stabilizer resin as used for the non-aqueous dispersion. However, since the copolymer does not have to have a stabilizer action or contain double bonds for bonding to the polymer, ie the copolymer does not have to meet the conditions of use as a dispersion stabilizer, the copolymer is used for dispersion stabilizers. It can be prepared from more various monomers. The solution-form vinyl copolymer is used in an amount of about 0 to about 100 parts by weight per 1 part by weight of the solid of the non-aqueous dispersion. Solution-form vinyl copolymers, if present, impart improved appearance to the resulting cured product.

Examples of the compound having at least two alicyclic oxirane groups in the molecule used in the present invention are

Compounds given the like and the like; Adducts with polyisocyanates; And adducts of polybasic acids; In the molecule Or a product prepared by oxidizing an ester having a similar unsaturated group with peracetic acid or the like; And the like. Examples of useful polyisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, alicyclic diisocyanates such as xylylene diisocyanate and isophorone diisocyanate, tolylene diisocyanate and 4,4′-di Organic diisocyanates including aromatic diisocyanates such as phenylmethane diisocyanate. Moreover, the adduct of this organic diisocyanate with polyhydric alcohol, low molecular weight polyester resin, water, etc., the polymer isocyanate biuret compound of this organic diisocyanate, etc. are useful. Typical examples of such compounds are commercially available "BURNOCK D-750 and -800, DN-950 and -970, and 15-455" (Dainippon Ink Chemicals Inc.), "DESMODUL L," NHL, IL and N 3390 ”(from West Germany Bayer),“ TAKENATE D-102, -202, -110N and -123N ”(from Takeda Chemical Industries, Ltd.),“ COLONATE L, HL, EH and 203 ”(manufactured by Nippon Polyurethane Kogyo Co., Ltd.) and“ DURNANTE 24A-90CX ”(Asahi Chemical Industry Co., Ltd.). Examples of esters having an unsaturated group are obtained by esterifying, for example, tetrahydrophthal anhydride, trimethylolpropane or 1,4-butanediol.

The alicyclic oxirane-containing compound, if present, imparts improved curability to the composition even if the oxirane group contained in the stabilizer of the non-aqueous dispersion is not an alicyclic oxirane group.

The solution-form vinyl copolymer resin preferably has a number average molecular weight in the range of about 1000 to about 50000. If the molecular weight is 1000 or less, it is difficult to produce the copolymer resin by the radical polymerization method which is easily used industrially. If the molecular weight is about 50000 or more, the composition is difficult to apply effectively and exhibits a damaged appearance upon curing.

The alicyclic oxirane-containing compound preferably has a number average molecular weight of 1000. If the molecular weight exceeds 1000, the compound becomes difficult to blend with the stabilizer and solution-form vinyl copolymer of the non-aqueous dispersion.

The alicyclic oxirane-containing compound is used in an amount of about 0 to about 200 parts by weight per 100 parts by weight of the total resin solids of the dispersion and solution-form vinyl copolymer. While the alicyclic oxirane-containing compound is not an essential component in the compositions of the present invention, compounds such as glycidyl methacrylate containing only aliphatic oxirane groups may be added to the resin and solution-type vinyl copolymer of the non-aqueous dispersion. If present, the composition exhibits low temperature curability in the presence of an alicyclic oxirane-containing compound. In general, glycidyl methacrylate is the least expensive among other oxirane-containing vinyl monomers, so that the cycloaliphatic oxy when glycidyl methacrylate copolymers are used for non-aqueous dispersions and as liquid-type vinyl copolymers It is highly desirable to add the lan-containing compound to the composition. Even when the non-aqueous dispersion and solution-form vinyl copolymer contain an alicyclic oxirane group, the presence of the alicyclic oxirane-containing compound is useful for increasing the solid concentration of the composition and imparting an improved appearance to the coating to be obtained. On the other hand, if the amount of the oxirane-containing compound exceeds 200 parts by weight, the composition contains an excess of low molecular weight components and exhibits lower curability.

If desired, the composition may be formulated with epoxy-containing resins such as Epikote 1001 (available from Shell Chemical), hydroxyl-containing resins such as styrene-allyl alcohol copolymers, triphenyl methoxysilane and diphenyldimethoxysilane. The same low molecular weight silane compounds, conventional alkoxysilane-containing silicone resins, and other resins can be introduced.

In addition, in order to impart improved storage stability, it may be added to a composition compound which provides a ligand for a chelating compound, such as the above compounds, which can form keto-enolautomers.

In addition, if necessary, surface modifiers, flow control agents, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, colored pigments, metal powder pigments, mica powder pigments, dyes and the like known in the present composition may be introduced.

The composition is usually used after diluting the organic solvent. Examples of preferred organic solvents include hydrocarbon solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; Ester solvents such as ethyl acetate and butyl acetate; Ether solvents such as dioxane and ethylene glycol diethyl ether; Alcohol solvents such as butanol and propanol, and the like. In consideration of the stability of the non-aqueous dispersion, these solvents may be used alone or in combination as appropriate. When using an alcohol solvent, it is preferable to mix | blend with another solvent from the viewpoint of the solubility of resin. Although depending on the intended use, the resin content in the resin solution is typically about 10 to about 70% by weight.

The method of applying the present composition is not particularly limited, and conventional coating methods such as spray coating, roll coating and brush coating can be used.

When copolymer Y is introduced as a dispersion stabilizer resin, the composition of the present invention can be easily cured by crosslinking at low temperatures up to 100 ° C. For example, the composition can be sufficiently cured at room temperature, typically from about 8 hours to about 7 days, without heating. When heated at about 40 to about 100 ° C., the composition can be fully cured in about 5 minutes to about 3 hours.

It is believed that the curing reaction of the composition of the present invention begins with evaporation of the solvent and proceeds in the form of a chain reaction by evaporation of the chelating agent from the crosslinker. Perhaps a crosslinker will advance the reaction through the following mechanisms. For example, if the crosslinking curing agent used is an aluminum chelate compound, after evaporation of the chelating agent, the reaction of the aluminum compound with silanol groups derived from the polysiloxane high molecular weight monomer proceeds to bond the first step. Creates.

Next, in the second step, silanol and Between Is polarized. Polarized silanol reacts with epoxy group To form an oxonium salt represented by Next, ion polymerization of the oxirane group and addition reaction of the oxirane group with the hydroxyl group occur.

In the case of the present composition, the copolymer which acts as a dispersion stabilizer resin and, optionally, the solution-formed vinyl copolymers, includes silanol groups and other functional groups derived from polysiloxane high molecular weight monomers, one of the monomer components, and an oxirane-containing vinyl air. It contains an oxirane group derived from coalescence.

Thus, in addition to the crosslinking reactions catalytically carried out by the crosslinking curing agents described above, several curing reactions, possibly below, will occur simultaneously.

(A) Condensation of silanol groups

(B) condensation of a silanol group with a hydroxyl group produced in an oxirane group

(C) addition of silanol groups to oxirane groups

(D) Addition of hydroxyl group to oxirane group

(E) Ion Polymerization of Oxylan Group

While these curing reactions occur simultaneously, the resin composition can be cured at about the same time near and inside the surface. This reduces the difference in degree of cure between the surface and the interior of the cured product, so that it has sufficient hardness and hardly shrinkage occurs. When the polysiloxane high molecular weight monomer in the present composition contains an alkoxyl group forming an alkoxysilane group, the composition is hydrolyzed to form silanol groups. This hydrolysis reaction proceeds sufficiently in the presence of a small amount of water, that is, moisture in the atmosphere. The hydrolysis reaction does not proceed easily inside the composition, and when the high molecular weight monomer does not have a silanol group, it is difficult to cause a curing reaction in which the silanol groups participate in the composition, whereas the inside is sufficient by a reaction in which the epoxy group participates. Can be cured.

When introducing copolymer X which acts as a dispersion stabilizer resin, the composition of the invention can be easily cured by crosslinking at low temperatures in the presence of water. More specifically, the composition of the present invention is usually sufficient within about 8 hours to about 7 days by simply applying water to the composition without heating and applying the composition, or by applying the composition and exposing the coating to the atmosphere. It can be cured. Alternatively, when heated at, for example, about 40 to about 100 ° C., the composition may cure in about 5 minutes to about 3 hours. The water required for curing is a small amount of water in the atmosphere. When water is added to the composition prior to application, about 0.1 to about 1 weight percent water typically yields satisfactory results. Perhaps for the following reasons the compositions of the present invention can be easily cured by crosslinking at low temperatures in the presence of small amounts of water. When the aluminum chelate compound is present, the alkoxyl groups derived from monomer A are hydrolyzed in the first step in the presence of water by the catalysis of the aluminum chelate compound to produce silanol groups. In the second step, the same reaction as described above proceeds.

Conventional curable compositions in the same form as the present compositions are cured only by a second stage reaction, while monomers B and alicyclic oxirane-containing compounds present in the composition are in a second stage reaction and usually in a chain-like form. By allowing the third stage reaction to proceed, the composition is crosslinked and cured. Perhaps for this reason the composition can be preferably cured at low temperatures in the presence of small amounts of water.

The composition of the present invention is obtained by polymerizing a liquid phase and a radically polymerizable unsaturated monomer in the form of a dispersion stabilizer resin solution in an organic liquid, and solid phases of polymer particles stably dispersed in a liquid phase; And a non-aqueous dispersant composed of a chelating compound introduced into the dispersion. As a result, when the composition is applied, the composition has a greatly increased solids content and at the same time the applied composition increases in viscosity to form a good finish or appearance coating without sagging or running. The coating formed from the composition has siloxane bonds, has stable continuity to light and chemicals, and contains certain polymers that are stabilized by continuous phase and coating reinforcement, thereby providing excellent light and chemical resistance. Membrane has improved mechanical properties, possibly by stress relaxation, such as absorption of external energy resulting from significant thermoplastic deformation of the polymer particles and absorption of impact energy due to breakage caused by the polymer particles. Since the above mentioned first to third stage chain reactions in the non-aqueous dispersion system take place in the continuous phase, the composition is cured even with a reduced amount of water.

The composition of the present invention is useful, for example, as a coating composition, an adhesive, an ink, or the like. Since the cured product of the present invention has excellent weather resistance, water resistance, etc., the composition is suitable for use in the coating or repair of motor vehicles and containers, the coating of building exterior materials, and the preparation of precoated materials (PCM). .

The composition of the present invention has the following excellent aspects.

(1) The composition can be easily cured by crosslinking at a low temperature up to 100 ° C. For example, when cured at 80 ° C. for 30 minutes, the composition yields a cured product having a gel fraction of at least 95%.

(2) The curing reaction does not require water or proceeds in the presence of a small amount of water, ie moisture in the atmosphere.

(3) Since the composition is cured with evaporation of the solvent, the composition can be stored with good stability when prepared as a single packaging composition. For example, the composition is stable for at least one year in the absence of water.

(4) The composition does not have a hardening agent such as isocyanate which is highly toxic.

(5) The composition is in the form of a solution having a low viscosity and thus has a high solid concentration.

(6) Condensation reaction of silanol groups, ion polymerization reaction of epoxy groups, and other curing reactions occur simultaneously, resulting in reducing the difference in the degree of curing between the surface and the interior, without shrinkage, and producing a coating with increased thickness. A satisfactorily useful composition.

(7) Due to the reduced amount of alcohol and other by-products, the composition provides a cured product having excellent properties, especially weather resistance, water resistance and impact resistance, flowability, fouling resistance or sewage resistance.

(8) When cured, the composition provides a cured product with little or no possibility of being uncured in the surface layer, excellent in overcoating and recoating, and excellent in adhesion.

(9) The presence of certain polymers in the composition imparts good storage stability and allows the composition to form a well finished coating without running or sagging.

(10) The formed coating contains a specific polymer, and since the continuous phase thereof has siloxane bonds, the coating is excellent in properties, that is, weather resistance and the like.

The invention will be explained in more detail by the following examples in which parts and percentages are by weight.

[Production of non-aqueous dispersant (a-1)]

The following monomers are polymerized in a solvent mixture of xylene / n-butanol (125 parts / 35 parts) using α, α'-azobisisobutyronitrile (AIBN) as the initiator.

Glycidyl methacrylate part 30

2-ethylhexyl methacrylate 45 parts

Styrene part 10

2-hydroxyethyl methacrylate 5 parts

The resulting copolymer had a number average molecular weight of 12,000, its solution having a solids content of 50% and a Gardner viscosity (25 ° C.). Methacrylic acid is used with the copolymer to introduce 0.3 polymerizable double bonds per molecule of the copolymer, calculated on the basis of the number average molecular weight. The resulting mixture is used as a dispersion stabilizer solution with a solid concentration of 50%. Subsequently, 100 parts of the stabilizer solution and 200 parts of ethylcyclohexane are placed in a flask, and the monomers and polymerization initiators given below are added dropwise to the mixture over 4 hours at reflux temperature. After adding 0.2 part of tert-butyl peroctoate, the reaction mixture was cured for 3 hours to obtain a non-aqueous dispersant (a-1).

Styrene part 10

Methyl methacrylate 40 parts

20 glycidyl methacrylates

20 parts of 2-hydroxyethyl acrylate

10 parts acrylonitrile

AIBN Part 1

The dispersant (a-1) has a solid concentration of 55% and a Gardner viscosity (25 ° C.).

[Production of non-aqueous dispersant (a-2)]

A dispersion stabilizer having the following monomers is prepared in the same manner as above. No polymerizable double bond is introduced into the stabilizer.

Lauryl methacrylate part 20

20 parts 2-ethylhexyl methacrylate

2-hydroxyethyl methacrylate 5 parts

Isobutyl methacrylate 15 parts

The dispersion stabilizer obtained had a solids content of 50%, a Gardner viscosity (25 ° C) of G, and a number average molecular weight of its resin component of 9,500.

A non-aqueous dispersant (a-2) is prepared in the same manner as in the dispersant (a-1) using the dispersion stabilizer and the following mixture as specific components.

Styrene part 12

Methyl methacrylate 31 parts

15 parts acrylonitrile

15 parts of 2-hydroxyethyl acrylate

The dispersant has a 55% solids content and a Gardner viscosity (25 ° C.).

[Production of non-aqueous dispersant (a-3)]

A non-aqueous dispersant (a-3) is prepared in the same manner as in the dispersant (a-2) except that the monomer mixture added dropwise in the presence of a dispersion stabilizer for forming the particles has the following composition.

Methyl methacrylate 70 parts

10 parts acrylonitrile

Ethylene Glycol Dimethacrylate 5 Parts

Glycidyl methacrylate part 15

The non-aqueous dispersant (a-3) has a solid concentration of 55% and a Gardner viscosity (25 ° C.).

[Production of non-aqueous dispersant (a-4)]

The following mixture was reacted at 80 ° C. for 5 hours to prepare polysiloxane high molecular weight monomer M1.

2,720 parts (20 mol) of methyl trimethoxysilane

γ-methacryloxypropyltrimethoxysilane 256 parts (1 mol)

1,134 deionized water

36% hydrochloric acid 2 parts

Hydroquinone part1

High molecular weight monomers have a number average molecular weight of 2,000 and have an average of one polymerizable double bond and four hydroxyl groups per molecule.

100 parts of styrene

2-ethylhexyl methacrylate 400 parts

100 parts of 2-hydroxyethyl acrylate

20 parts of 2,2'-azobis isobutyronitrile

200 parts of the mixture and the high molecular weight monomer M1 were added dropwise to 1000 parts of xylene at 120 ° C. during the polymerization reaction to obtain a clear copolymer solution. The copolymer has a number average molecular weight of 19,000 and the solution has a solids content of 50% and a Gardner viscosity (20 ° C.). Isocyanoethyl methacrylate is used with the copolymer to introduce 0.3 polymerizable double bonds per molecule as calculated based on the number average molecular weight. A non-aqueous dispersant (a-4) is produced by the following method using a vinyl copolymer as the dispersion stabilizer.

A vinyl copolymer solution (100 parts, a dispersant solution), 180 parts of ethylcyclohexane and 20 parts of n-butanol are placed in a flask. The following monomers and polymerization initiators are added dropwise to the mixture over reflux at 4 hours. After addition of 0.2 part of tert-butyl peroctoate, the reaction mixture is cured for 3 hours. The solvent is then removed from the mixture in vacuo to afford a non-aqueous dispersant (a-4).

Styrene part 10

Methyl methacrylate 45 parts

10 parts of 2-hydroxyethyl acrylate

15 parts acrylonitrile

High molecular weight monomer M1 10 parts

2,2'-azobisisobutyronitrile 1 part

The non-aqueous dispersant (a-4) has a solid concentration of 55% and a Gardner viscosity (25 ° C.) is QR.

[Production of non-aqueous dispersant (a-5)]

In the same manner as in the dispersant (a-4), phenyltrimethoxysilane (48 moles) is reacted with 2 moles of β-methacryloxyethyltrimethoxysilane to obtain a polysiloxane high molecular weight monomer M2. The high molecular weight monomer M2 obtained has a number average molecular weight of about 5,000, and on average has one vinyl group and 5 to 10 methoxy groups per molecule.

High molecular weight monomer M2 (300 parts) is mixed with the following compound.

200 parts glycidyl methacrylate

Lauryl methacrylate 400 parts

100 parts of 2-hydroxyethyl methacrylate

Tert-butyl peroctoate 30part

The mixture is added to 1,000 parts of xylene at 120 ° C. during the polymerization reaction to obtain a copolymer solution. The copolymer obtained had a number average molecular weight of 15,000, the solution had a solid concentration of 50% and a Gardner viscosity (25 ° C.) of N.

The vinyl copolymer solution (120 parts, dispersant solution), 180 parts of ethyl cyclohexane and 20 parts of n-butanol are placed in a flask. The following monomers and polymerization initiators are added to the mixture over 4 hours at reflux temperature. The mixture is cured for 3 hours with addition of 0.2 parts of tert-butyl peroctoate. The solvent is then removed from the mixture in vacuo to afford a non-aqueous dispersant (a-5).

Styrene part 15

Methyl methacrylate 40 parts

10 parts of 2-hydroxyethyl acrylate

15 parts acrylonitrile

Glycidyl methacrylate part 10

High molecular weight monomer M2 10 parts

2,2′-azobis isobutyronitrile 1 part

The non-aqueous dispersant (a-5) has a solid concentration of 55% and a Gardner viscosity (25 ° C.).

[Production of non-aqueous dispersion liquid (a-6)]

An aqueous dispersion (a-6) was prepared in the same manner as the dispersion (a-4) except that the dispersion stabilizer having the monomer component shown below and the following monomer composition for particle formation were used.

Monomer Composition of Dispersion Stabilizer

High molecular weight monomer M1 200 parts

100 parts of styrene

2-ethylhexyl methacrylate 400 parts

100 parts of 2-hydroxyethyl acrylate

[Molecular Composition for Particle Formation]

Styrene part 10

Methyl methacrylate 65 parts

10 parts acrylonitrile

Ethylene Glycol Dimethacrylate 5 Parts

Glycidyl methacrylate part 10

The resulting non-aqueous dispersion (a-6) had a solid concentration of 55% and a Gardner viscosity (25 ° C.).

[Production of Solution Type Vinyl Copolymer (b-1)]

AIBN was used as an initiator to prepare a vinyl copolymer solution (b-1) having the following monomeric composition in a solvent mixture of xylene / n-butanol (4/1).

Glycidyl methacrylate part 30

Styrene part 20

20 parts n-butyl methacrylate

10 parts of 2-hydroxyethyl methacrylate

The solution (b-1) had a solid concentration of 50%, a Gardner viscosity (25 ° C.) of UV, and a number average molecular weight of the resin component of 21,000.

[Production of solution type vinyl copolymer (b-2)]

In the same manner as in the copolymer (b-1), a vinyl copolymer solution (b-2) having a monomer composition given below is prepared.

2-hydroxypropyl methacrylate 10 parts

Styrene part 10

20 parts n-butyl methacrylate

20 parts 2-ethylhexyl methacrylate

The solution has a solid concentration of 50%, a Gardner viscosity of R and a number average molecular weight of the resin component of 15,600.

[Production of Solution Type Vinyl Copolymer (b-3)]

In the same manner as in the solution (b-1), a vinyl copolymer solution (b-3) having the following monomer composition was prepared.

Styrene part 20

20 parts n-butyl methacrylate

Solution (b-3) has a solid concentration of 50%, a Gardner viscosity (25 ° C) of W, and a number average molecular weight of the resin component of 32,000.

[Production of Solution Type Vinyl Copolymer (b-4)]

In the same manner as in the solution (b-1), a vinyl copolymer solution (b-4) having the following monomer composition was prepared.

Styrene part 20

40 parts of n-butyl methacrylate

The solution (b-4) has a solid concentration of 50%, a Gardner viscosity (25 ° C) of M, and a number average molecular weight of the resin component of 13,500.

[Production of Solution Type Vinyl Copolymer (b-5)]

AIBN is used as an initiator to prepare a vinyl copolymer solution (b-5) having the following monomeric composition in a solvent mixture of xylene / n-butanol (4/1).

High molecular weight monomer M1 20 parts

Styrene part 20

20 parts 2-ethylhexyl methacrylate

10 parts of 2-hydroxyethyl methacrylate

The solution (b-5) had a solid concentration of 50%, a Gardner viscosity (25 ° C) of T, and a number average molecular weight of the resin component of 16,000.

[Production of Solution Type Vinyl Copolymer (b-6)]

In the same manner as in the solution (b-5), a vinyl copolymer solution (b-6) having the following monomer composition was prepared.

Glycidyl methacrylate part 25

High molecular weight monomer M2 10 parts

Styrene part 10

35 parts of n-butyl methacrylate

20 parts 2-ethylhexyl methacrylate

The solution (b-6) had a solid concentration of 50%, a Gardner viscosity (25 ° C) of P, and a number average molecular weight of the resin component of 14,000.

[Production of Solution Type Vinyl Monomer (b-7)]

In the same manner as in the solution (b-5), a vinyl copolymer solution (b-7) having the following monomer composition was prepared.

High molecular weight monomer M1 20 parts

Styrene part 20

Methyl methacrylate 20 parts

The solution (b-7) has a solid concentration of 50%, a Gardner viscosity (25 ° C.) of X and a number average molecular weight of the resin component of 29,000.

[Production of Solution Type Vinyl Copolymer (b-8)]

In the same manner as in the solution (b-5), a vinyl copolymer solution (b-8) having the following monomer composition was prepared.

Styrene part 20

40 parts of n-butyl methacrylate

The solution (b-8) had a solid concentration of 50%, a Gardner viscosity (25 ° C) of M, and a number average molecular weight of the resin component of 13,500.

Example 1

The product is prepared from the following components.

64 parts of non-aqueous dispersion (a-1) (55% solids)

70 parts of vinyl copolymer solution (b-1) (50% solid)

Tris (ethylacetoacetate) aluminum 1 part

Acetyl Acetone Part 5

The viscosity of the composition is adjusted to a # 4 pod cup 35 seconds (20 ° C.) using a diluent, i.e., isobutyl acetate / cellosolve acetate mixture (1/1 weight ratio), and used for coating.

Steel panels treated with zinc phosphate are electrophoretically coated to a thickness of 20 μ when dried with a cationic electrophoretic epoxy coating composition and calcined at 170 ° C. for 20 minutes.

The cloth is treated with # 400 sandpaper and then degreased by wiping with gauze moistened with petroleum benzine.

Next, the amino polyester coating composition for automobiles is applied to the coating with a thickness of 30 mu when dried, and baked at 140 ° C. for 30 minutes.

The resulting coating is wet treated with # 400 sandpaper, dehydrated, dried and washed with petroleum benzine to obtain a substrate.

The composition whose viscosity is adjusted as described above is air-sprayed to a thickness of about 50β upon drying on a substrate, and then left at room temperature for 10 minutes and calcined at 100 ° C for 30 minutes. The coatings were tested and evaluated and the results are shown in Table 1.

In Examples 2 to 7 and Comparative Examples 1 and 2, unless otherwise stated, the substrate was prepared in the same manner as in Example 1 and the viscosity of the composition was adjusted.

Example 2

The composition is prepared from the following components. Titanium white is dispersed in the vinyl copolymer solution (b-1). The composition is applied to the substrate with a thickness of 50 mu when dried and baked at 80 ° C. for 30 minutes.

73 parts of non-aqueous dispersion (a-2) (55% solid)

120 parts of vinyl copolymer solution (b-2) (50% solid)

Tris (ethylacetoacetate) aluminum 2 parts

60 parts of titanium white (JR-602) (product of Teikoku Kako Co., Ltd.)

Example 3

The base coating composition for wet-on-wet application is prepared from the following components.

90 parts of non-aqueous dispersion (a-3) (55% solid)

100 parts of vinyl copolymer solution (b-2) (50% solid)

Tris (acetylacetonato) aluminum 1 part

Aluminum paste # 4919 (Toyo Aluminum K.K.) 5 parts

Aluminum paste # 55-519 part 10

(Product of Toyo Aluminum K.K.)

Using xylene, the viscosity of the composition is adjusted to # 4 Pod Cup 15 seconds (20 ° C.) and used for coating. A two-pack transparent transparent finish coating composition containing acrylic polyol / polyisocyanate is prepared separately.

The backing coating composition is air sprayed to a thickness of about 18μ on drying the substrate and left for 5 minutes at room temperature. Next, upon drying the transparent coating on the base coating, it was air sprayed to a thickness of about 30 mu, left at room temperature for 10 minutes and fired at 80 ° C. for 30 minutes.

Example 4

A transparent finish coating composition for wet-on-wet application is prepared from the following components.

73 parts of non-aqueous dispersion (a-2) (55% solid)

80 parts of vinyl copolymer solution (b-2) (50% solid)

Tris (acetylacetoacetate) aluminum 2 parts

Alicyclic oxirane-containing compound ( ^* 1) 20 parts

Acetyl Acetone Part 5

Using a diluent, a mixture of a mixture of Swasol 1000 (aromatic solvent, manufactured by Cosmo Oil Co., Ltd.) and n-butanol (80/20 weight ratio), adjust the viscosity of the clear composition to 35 seconds with a # 4 pod cup and paint Used for

Metallic base coating compositions consisting of acrylic polyols, cellulose acetate butyrate, polyisocyanates and aluminum pastes are prepared separately. The backing coating composition is air sprayed to the substrate with a dry thickness of about 18μ and left at room temperature for 5 minutes. The base coating composition was air sprayed to a dry coating with a thickness of 40 µ, left at room temperature for 10 minutes, and baked at 80 ° C for 30 minutes.

The alicyclic oxirane-containing compound ( ^* 1) has a terminal alicyclic oxirane group and has a number average molecular weight of 650, It is a compound obtained by making 1 mol of adipic acid react.

Example 5

The composition is prepared from the following components.

55 parts of non-aqueous dispersion (a-1) (55% solid)

80 parts of vinyl copolymer solution (b-3) (50% solid)

Tetrakis (acetylacetonato) zirconium0.5part

Alicyclic oxirane-containing compound ( ^* 2) 30 parts

Acetyl Acetone Part 3

The composition is applied to the substrate with a dry thickness of about 50 mu and fired at 90 DEG C for 30 minutes.

The cycloaliphatic-oxirane-containing compound ( ^* 2) has a terminal cycloaliphatic oxirane group and has a number average molecular weight of 392 and 2 moles of And a compound prepared by reacting 1 mol of hexamethylene diisocyanate.

Example 6

The composition is prepared from the following components.

182 parts of non-aqueous dispersion (a-2) (55% solid)

Tris (ethyl acetate acetate) aluminum 1 part

Acetyl Acetone Part 3

The composition is applied to the substrate with a dry thickness of 50 mu and then baked at 80 ° C. for 30 minutes to cure.

Example 7

The composition is prepared from the following components.

91 parts of non-aqueous dispersion (a-1) (55% solid)

100 parts of vinyl copolymer solution (b-1) (50% solid)

Tris (ethylacetoacetate) aluminum 2 parts

Acetyl Acetone Part 3

The composition is applied to the substrate with a dry thickness of 50 mu and then baked at 120 ° C. for 30 minutes to cure.

Comparative Example 1

The composition is prepared from the following components.

200 parts of vinyl copolymer solution (b-4) (50% solid)

Tris (ethylacetoacetate) aluminum 1 part

The composition is applied to the substrate with a dry thickness of 50 mu and then baked at 80 ° C. for 30 minutes to cure.

Comparative Example 2

The copolymer solution (b) in exactly the same manner as in the solution type vinyl copolymer (b-2) except for replacing all monomer components of the following general formula used in the solution (b-2) with n-butyl methacrylate. -9) is prepared.

The obtained solution had a solid concentration of 50%, a Gardner viscosity of N and a number average molecular weight of the resin component of 14,500.

The composition is prepared from the following components.

200 parts of vinyl copolymer solution (b-9) (50% solid)

Tris (ethylacetoacetate) aluminum 1 part

The composition is applied to the substrate with a dry thickness of 50 mu and fired at 100 캜 for 30 minutes.

Table 1 shows the results obtained by testing the cured coatings obtained in Examples 1 to 7 and Comparative Examples 1 and 2 (note in Table 1).

1) The appearance of the coating is visually evaluated at the time of finishing.

2) friction resistance

Using a gauze moistened with Nisseki Silver Gasoline, the sheath was observed after vigorously reciprocating eight times with a stroke length of 10 cm. The cladding is rated as “excellent” when the color is almost not blurred.

3) impact resistance

The coating is tested using a DuPont Impact Tester with a 1/2 inch needle tip radius and a weight of 500 g. Resistance is expressed by the maximum fall distance (5 cm increase) in which the coating remains uncracked.

4) water resistance

The test pieces were immersed in a 40 ° C. constant temperature water bath for 240 hours and then removed from the water. If no abnormalities such as fading or blistering are found, the coating is rated as “excellent”.

5) Acid Resistance

The coating is dotted with 0.5 cc of 10% sulfuric acid, left at 75% RH, 20 ° C for 48 hours, and rinsed with water for inspection.

6) Weather resistance

The sunshine weather-O-meter was used to irradiate the coating with light for 800 hours and then check gloss retention.

TABLE 1

Example 8

The composition is prepared from the following components.

109 parts of non-aqueous dispersion (a-4) (55% solid)

80 parts of vinyl copolymer solution (b-5) (50% solid)

Tris (ethyl acetoacetate) aluminum 1 part

Acetyl Acetone Part 5

Adjust the viscosity of the composition to 35 seconds (20 ° C.) with # 4 Pod Cup using a diluent, i.e., a mixture of isobutyl acetate and Swasol 1000 (aromatic solvent, manufactured by Cosmo Oil Co., Ltd.), at 1/1 weight ratio. It is used for painting.

The cationic electrophoretic epoxy coating composition was coated on a zinc phosphate-treated steel plate by electrophoresis to a thickness of 20 mu and dried at 170 ° C. for 20 minutes.

The cloth is treated with # 400 sandpaper and then degreased by wiping with gauze moistened with petroleum benzine.

Next, the automotive aminopolyester coating composition is applied to the coating with a thickness of 30 mu when dried, and baked at 140 ° C. for 30 minutes.

The resulting coating is wet treated with # 400 sandpaper, dehydrated, dried and washed with petroleum benzine to obtain a substrate.

The composition of which viscosity is adjusted as described above is air sprayed to a thickness of about 50 mu when dried on a substrate, then left at room temperature for 10 minutes and fired at 80 ° C. for 30 minutes. The coatings were tested and evaluated and the results are shown in Table 2.

In Examples 9 to 13 and Comparative Examples 3 and 4, unless otherwise stated, the substrate was prepared in the same manner as in Example 8 and the viscosity of the composition was adjusted.

Example 9

The composition is prepared from the following components. Titanium white is dispersed in a vinyl copolymer solution (b-6).

73 parts of non-aqueous dispersion (a-5) (55% solid)

80 parts of vinyl copolymer solution (b-6) (50% solid)

Tris (ethylacetoacetate) aluminum 2 parts

60 parts of titanium white JR-602 (product of Teikoku Kako Co., Ltd.)

Acetyl Acetone Part 5

Example 10

A base coating composition for wet-on-wet application is prepared from the following components.

90 parts of non-aqueous dispersion (a-6) (55% solid)

100 parts of vinyl copolymer solution (b-7) (50% solids)

Tris (acetylacetonato) aluminum 1 part

Aluminum paste # 4919 (Toyo Aluminum K.K.) 5 parts

10 parts of aluminum paste # 55-519 (Toyo Aluminum K.K.product)

Acetyl Acetone Part 3

Using xylene, the viscosity of the composition is adjusted to # 4 Pod Cup 15 seconds (20 ° C.) and used for painting.

A transparent finishing coating composition for wet-on-wet application is prepared from the following components.

91 parts of non-aqueous dispersion (a-4) (55% solid)

100 parts of vinyl copolymer solution (b-5) (50% solid)

Tris (acetylacetonato) aluminum 1 part

Acetyl Acetone Part 3

Using a diluent, a mixture of Swasol 1000 (aromatic solvent, manufactured by Cosmo Oil Co., Ltd.) and n-butanol (80/20 weight ratio), adjust the viscosity of the clear composition to 35 seconds with a # 4 pod cup and use it for painting. do.

The backing coating composition is air sprayed to the substrate with a dry thickness of about 18μ and left at room temperature for 5 minutes. The base coating composition was air sprayed to a base coating with a dry thickness of about 40 mu, left at room temperature for 10 minutes and fired at 80 ° C. for 30 minutes.

Example 11

The composition is prepared from the following components.

73 parts of non-aqueous dispersion (a-4) (55% solid)

80 parts of vinyl copolymer solution (b-5) (50% solid)

Tetrakis (acetylacetonato) zirconium part 2

Alicyclic oxirane-containing compound ( ^* 1) 20 parts

Acetyl Acetone Part 5

The composition is applied to the substrate with a dry thickness of about 50 μ and fired at 90 ° C. for 30 minutes.

Example 12

The composition is prepared from the following components.

109 parts of non-aqueous dispersion (a-5) (55% solids)

Tris (ethyl acetate acetate) 2 parts

40 parts alicyclic oxirane-containing compound ( ^* 2)

Acetyl Acetone Part 5

The composition is applied to the substrate with a dry thickness of about 50 μ and fired at 100 ° C. for 30 minutes.

Example 13

The composition is prepared from the following components.

91 parts of non-aqueous dispersions (a-5)

100 parts of vinyl copolymer solution (b-6)

Tris (ethylacetoacetate) aluminum 2 parts

Acetyl Acetone Part 2

The composition is applied to the substrate with a dry thickness of about 50μ and baked at 120 ° C. for 30 minutes to cure.

Comparative Example 3

The composition is prepared from the following components.

200 parts of vinyl copolymer solution (b-8) (50% solid)

Tris (ethylacetoacetate) aluminum 1 part

The composition is applied to the substrate with a dry thickness of about 50 mu and then baked at 80 ° C. for 30 minutes to cure.

[Comparative Example 4]

Copolymer solution (b) in exactly the same manner as in solution-type vinyl copolymer (b-5), except that the polysiloxane high molecular weight monomer M1 used in solution (b-5) was replaced with all n-butyl methacrylate. -10) is prepared. The obtained solution had a solid concentration of 50%, a Gardner viscosity (25 ° C) of Q, and a number average molecular weight of the resin component of 15,000.

The composition is prepared from the following components.

200 parts of vinyl copolymer solution (b-10) (50% solid)

Tris (ethylacetoacetate) aluminum 1 part

The composition is applied to the substrate with a dry thickness of about 50 μ and fired at 100 ° C. for 30 minutes.

Table 2 shows the results obtained by testing the cured coatings obtained in Examples 8 to 13 and Comparative Examples 3 and 4 in the same manner as mentioned above.

TABLE 2

Claims (10)

(a) about 70 to about 99.999 mol% of compound (A) of the following general formula (II) as a monomer component: (a) and about 30 to about 0.001 mol% of compound (B) of the following general formula (III) Polysiloxane high molecular weight monomer having at least two functional groups selected from molecular weight hydroxyl and alkoxyl and having a number average molecular weight of about 400 to about 100000, and ii) a vinyl copolymer containing an oxirane-containing vinyl monomer (hereinafter “copolymer Y A non-aqueous dispersion of particulate polymer insoluble in the organic liquid and polymerized with a radical-polymerizable unsaturated monomer in the presence of a dispersion stabilizer resin, and (b) a chelate mixed with the non-aqueous dispersion. A low temperature curable composition comprising a compound. Wherein R ₆ is an aliphatic hydrocarbon group or phenyl having 1 to 8 carbon atoms, R ₇ , R ₈ and R ₉ are each alkoxyl or hydroxyl having 1 to 4 carbon atoms and R ₁₀ is hydrogen or methyl, R ₁₁ , R ₁₂ and R ₁₃ are each hydroxyl, an alkoxyl having 1 to 4 carbon atoms or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and at least one of R ₁₁ , R ₁₂ and R ₁₃ is hydroxyl or alkoxyl M is an integer from 1 to 6). The composition of claim 1 wherein the oxirane-containing vinyl monomer is a vinyl monomer containing an alicyclic oxirane group. The composition of claim 1 wherein the oxirane-containing vinyl monomer is an acrylic or methacrylic acid ester containing an alicyclic oxirane group. The compound (A) according to claim 1, wherein the compound (A) is methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, phenyltrisilol and methyltrisilol At least one compound selected from the group consisting of. The compound (B) is a β-acryloxyethyltriethoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, or γ-methacryloxypropyl tree. A resin composition which is at least one compound selected from the group consisting of ethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxybutyltriethoxysilane and γ-acryloxypropyltrisilol. The composition of claim 1, wherein the polysiloxane high molecular weight monomer has, on average, from about 0.2 to about 1.9 polymerizable unsaturated bonds per molecule. The composition of claim 1 wherein the vinyl copolymer is prepared from about 0.01 to about 98 weight percent polysiloxane high molecular weight monomer and about 99.9 to about 2 weight percent oxirane-containing vinyl monomer. The composition of claim 1 wherein the number average molecular weight of the vinyl copolymer is from about 2000 to about 200000. The compound of claim 1, wherein the chelate compound is at least one of an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound. The composition of claim 1 which contains from about 0.01 to about 30 parts by weight of the chelate compound per 100 parts by weight of the resin solid in the composition.