JP2526903B2 - Coating resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel and useful coating resin composition. More specifically, the present invention relates to at least one polymerizable unsaturated double bond / siloxy group-containing vinyl-based monomer in each molecule, and another vinyl-based monomer copolymerizable with the monomer. A coating resin composition comprising a vinyl polymer obtained by copolymerizing a monomer, and a polyvalent metal alkoxide and / or chelate compound having reactivity with a hydroxyl group formed by the polymer. Regarding

[Conventional technology]

2. Description of the Related Art In recent years, plasticization of outer plates, parts, and the like has been rapidly progressing in the automobile industry and the home appliance industry. When the material is a steel plate, a baking one-pack type paint using an aminoplast type curing agent is usually adopted as the paint resin system used. However, when the material is made of plastic, there is a case where the heat resistance temperature of the material is low, and it is not appropriate to use a normal baking one-pack type paint for plastic. For plastics, room temperature curing type and low temperature curing type coatings have been studied or partially used. Examples of these paint-based resins include a combination of a polyol type resin and an isocyanate prepolymer, a combination of an acrylic resin having a tertiary amino group and a polyfunctional epoxy resin, and a curing system using aminoplast using a low-temperature curing catalyst. However, among such paint systems, the polyol type resin-isocyanate prepolymer system and the tertiary amino group-epoxy resin cured system are both two-pack types and have major drawbacks in workability such as pot life.

On the other hand, an aminoplast system using a low-temperature curing catalyst is a one-pack type as a form, but the functional groups involved in the reaction are not blocked, it is rich in activity, and its storage stability for a long time is extremely poor. It has drawbacks and cannot be cured at temperatures around room temperature.

If an isocyanate prepolymer obtained by blocking an isocyanate prepolymer with a suitable blocking agent is used, a one-pack type polyol-type resin-isocyanate prepolymer curing system can be obtained, but at present, the dissociation temperature of the blocking agent is high and the room temperature or low temperature. It is hard to say that it is a curable resin system.
As described above, from the viewpoint of workability of coating materials in the industrial world, and from the viewpoint of material conversion and energy saving, it is a one-pack type that is excellent in long-term storage stability, various physical properties, weather resistance, etc. The reality is that there is a demand for rapid development.

[Problems to be solved by the invention]

Thus, as long as the conventional technology is followed,
It has curability at room temperature or at low temperature, has excellent stability, and also has excellent coating film properties.
It has been extremely difficult to obtain a resin composition for coating having extremely high practicality.

However, the present inventors
Curability is good, stability is excellent, and in addition,
In search of a novel coating resin composition that is also excellent in various physical properties of the coating film, the inventors eagerly started research.

Therefore, the problems to be solved by the present invention are, in part, to have such curability at room temperature or at low temperature, excellent stability, and in addition to physical properties of the coating film. It is intended to provide a resin composition for coating which is excellent and has extremely high practicality.

[Means for solving problems]

Therefore, the present inventors focused their attention on the problems to be solved by the invention as described above, in order to obtain a vinyl-based coating material that meets the requirements as described above, as a result of earnest studies, as a result, A polymer obtained by using at least one specific monomer of a polymerizable unsaturated double bond / siloxy group-containing vinyl monomer in one molecule is surprisingly
The present invention has been completed here by discovering that these required performances can be improved.

That is, the present invention basically comprises 1 to 1 vinyl-based monomers (A) each having at least one polymerizable unsaturated double bond and a siloxy group in a molecule.
A vinyl-based polymer (I) obtained by copolymerizing 100% by weight with 99 to 0% by weight of another vinyl-based monomer (B) copolymerizable with the monomer, and a polyvalent metal alkoxide. And / or a chelate compound (II) are contained in the resin composition for coating.

In the coating resin composition according to the present invention, in the vinyl polymer (I), the siloxy group in the portion which is the structural unit based on the vinyl monomer (A) reacts with moisture in the air. To generate a hydroxyl group in the vinyl polymer (I) and react with the hydroxyl group and a polyvalent metal alkoxide and / or a chelate compound (II) to form a strong coating film. It is intended to provide a resin composition for coating, which has excellent storage stability and can also be used as a one-component paint.

Here, as the vinyl-based monomer (A),
A vinyl-based monomer having at least one polymerizable unsaturated double bond in each molecule and typically a siloxy group bonded to a carbon atom represented by the following formula.

The method for preparing these vinyl-based monomers (A) is not particularly limited, but if only representative ones are exemplified, triethylamine, pyrimidine, etc. like,
In the presence of a so-called hydrochloric acid scavenger, a compound group (a) of so-called halogenated silane compounds (halosilanes) such as trialkylchlorosilane, triarylchlorosilane, dialkylchlorosilane, dialkyldichlorosilane or dialkylhydrosilane. And a compound in the form of being obtained by reacting with a hydroxyl group-containing right vinyl-based monomer (b). Of these, particularly representative ones are exemplified, trimethylsiloxyethyl (Meth) acrylate,
Examples include trimethylsiloxypropyl (meth) acrylate, trimethylsiloxybutyl (meth) acrylate, triethylsiloxyethyl (meth) acrylate, tributylsiloxypropyl (meth) acrylate, and triphenylsiloxyalkyl (meth) acrylate. These can be used alone or as a mixture of two or more kinds.

Moreover, as the hydroxyl group-containing vinyl-based monomer (b), β-hydroxyethyl (meth) acrylate, β-
Hydroxypropyl (meth) acrylate or β-
Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate or N-methylolated (meth) acrylamide; β-hydroxyethyl (meth) acrylate to which ε-caprolatone is added [eg Praxel FM, FA series ( DAICEL CHEMICAL INDUSTRIES CO., LTD. And TONE ^TM M-100 (manufactured by Union Carbide Co.)]; BLEMMER PP-1000 represented by generic name polypropylene glycol monomethacrylate and BLEMMER PE series represented by generic name polyethylene glycol monomethacrylate (both Kyo Nippon Oil & Fat Co., Ltd.);
Unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid or itaconic acid, and "Cadura E" (manufactured by Shell Chemical Co., Ltd., glycidyl ester of branched fatty acid), glycidyl octylate or coconut oil Typical examples are adducts with monoepoxy compounds represented by monoglycidyl esters of monovalent carboxylic acids such as fatty acid glycidyl esters or monoglycidyl ethers such as butyl glycidyl ether. The amount of the vinyl monomer (A) used is preferably 1 to 100% by weight, and more preferably 5 to 90% by weight. If the amount is less than 1% by weight, the effect of the monomer cannot be expected.

Typical examples of the vinyl monomer (B) include alkyl (meth) acrylates having 1 to 22 carbon atoms, styrene, vinyl toluene, t-butylstyrene,
unsaturated carboxylic acids such as α-methylstyrene, glycidyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylonitrile, cyclohexyl (meth) acrylate, (meth) acrylic acid, maleic acid, fumaric acid or itaconic acid (Meth) acrylamides such as acids, diesters of maleic acid or fumaric acid and C _{1 to} C ₁₈ monohydric alcohols, (meth) acrylamide or N-alkoxymethylated (meth) acrylamide, N, N dialkylamino Examples include alkyl (meth) acrylates or (meth) acrylates containing a phosphoric acid group, and vinyl-containing monomers such as vinyl acetate, hexafluoropropylene, and tetrafluoroethylene.

These vinyl-based monomers (B) can be used alone or as a mixture of two or more types depending on the desired coating film performance. It is possible to use the above-mentioned hydroxyl group-containing vinyl monomer (b) as the vinyl monomer (B) component, but in the present invention, since a polyvalent metal alkoxide and / or a chelate compound is used as a curing agent, the storage stability of the coating composition is improved. Vinyl monomer (B)
Care should be taken in using the monomer as a component.

In order to obtain the vinyl polymer (I) which constitutes the composition of the present invention, a known and conventional method using the above-mentioned monomers, for example, a solution polymerization method using a radical generator is carried out. You can

As the radical generator, any of those usually used for the polymerization of vinyl-based monomers may be used, but among them, representative ones include azobisisobutyronitrile and di-tert-butyl. Peroxide or benzoyl peroxide, etc., and as the solvent, aromatic hydrocarbons such as toluene or xylene; acetic acid ester such as ethyl acetate, butyl acetate or cellosolve acetate; ketone based such as methyl ethyl ketone or methyl isobutyl ketone Or a cellosolve system such as methyl cellosolve or ethyl cellosolve can be used.

If necessary, mercaptans, α-methylstyrene and “dipentene T” (products of Nippon Terpene Chemical Co., Ltd.)
It is also possible to use a commonly used chain transfer agent such as, for example.

The vinyl polymer (I) thus obtained preferably has a number average molecular weight (n) of 500 to 50,000.

When n of the polymer (I) is less than 500,
The physical properties of the coating film cannot be sufficient, and the hydroxyl value generated after the trialkylsiloxy groups and the like of the polymer (I) are liberated in an attempt to bring out the physical properties of the coating film (hereinafter referred to as "OH value" If the value exceeds 50,000, on the contrary, the appearance of the coating film,
It is not preferable because defects tend to appear in gloss, feeling of holding, painting workability, and the like.

Next, as a polyvalent metal alkoxide and / or chelate compound which is a curing agent having reactivity with a hydroxyl group generated from the vinyl polymer (I), aluminum,
Titanium, zirconium, cobalt, zinc, copper, lead,
Typical examples are alkoxides or chelate compounds of magnesium, vanadium, iron or nickel. Among them, alkoxides or chelate compounds of aluminum, titanium, zirconium are particularly preferable from the viewpoints of curability, low toxicity and low coloring property. Is preferred. Specific examples of the metal alcoholate include aluminum isopropylate, aluminum-n-butyrate,
Aluminum-sec-butylate, aluminum isobutyrate, aluminum-t-butylate, tetra-n
-Propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate dimer, tetra-n-butyl titanate tetramer, tetra-sec-butyl titanate, tetramethyl zirconate, tetraethyl zirconate, Examples thereof include tetra-i-propyl zirconate, tetra-n-butyl zirconate, and tetra-i-butyl zirconate.

On the other hand, a polyvalent metal chelate compound can be prepared by reacting the above-mentioned alcoholates with a chelating agent. Specific examples of such a chelating agent include monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol. Such as alkanolamines, methyl acetoacetate, acetoacetates such as ethyl acetoacetate, acetyl-acetone, β-diketones such as benzoylacetone, dimethyl malonate, malonates such as diethyl malonate, methyl salicylate, Salicylic acid esters such as ethyl salicylate, ethylene glycol, 1,3-propanediol, 1,3-butanediol, glycols such as octylene glycol, lactic acid, oxyacids such as tartaric acid and esters thereof, and Diacetone alcohol,
Catechol and the like.

Specific examples of the complex compound obtained from the alcoholates and the chelating agent include aluminum bis (ethylacetoacetate) monoisopropylate, aluminum tris (ethylacetoacetate), and aluminum bis (ethylacetoacetate) monoacetoacetonate. Di-i-propoxy-bis (acetylacetone) titanate, di-i-propoxy-bis (ethylacetoacetate) titanate, di-n-butoxy-bis (acetylacetone) titanate, di-n-butoxy-
Bis (triethanolamine) titanate, tetraoctylene glycol titanate, n-butoxy-tris (acetylacetone) zirconate, n-butoxy-tris (ethylacetoacetate) zirconate, tetrakis (acetylacetone) zirconate, tetrakis (ethylacetoacetate) zirconate, Examples thereof include tris (acetylacetone) monoethylacetoacetate zirconate and bis (acetylacetone) bis (ethylacetoacetate) diclonate.

The compounding amount of the curing agent (II) with respect to the vinyl polymer (I) is set so as to fall within the range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the vinyl polymer (I). Preferably. If the amount used is less than 0.01% by weight, the curability is inferior. If the amount exceeds 10% by weight, the cured product becomes extremely brittle, which is not preferable.

A dissociation promoting catalyst can be added to the composition of the present invention in order to dissociate a silane compound bonded to a hydroxyl group with water in the air or the like to generate a hydroxyl group and a silanol compound. When curing the composition of the present invention in a temperature range from room temperature to less than 60 ° C, it is preferable to use a catalyst,
At a temperature of ° or higher, the above performance can be obtained without using a catalyst. However, it does not impede its use. As the catalyst, phosphoric acid, phosphoric acid ester, phosphorous acid ester, unsaturated group-containing phosphoric acid ester, p-toluenesulfonic acid and its amine salt, benzoic acid, trichloroacetic acid, trifluoroacetic acid, naphthalenedisulphonic acid and its Acidic catalysts such as amine salts, ethylenediamine, N-
amines such as β-aminoethyl-γ-aminopropyltrimethoxysilane, butylamine, dibutylamine, t-butylamine, hexylamine and triethylamine,
Alkali catalysts such as potassium hydroxide, lithium hydroxide, sodium hydroxide, alkyl titanates, octylates,
Dibutyltin dilaurate, and metal salt of carboxylic acid such as lead octylate, monobutyltin sulfide, sulfide type such as dioctyltin mercapite, mercaptide type organotin compound, tetraethylammonium fluorite,
Compounds that generate fluorine ions such as cesium fluoride are effective. The amount of these catalysts used is the vinyl polymer (I).
To 0.001 to 10% by weight, preferably 0.005 to 8% by weight
It is said.

Since the composition of the present invention does not generate a hydroxyl group that can react with the curing agent unless exposed to the atmosphere, a one-pack type and highly stable coating composition can be obtained from the composition of the present invention. However, in order to ensure long-term storage stability, it is only necessary to capture a small amount of water that enters for some reason.
That is, long-term stability is ensured by adding a water binder having reactivity with water. The water binder is
It does not matter if the vinyl polymer (I) is used by mixing it in the initial stage in advance. Examples of the water-binding agent having reactivity with water include trialkyl orthoformates such as trimethyl orthoformate, triethyl orthoformate and tributyl orthoformate; trialkyl orthoacetate such as trimethyl orthoacetate, triethyl orthoacetate and tributyl orthoacetate. Trialkyl orthoborates such as tributyl orthoborate and triethyl orthoborate; tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate, tetra (2-methoxyethyl) silicate or tetra (2-chloroethyl)
Tetra (substituted) alkyl silicates such as silicates alone; above-mentioned tetra (substituted) alkyl silicates such as tetraphenyl silicates and tetrabenzyl silicates, same-effect substances (hereinafter abbreviated as same-effect single substances); or tetraethyl silicate dimers, trimers , Tetramer,
Hexamer “Ethyl silicate 40” (Colcoat Co., Ltd.)
Products, tetramers of tetraethyl silicate, pentamers, mixtures of hexamers, etc.), each of the above-mentioned tetra (substituted) alkyl silicates alone, hydrolyzable ester compounds such as condensates of the same effect simple substance of the silicates, phenyl isocyanate , P-chlorophenyl isocyanate, benzene sulfonyl isocyanate, p-triene sulfonyl isocyanate, isocyanate ethyl methacrylate (NCO group-containing monomer manufactured by Dow Chemical Co., Ltd.) and the like.

The amount used is 0.1 to the vinyl polymer (I).
-30% by weight, preferably 0.5-20% by weight.

The composition of the present invention thus obtained can be used as it is as a clear paint, and can also be used as an enamel paint by mixing a pigment. In addition, various conventional additives such as a leveling agent, an ultraviolet absorber and a pigment dispersant can be added to the composition of the present invention as required.

Further, known and commonly used cellulosic compounds, plasticizers, polyester resins and the like can also be used.

As a coating method, a conventional method such as brush coating, spray coating or roll coating can be adopted, and as a curing method, in a wide range from normal temperature drying to heat drying, a polymer component and a curing agent constituting the composition of the present invention are used. Optimal curing conditions can be designed according to the combination with the components.

The composition of the present invention thus obtained is a plastic,
It can be widely used for metals, wood, building materials, inorganic materials and the like. In particular, the effect is remarkable in the field where one-component type, room temperature / low temperature curing type, and storage stable production are required.

[Examples, etc.]

Next, the present invention will be specifically described with reference to Reference Examples, Production Examples, Examples and Comparative Examples, and all parts below are by weight unless otherwise specified.

Production Example 1 [Preparation of vinyl polymer (I)] A four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet was charged with 667 parts of xylene.
The temperature was raised to ° C. At that temperature, 200 parts of styrene, 443 parts of n-butyl methacrylate, 150 parts of Acryester SL [vinyl monomer manufactured by Mitsubishi Rayon Co., Ltd.], 207 parts of trimethylsiloxyethyl methacrylate, t-butyl peroxyoctoate. A mixture of 10 parts [hereinafter abbreviated as TBPO] and 333 parts of xylene was added dropwise over 4 hours.
Then, the reaction was continued at the same temperature for 8 hours, and the nonvolatile content [hereinafter,
Abbreviated as NV] 50% number average molecular weight [hereinafter abbreviated as n] 13
000 resin solution was obtained.

Production Examples 2 to 4 [Preparation of vinyl polymer (I)] and Production Example 5 [Preparation of comparative vinyl polymer (I)] 200 parts of styrene used in Production Example 1, n-butyl methacrylate Instead of 443 parts, Acryester SL 150 parts, trimethylsiloxyethyl methacrylate 207 parts and TBPO, the same operations as in Production Example 1 were repeated except that the monomers and the amount of the initiator shown in Table 1 were used. , Vinyl polymers (I) were obtained. In Table 1, n is also described.

Production Example 6 [Preparation of vinyl polymer (I) for comparison] Instead of the vinyl monomer mixture used in Production Example 1,
The same operation as in Production Example 1 was repeated except that 200 parts of styrene, 590 parts of n-butyl methacrylate, 100 parts of Acryester SL and 110 parts of β-hydroxyethyl methacrylate were used to obtain a resin solution having NW of 50% and n15000. . Hereinafter, this is abbreviated as [I-6].

Examples 1 to 5 and Comparative Examples 1 to 2 Clear paints were separately prepared according to the compounding ratios (parts by weight) shown in Table 2 by a conventional coating method, and xylene / toluene / ethyl acetate = 30/50. / 20 (weight ratio) diluted to a spray viscosity with a mixed solvent and spray-coated on a zinc phosphate-treated steel plate so that the dry coating film becomes 30 μm,
A cured coating film was obtained by heating at 60 ° C. for 30 minutes. The results of physical property evaluation of each coating film thus obtained are shown in Table 2. The evaluation of the physical properties was performed after the forced drying was allowed to stand at room temperature for 3 days.

[Effect of the present invention] From the performance evaluation results shown in Table 2, the composition of the present invention is excellent in the physical properties of the cured coating film and long-term storage stability, and has one-component room temperature or low temperature curability. I understand.

Claims (1)

(57) [Claims] 1. A copolymerizable with 1 to 100% by weight of a vinyl-based monomer (A) having at least one polymerizable unsaturated double bond and a siloxy group in each molecule, and the monomer. Naruto other vinyl monomers (B)
Of 99 to 0% by weight of a vinyl-based polymer (I) obtained by copolymerization with a polyvalent metal alkoxide and / or a chelate compound (II). Stuff.