JPS59176357A - Hard coating paint having excellent workability - Google Patents

Abstract

PURPOSE:To provide the titled paint which has good stability and gives a coating film having chafing resistance and high hardness without requiring heating, by using a specified Si atom-contg. resin as a base. CONSTITUTION:The titled paint consists of 100pts.wt. silyl group-contg. vinyl resin (A) whose main chain is composed of a polyvinyl linkage and which has at least one Si atom attached to a hydrolyzable group at its terminal or on its side chain (e.g. a resin obtd. by reacting a hydrosilane compd. such as methyldichlorosilane with a vinyl resin such as PVC in the presence of a group VIIItransition metal, e.g. platinum, as catalyst) as a base, 0.01-20pts.wt. curing catalyst (B) such as tin caprylate and 0-900pts.wt. solvent (C) such as xylene. The paint has good stability, gives a hard coat having high chafing resistance and hardness without requiring heating and allows in-situ application to be carried out without requiring any instrument for exclusive use.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides at least one silicon atom bonded to a hydrolyzable group at the terminal or side chain in one molecule, preferably 10 to 70 mol% in the solid content of the resin. contains, its molecular weight is 2
,000 to 70,000, 4,000 to make a good shelter for Sarah
The present invention relates to a paint that satisfies both workability and physical properties when used as a hard coating paint based on a resin having a molecular weight of ~50,000 yen.

Items that have traditionally been easily damaged (e.g. plastic, wood, aluminum, etc.) l/il: Coating to prevent scratches or add functions such as color retention, weather resistance, chemical resistance, etc. 1~, its commercial value It has often been done to increase On the other hand, in order to achieve the above purpose, No. 1. Typical paints that can be obtained include silicone-based paints and radically crosslinked polyfunctional acrylic paints. The former VC includes a method of partially hydrolyzing and condensing tetraalkoxysilane using water, alcohol, and a small amount of mineral acid, and a method of using alkyl trisilane mainly to improve flexibility. Various proposals have been made, including methods using co-hydrolyzed alkoxysilane, and methods using so-called orcas silica sol, which is a colloidal dispersion of silica with a particle size of several tens of microns in a hydrolyzate of alkyltrialkoxysilane. being done. These methods have many characteristics such as hardness, scratch resistance, weather resistance, and antistatic properties, but basically they have poor stability and short pot life due to the silanol being already partially condensed. There is a serious drawback of σ. If the paint is not stored under strict storage conditions, it will gradually thicken after being stored at room temperature for about 10 days, and even if it is applied, the hardness and scratch resistance, which are the most important features of silica-based paints, will not be maintained. I can't get it at all. Also, to improve this point, use alcohol solvent, colloidal silica, acetic acid, etc. 11. Adjustment of pH and methods of instantly solidifying the partial hydrolyzed condensate using a thin film evaporator and redissolving it have been tried, but most of the products that can be solidified have hydrophobic groups on the particle surface. Perhaps because of this, the curing properties tend to deteriorate, and there are still many problems. In addition, in order to obtain high hardness, thermosetting is essential. In general, for materials with high heat resistance such as PC (polycarbonate), 130 to 1
It is sufficient to bake at 40℃ for about 1 to 2 hours, but in the case of MMA (metal methacrylate), which has a low heat resistance temperature, bake at 70℃.
It requires baking at ~90°C for several to ten hours.
Furthermore, in order to prevent cracking and adhesion of the paint film, a single layer of primer is used, resulting in a multilayer paint film. 1) VC cannot be used for applications such as wood products where the permissible heating temperature is 50°C or less due to the characteristics of the base material, despite the strong need. Due to the poor workability as described above, its practical use is limited to high value-added products such as plastic eyeglass lenses.

On the other hand, the latter method uses monomers or oligomers having 2 to 4 acryloyl or methacryloyl groups in one molecule, such as pentaerythritolte I-la acrylate, trinotyrolpropane triacrylate, etc., as a reaction initiator and a photosensitizer. It is mainly cured using UV wavelength light.

Although its hardness and scratch resistance are somewhat inferior to the former, it is considered to be sufficiently durable for practical use, and there are few drawbacks such as instability of the paint liquid and short pot life, but it is cured by light irradiation. With so-called enamel paints that contain pigments, or with articles that have already been molded, there are fundamental problems such as not allowing light to pass through or creating shadows. .

For example, it is thought that it is most suitable for applications such as wood products that cannot be heated, but in these applications, it is the top coat that can meet the high hardness requirements, and the cold manufacturing method for l/rough coat mainly finishes up to the intermediate coating. This method is difficult to apply considering the process of assembling and processing the base materials and applying the top coating mainly by spray painting. Although it is a light-curing type, it is not possible to obtain a coating with a uniform thickness and smoothness due to the use of highly viscous acrylate. Currently, the solvent is diluted by about 50% and some kind of thermal energy is used in order to evaporate the solvent. Furthermore, in order to advance the reaction, reactive initiators and sensitizers blended into the paint remain in the cured coating film and reduce weather resistance, which impedes its practical use.

A common problem with both methods is that the VC coating work must be carried out using specialized equipment and under strict process control to avoid the problem of collecting dust and the like.

Although such an operation is possible inside a factory, it is nearly impossible when carried out on-site for large structures or repairs.

As a result of intensive research, the inventors of the present invention have found that the main chain consists essentially of polyvinyl-type bonds, and the terminal or side chain is bonded to a hydrolyzable group/at least one silicon atom per molecule, preferably A paint based on a resin containing 10 to 70 mol % in the solid content of the resin and whose molecular weight is 2,000 to 70,000, preferably 4,000 to 50,000, is used as a paint. It has good stability and does not require heat curing.
What's more, it was discovered that it has scratch resistance and hardness comparable to that of decoat. Furthermore, since no dedicated equipment operation is required, the present invention was achieved based on the results that it can be used in the same way as current paints, such as on-site application. The details will be explained below.

The resin used in the present invention has a main chain consisting essentially of a vinyl polymer, and a terminal or ((-1(f4jl) chain having a force [
] At least one silicon group bonded to a water-decomposable group in one molecule
, preferably 2 or more, (R1)
3-n(R2) 1 Most of the cy,.lyl groups are X n S + C
I(- (where X is a hydrolyzable group, R1,
R2 represents hydrogen or an alkyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms, and n is an integer of 1.2.3).

Examples of the hydrolyzable group include noroge/, alkoxy, acyloxy, ketoximate, amine, acid amide, amino acid, mercap+-, and alkenyloxyno-11-.

The production of the silyl group-containing vinyl resin of wood Iνj is a divine method, but the following steps are performed: (2) A method based on copolymerization of a vinyl compound and a silyl compound having a polymerizable double bond is an industrially effective method.

The details will be explained below.

(1) The silyl group-containing vinyl resin of the present invention is easily produced by reacting a hydrosilyl compound with a vinyl resin having a carbon-carbon double bond in the presence of all transition metals. The hydrosilane compound used in the present invention has the following general formula.

(R1)3.

Xn-5i-H (wherein, R1 is hydrogen or a monovalent hydrocarbon group selected from alkyl groups, aryl groups, and aralkyl groups having 1 to 101 carbon atoms, X is a hydrolyzable group, and n is 1 to 3 Specific examples of hydrosilane compounds containing -1h in this general formula include methyldichlorosilane, trichlorosilane 7, phenyldichlorosilano-like chino-logogenated silanes; methyljethoxysilane; /, alkoxysilanes such as methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilano, triethoxysilano, acyloxysilanes such as methyldiacetoxysilano, phenyldiacetoxysilane, triacetoxysilano, methyl/
Aminoxysilane, triaminoxysilane, methyldiaminosilane, l-riaminosilano, bis(dimethylketoximate)methylsilano, bis(cyclohexylketoximate)methylsilane, methylsilaneglopenoxysilane, triisopropenosilane Examples include various silanes such as.

The amount of the hydrosilane compound to be used may be any arbitrary amount with respect to the carbon-carbon double bonds contained in the vinyl resin, but it is preferably used in an amount of 0.5 to 2 times the molar amount of carbon-carbon double bonds contained in the vinyl resin. 1. Collect unreacted hydrosilane to check if it prevents the use of a larger amount of silane. It's Rutake.

As a polymerization initiator, azobisisobutyronitrile, 2,
Azo initiators such as 2' azohis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, (-butyl peroxide-1, [-butylperoxy 2-ethylhexanoate, (-butyl A peroxide initiator such as peroxybenzoate is used.The above polymerization initiator; The molecular weight can be adjusted by adding a chain transfer agent.

Silyl group-containing vinyl resins obtained using halogenated silanes harden quickly at room temperature while generating hydrogen chloride when exposed to the air, but they do not produce a pungent odor due to hydrogen chloride or may be difficult to contact. Since it can be practically used only in limited applications due to the problem of corroding nearby substances, it is desirable to further convert the rogen functional group into another hydrolyzable functional group. For example, JP-A-54-915
Alkoxy, acyloxy,
Can be converted to aminooxy, amino, acid amide, ketoximate, and mercapto groups.

The vinyl resin used in method G) of the present invention is not particularly limited, except for vinyl compounds containing hydroxyl groups, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Acrylic acids such as butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl tuccrylate, tucacrylic acid esters, acrylic acid, methacrylic acid, itaconic acid,
Carboxylic acids such as fumaric acid and acid anhydrides such as maleic anhydride, epoxy compounds such as glycidyl acrylate and glycidyl methacrylate, amine compounds such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and aminoethyl vinyl ether, acrylamide, methacrylamide, itaconic acid diamide, α-
Amide compounds such as ethyl acrylamide, crotonamide, fumaric diamide, maleic diamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, acrylonitrile, iminol methacrylate, styrene, α-methylstyrene, vinyl chloride, 1
A resin whose main component is a copolymer selected from vinyl acid, vinyl propionate, etc. is legitimate. When producing these vinyl compounds alone or as a copolymer, by radical copolymerizing some allyl acrylate, methacrylamide, diallyl phthalate, etc., carbon-carbon double bonds for hydrosilylation reaction are created in the vinyl resin. can be introduced into the terminal or side chain of the molecule. The amount of monomer necessary for this purpose can be arbitrarily determined depending on the number of silyl groups in the target resin. When polymerizing these vinyl compounds, a solvent may or may not be used, but when used, it is preferable to use a non-reactive solvent such as ethers, hydrocarbons, and acetic esters.

In the present invention, a transition metal complex catalyst is required in the step of reacting a hydrosilane compound with a carbon-carbon double bond. As the transition metal complex catalyst, a complex compound of a group transition metal selected from platinum, ronlum, cobalt, palladium, and nickel is effectively used. This hydrosilylation reaction is achieved at any temperature from 50 to +50°C, and the reaction time is about 1 to 10 hours.

苧) 3-n ■ Another method of the present invention is the formula (R2) SI
n (wherein the angle is a monovalent hydrocarbon group selected from alkyl groups, aryl groups, and aralkyl groups having 1 to 10 carbon atoms, (R2) is an organic residue having a polymerizable double bond, and X is a hydrocarbon group) A decomposable group, n is an integer of 1.2.3) is produced by radical polymerization of a silane compound represented by the following formula and various vinyl compounds.

Examples of the silane compounds used in the present invention include H3CH3 CH2=CH5i(OCH3)2, CH2=CH5
iCI2.

CH2=CH5i(OCH3)3, CH2=CH3
iC13.

CH3 I CH2=CHC00(CH2)3 S i (OCT-
I3) 2.

CH2=Cl-1cOO(CH2)3S i (OC
H3)3.

CH3 CH2=CHC00(CH2)35iC12.

CH2=CHC00(CH2) 3 S i Cl 3
.

CH3 CH2=C(CH2)Coo(CH2)35i(OCH
3)2.

CH2=C(CH2)Coo(CH2)3 S i (
OCH3)3.

CH3 CH2=C(CH2)Coo(CH2)35iC12.

CH2=C(CH2)COO(CH2)35iC13.

Q　Q　　a+3 II 11 O 111 00CH3 11II 1 　　　0 111 etc.

These silane compounds are synthesized by various methods, but for example, acetylene, allyl acrylate, allyl methacrylate, diallyl phthalate and methyldichlorosilane, methyldichlorosilane, trimethoxysilane, trichlorosilane are synthesized by group transition. It can be produced by reaction under the presence of a metal catalyst.

As the vinyl compound used in the present invention, it is possible to use the compounds used in the synthesis of vinyl resin in the method (1) above, but in addition to those described in the method (2), 2-hydroxyethyl Vinyl containing hydroxyl groups such as acrylate-2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate-1, 2-hydroxy vinyl ether, N-methylolacrylamide, Aronix 5700 (manufactured by Toagosei ■) Compounds can also be used.

Synthesis of a copolymer of these vinyl compounds and a silane compound (d) is carried out by a normal solution polymerization method.

The molecular weight can be controlled by selecting an appropriate polymerization temperature and amount of radical initiator, and optionally using a chain transfer agent such as n-dodecylmercaptan or di-dodecylmercaptan. The polymerization temperature can be selected between 50 and 150°C.

A solvent may or may not be used, but when used, it is preferable to use a non-reactive solvent such as ethers, hydrocarbons, and acetic esters.

The hydrolyzable groups of the silyl group-containing vinyl resin thus obtained can be converted, for example, by the method disclosed in JP-A-54-91546.

In this way, a silyl group-containing vinyl resin whose main chain is substantially composed of a vinyl polymer and which has at least one silicon group in one molecule bonded to a hydrolyzable group at the terminal or side chain. is obtained.

The molecular weight of the silyl group-containing vinyl resin used in the present invention is preferably in the range of 2,000 to 70,000; 4,000~50,000
A relatively high molecular weight range is more preferable. In addition, the silyl group-containing vinyl resin contains, as a copolymerization component, an ethylenically unsaturated organic monomer containing active hydrogen such as the carboxylic acid group, hydroxyl group, amine group, acid amide group, etc. exemplified above. Furthermore, it is possible to improve bot life and adhesion.

When curing the coating composition of the present invention, a curing agent may or may not be used depending on the curing conditions, but in order to satisfy physical properties such as room temperature curing, high hardness, and workability, a curing catalyst may be used. is practical.

Examples of organic tin compounds used as curing catalysts include carboxylic acid type compounds such as tin octylate and dibutyltin dilaure-l, sulfide type organic tin compounds such as monobutyltin sulfide and dibutyltin dioctyl mercaptide, and methylcaptide type organic tin compounds. Ru. Acidic phosphate esters include monomethyl acid phosphate, dinotyl acid phosphate, monoethyl F2 phosphate, diethyl acid (Jg 'J acid ester, monopropyl acid phosphate, dipropyl acid phosphate, monobutyl acid ester) Examples include phosphoric acid esters, dibutyl acidic phosphoric esters, monooctyl acidic phosphoric esters, dioctyl acidic phosphoric esters, etc. Reactants of the amines and acidic phosphoric esters include the above acidic phosphoric esters and methylene diamine. , reactants with primary amines such as diethylenetriamine, triethylenetetramine, metaphenylenediamine, and n-laurylamine; reactants with secondary amines such as piperidine, diethylamine, cy-2-ethylhexylamine, and distearylamine; Examples include reactants with tertiary amines such as N,N dimethyldodecylamine, triethylamine, dimethyloctylamine, and trilobylamine.

Saturated or unsaturated polycarboxylic acids and their acid anhydrides include aliphatic polycarboxylic acids and their acid anhydrides such as adipic acid, azelaic acid, sebacic acid, maleic acid, itaconic acid, citric acid, and succinic acid. Examples include aromatic carboxylic acids such as phthalic acid, l-limeriso[-acid, and pyromellitic acid, and their acid anhydrides. As a reactive silicone compound, as a silane coupling agent, for example, Nippon Unicar (A-143, A-151, A-172, A
=174, A-186, A-187, A~189, A-
1100, A-1120, A-1160, etc.

Examples of silicon-based primers include AP-133, AP-3109, Y-5106, and Y- manufactured by Nippon Unicar.
Amines having at least one silicon atom bonded to a hydrolyzable group in one molecule, such as 5252, such as Nippon Unicar (
A reaction product of a silane coupling agent containing an amine group such as A-+ loo, A-1120 manufactured by m, and a silane coupling agent containing an epoxy group such as A-186, A-187, for example, a reaction product containing the above amine group. Contains silane coupling agent, ethylene oxide, butylene oxide, epichlorohydrin, epoxidized soybean oil, and other Epikote 8 manufactured by Shell ■
28. Reaction products with compounds containing epoxy groups such as Epicote 1001, such as the above-mentioned epoxy group-containing silane coupling agents and ethylamine, diethylamine, triethylamine, ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. Reactants with aliphatic amines, aromatic amines such as aniline and diphenylamine, alicyclic amines such as cyclopentylamine and cyclohexylamine, and amines such as ethanolamine, such as silane coupling containing the above amine groups. Agents and acid anhydrides such as methyltetrahydrophthalic anhydride, methyl iminocic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, phenylmaleic anhydride, dodecylsuccinic anhydride reaction products with acid anhydrides such as the above amine group-containing silane coupling agent and ethyl silicate, ethyl silicate 40, methyltrimethoxysilane, methyltriethoxysilane, the above A-1511A-172
, A-174, 8-186, A-1'87, A-189
, A-1160, etc., a reaction product obtained by adding water and, if necessary, an acidic or alkaline acid catalyst to a compound containing a hydrolyzable silyl group, and subjecting the mixture to fractional water decomposition to 141, is used. Examples of organic titanate compounds include isopropyl triine stearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate,
Isopropyl tris (dioctyl pyrophosphate)
Monoalkoxy type such as titanate.

Monoalkoxypyrophosqate type such as isopropyl tri(dioctyl pyrophosphate) titanate, isopropyl tri(dibutyl pyrophosphate) titanate,
Chelate types such as bis(dioctyl pyrophosphate) oxyacetate titanate and bis(dioctyl pyrophosphate) ethyl silicate; coordinated types such as tetraisoprovir di(lauryl phosphite l-) titanate and tetraisoprovir di(dioctyl phosphite) titanate can be mentioned. Also used are amines such as tetraethylene bencumino and triethylene diamine, and alkaline curing catalysts such as potassium hydroxide and sodium hydroxide. These curing catalysts are preferably added in an amount of 0.01 to 20% by weight based on the resin.

In the present invention, in addition to the component (B), a solvent can be used depending on the case, but the solvent may be a solvent that dissolves both the silyl group-containing vinyl resin and the curing catalyst, or a solvent that can be mixed with other solvents even if it does not dissolve the silyl group-containing vinyl resin and the curing catalyst. Any solvent that does not form a precipitate when converted into a single liquid may be used, such as aliphatic hydrocarbons, aromatic hydrocarbons, etc. used in general paints, coatings, etc.
logenated hydrocarbons, alcohols, ketones, esters, ethers, alcohol esters, ketone alcohols, ether alcohols, ketone ethers,
Ketone esters and ester ethers can be used. Furthermore, when these solvents contain an alkyl alcohol or a hydrolyzable ester, the stability of the paint of the present invention can be further improved. As the alkyl alcohol, alcohols in which the alkyl has 1 to 10 carbon atoms are preferred, such as methyl alcohol, ethyl alcohol, +1-furobyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, Sec-butyl alcohol, and tert-butyl alcohol. -#, n-7 methyl alcohol, isoamyl alcohol, hexyl alcohol, octyl alcohol, cellosolve, etc. are used. Hydrolyzable esters include trimethyl orthoformate,
Trialkyl orthoformates such as tributyl orthoformate, tripropyl orthoformate, tributyl orthoformate: trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, etc., trikyl orthoacetate, tetramethyl orthosilicate, orthosilicate Tetraalkyl orthosilicate such as tetraethyl, tetrapropyl orthosilicate, tetrabutyl orthosilicate, γ-700propyltrimethoxysilane, vinyltriethoxysilane, vinyltriβ-methoxyethoxysilane, γ-methacryloxyglopyltrimethoxysilane, γ- Silane coupling agents such as glycidoxypropyl I-litoxysilane, γ-aminoglopyltriethoxysilane, and γ-ureidopropyltriethoxysilane are used. In addition, from the viewpoint of dehydration, we have previously applied for a patent showing that a paint with excellent storage stability can be obtained by adding a reaction accelerator to promote the selective reaction between the calohydrolyzable ester compound and water. . The amount of solvent varies depending on the molecular weight or composition of the silyl group-containing vinyl resin, and is used in accordance with the practically required solid content concentration or viscosity.

The hard coating paint of the present invention cures at room temperature or low temperature and becomes a resin with excellent adhesion to the surface of the base material. Applicable to tiles, ceramic slates), organic materials (plastics, wood, paper, coatings of various organic paints), etc.

Furthermore, from the perspective of the purpose of the present invention, from the viewpoint that the base material itself has low scratch resistance and can be protected by coating, acrylic resin, polycarbonate resin, polystyrene resin, acrylonitrile styrene copolymer, polyethylene terephthalate resin, etc. translucent plastic, nylon, glass fiber reinforced polyester, vinyl chloride resin, polypropylene, polyethylene, etc.
It can be cured at room temperature, such as opaque plastics, and has low solvent selectivity, so it can be applied to most plastics, regardless of whether they are thermosetting, thermoplastic, or polar.

Plastic molded products are used in a wide variety of applications, taking advantage of their advantages such as light weight, workability, impact resistance, and low cost. For example, eyeglass lenses, automobile parts, cameras, audio scale carpers, showcases, window glasses, etc. can be considered. In addition to plastics, aluminum can be considered as a material that is relatively easily damaged, and includes ordinary aluminum (A1050), corrosion-resistant aluminum (A5052), and chemically treated products thereof. Aluminum molded products have high corrosion resistance, are lightweight, have high heat reflectance, reduce energy loss, and have a beautiful appearance, so they are used as roofing materials, handrails, gates, etc.
Like plastic, it is used in large quantities in window frames and large vehicles. Particularly for large vehicles, etc., room temperature hardening types are desired because baking is difficult.

In recent years, wood products have become more popular due to the increased use of resources, the extension of product life due to protection, and the expansion of uses for tables, chairs, furniture, entrance doors, etc. due to the Westernization of lifestyles. There is a growing need to make the surface scratch-resistant, but since the base material is wood, it is mainly necessary to cure at room temperature, it is difficult to control the work environment such as the reproduction of polishing residue of intermediate paint, and it is difficult to assemble. Currently, there is no paint form that meets the restrictive conditions of top coating after processing, and it has not yet been put into practical use.

In addition, among current products, melamine and polyurethane products have relatively good scratch resistance, but these do not have satisfactory scratch resistance and often suffer from pickpockets caused by vibration during transportation of the product. ing.

Considering the above-mentioned current situation, it can be seen how useful the hard coating paint of the present invention is. If we consider the case of painting a base material that has no surface, the main purpose is to use enamel paint to prevent corrosion and give an aesthetic appearance, but if the enamel paint has poor scratch resistance or scratch resistance, it may cause the paint to stick to the base material. There is a serious problem of losing its original characteristics. From the above point of view, there is a great need for enamel paints with high hardness and excellent scratch resistance, such as silica-based hard coating agents that are difficult to enamel, and pigments such as shattered photocurable polyfunctional acrylics that inhibit light transmission. Compared to paint systems that have the disadvantage of not being able to form a cured film, the hard coating paint of the present invention, which can be enamelized using a conventional method, is a much-awaited product.

It is something that exists.

Furthermore, although the hard coating paint of the present invention has excellent weather resistance by itself, it is also possible to add ultraviolet absorbers, antioxidants, etc. as the case requires. If necessary, it can be blended with fillers, additives (leveling agents), and various resins that are still used in current paints, coatings, primers, and adhesives.

As the coating method, various methods commonly used in the coating field can be used, such as spray coating, dip coating, brush coating, roll coating, and curtain flow coating.

Next, Mizumotori] will be specifically explained using examples.

Example 1 8 g of styrene, 32 g of allyl methacrylate, 40 g of methyl methacrylate, 8 g of n-butyl methacrylate, 8 g of n-butyl acrylate, 4 g of maleic anhydride, 2 g of AlBN, in a xylene solvent of 80 P under heating at 90° (Ic). was added dropwise and reacted for 10 hours to obtain an allylic unsaturated group-containing vinyl polymer with a molecular weight of 14,000.The infrared absorption spectrum of this polymer shows absorption due to a 1648-carbon-carbon double bond. was observed.The low boiling point solvent was removed from the obtained polymer solution under reduced pressure.

Obtained allylic unsaturated group-containing vinyl copolymer solution 1
6g K methyldimethoxysilane 3.0g, chloroplatinic acid 0
．． 000! A solution of M dissolved in isopropanol was added and reacted under sealed conditions at 90°C for 6 hours.

The infrared absorption spectrum of this substance is +648 (!I11
' absorption disappeared, and a silyl group-containing vinyl polymer was obtained. Add xylene to this to bring the solid content concentration to 5.
It was adjusted to 0%.

Example 2 Styrene 5g ethyl acrylate 5g butyl acrylate + (1 methyl methacrylate
50g N-methylol acrylamide
2 g γ-methacryloxyglopyltrimethoxysila 7 27 g Azobisisobutyronitrile 1 g The above mixture was mixed with 60 g of xylene.
, and reacted in Inglovil Alcohol 7y at 80°C for 10 hours to obtain a silyl group-containing vinyl resin with molecular weights a o and o o o.

Xylene was added to this to adjust the solid content concentration to 50%.

Example 3 Styrene 5g2 Hydroxyethyl methacrylate 4g Butyl acrylate Ioy Methyl methacrylate)
19γ-methacryloxypropyltrimethoxysilane 609 Vinyltriethoxysilane l (1 n-dodecyl mercaptan 2g azobisisobutyronitrile
2g of the above mixture in xylene 67°C at 100°C.
The molecular weight was 6. A silyl group-containing vinyl resin of OQO was obtained. Xylene was added to this to adjust the solid content concentration to 50%.

Example 4 Styrene 5g Acrylamide 2g Butyl acrylate 10g Methyl methacrylate 21. FM γ-mekuacryloxyprobyltrimethoxysilane
6 (1 azobisisobutyronitrile 1.5y of the above mixture
! The reaction mixture was reacted in 7 g of Inglobil alcohol at 90°C for 10 hours to obtain a silyl group-containing vinyl resin with a molecular weight of 10,500. Xylene was added to this to adjust the solid content concentration to 50%.

Comparative Example 1 Methyltriethoxysilane I' (8y water
534
Hydrochloric acid (0.1 normal) 2.
J The above mixture was heated under reflux at 70°C with good mixing in a Kolben with a stirrer. The reaction was carried out for about 5 hours, at which point the initially non-uniform layer became uniform and transparent.

Thereafter, by-produced ethanol and some water were evaporated, and a small amount of acetic acid was added as a stabilizer to adjust the solid content concentration to 50%.

Comparative Example 2 A commercially available polyurethane paint (TDI curing two-component type) was used according to the specifications.

(1) Preparation of paint (dispersion preparation of inorganic enamel) To 100 g of the copolymer solution obtained in Examples 1 to 4, 66 g of titanium oxide (manufactured by Ishihara Sangyo, R-90) and 1 xylene were added and dispersed in a paint shaker for 30 minutes. This was done to obtain white enamel.

(Dispersion preparation of organic enamel) To 100 g of the copolymer solution obtained in Examples 1 to 4 was added phthalocyanine blue (ChroTnofin manufactured by Inunichika Kogyo Co., Ltd.).
Blue enamel was obtained by dispersing xylene for 1 hour in a paint shaker.

When the dispersibility of the pigment was examined using a tube gauge, the dispersibility of each sample was found to be 10 μm or less, which was good.

Incidentally, the silica-based hard coating agent (methyltriethoxysilane partial hydrolysis condensate) obtained in Comparative Example 1 was pigment-dispersed in the same manner as above, but the pigment and the hydrolyzate underwent phase separation, No enamel paint was obtained.

(2) Performance evaluation of coatings and coated products The clear and enamel coatings obtained in Examples 1 to 4 and Comparative Examples 1.2 were blended with the curing agents shown in Tables 1 to 4, and diluted with a solvent to a paintable viscosity. The coating was spray-coated on substrates A to E shown below to a dry film thickness of approximately 10 μm, and cured at 20° C. for 4 days to evaluate coating performance. (In Comparative Example I, the curing temperature was raised because a cured coating film could not be obtained under the above drying conditions.
Because the coating film cracked, base materials A, C, and D were dip-coated with Kansai Paint Japanese-made acrylic melamine resin Magikron to a dry film thickness of about 5μ as a primer, and the top coat of Comparative Example 1 and Example 1.2 was applied. The coating film was also applied by dip coating to a dry film thickness of 5 μm, and was cured by heating at 130° C. for 4 hours. The results are shown in Table 2.

l) Base material 2) Performance evaluation fa) Pencil hardness According to JISK-5400, the hardness of the pencil with the lowest hardness that causes scratches on the coating film with pencils of different hardness was expressed.

(b) zd Scratch resistance Indicates the degree of scratching when the coating film is lightly rubbed with +oooo steel wool.

◎ No scratches at all: ○ Almost no scratches: Scratches but the surface maintains its luster: × Numerous scratches are observed (c) Scratch resistance Paint film made of kraft paper Indicates the degree of damage caused by strong rubbing.

◎ No scratches at all: ○ Hardly any scratches: △ Scratches, but the surface gloss is maintained: × Numerous scratches are observed (d) Adhesion Board cross-cut Sellotape peeling 2 100 pieces of square ○ Not peeled at all: Approximately 50% peeled: × Fully peeled (e) Impact resistance Using a DuPont impact tester, place a 300 g weight on a 1/2 inch diameter weight. When dropped onto a paint film, it is expressed in terms of the height of the drop that does not cause paint film cracking.

(f) Moisture and heat resistance blister box, 50°CX3
The coated plate is exposed to conditions for several days, and changes in appearance such as blistering and cracking of the coating film, as well as adhesion, are examined.

○ No change at all: △ Slight decrease in appearance or adhesion: × Significant decrease in appearance and adhesion (g) Cold check resistance -20°C1''-5
Appearance of coating film after 10 cycles of 2 hours each at 0°C
Check adhesion.

○ No change at all: △ A slight decrease in appearance or adhesion is observed: × Appearance and adhesion are also significantly reduced (h) Storage stability test The paints of Examples 1 to 4 and Comparative Examples I and 2 were placed in tin cans. Changes in viscosity after storage at 40'C for 2 weeks and evaluation of abrasion resistance by Steel Cool are shown.

As shown above, it can be seen that the paint of the present invention does not require special equipment, and can easily be cured at room temperature to provide a stable heart coat paint with considerably high hardness and scratch resistance. This has been a very difficult field with conventional paints (urethane, melamine, etc.) due to hardness and scratch resistance, and with silica and photocurable polyfunctional acrylics due to workability.

Patent applicant Kanebuchi Chemical Industry Co., Ltd. Agent: Patent Attorney Makoto Asano -

Claims (10)

[Claims] (1) Hardware based on silyl group-containing vinyl resin holes whose main chain consists essentially of polyvinyl-type bonds and which has at least one silicon atom in each molecule bonded to a hydrolyzable group at the terminal or side chain. Coating paint. (2) Based on 100 parts by weight of resin (5), curing catalyst (B) is 0.01 to 20 parts by weight, and solvent (C) is 0 to 9 parts by weight.
The paint according to claim 1, comprising 0.00 parts by weight. (3) The paint according to claim 1, wherein the content of the silyl group component having a silicon atom bonded to a hydrolyzable group in the solid content of the resin holes is 10 to 70 mol%. (4) Molecular weight of resin (A) is 2,000 to 70,000
The paint according to claim 1, which is (5) Resin (a) contains N-methylolacrylamide, acrylamide, maleic anhydride, 2 as copolymerization components.
The paint according to claim 1, which contains at least one member selected from -hydroxyethyl methacrylate and vinyl acetate. (6) The paint according to claim 1, wherein the hydrolyzable group to the resin is an alkoxy group. (7) The paint according to claim 1, wherein the resin pores contain an ethylenically unsaturated organic monomer containing active hydrogen as a copolymer component. (8) The curing catalyst (B) is an organotin compound, an acidic phosphoric acid ester, a reaction product of an acidic phosphoric acid ester and an amine, a saturated or unsaturated polycarboxylic acid or its acid anhydride, a reactive silicone compound 1, The paint according to claim 1, which contains at least one selected from organic titanate compounds. (9) Solvent (C) contains alkyl alcohol
1. The paint according to claim 1, which is 1. (10) The paint according to claim 1, wherein the solvent (C) is a solvent containing one or more selected from tetraalkyl orthosilicate, trialkyl orthoformate, and trialkyl orthoacetate. fJl) 'N Agent (c), which contains one or more selected from argyl alcohol and tetraalkyl hyorthosilicate, trialkyl orthoformate, trialkyl orthophosphate, Paints listed in section.