JP2002105147A - Low-odor resin composition and covering material comprising the same and covering method using the material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-odor resin composition having excellent curability and durability and affording favorable finish appearance with good workability, to provide a covering material such as corrosionproof material, waterproof material or flooring material using the composition, and to provide a covering method using the covering material. SOLUTION: This resin composition comprises (a) 100 pts.mass of an epoxy (meth)acrylate consisting of a reaction product from (α) an epoxy compound prepared by reaction between 1.0 mol of bisphenol and a total of 1.5-3.5 mol of an aliphatic diglycidyl ether-type epoxy compound and/or an aromatic polyfunctional epoxy resin and (β) (meth)acrylic acid, (b) 70-150 pts.mass of a low-odor polymerizable organic matter having double bond, (c) 0.6-10 pt(s).mass of a curing agent and (d) 0.2-5 pt(s). mass of a curing promoter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition suitable for a coating material, a coating material containing the resin composition, and a coating method using the coating material. More specifically, it has low odor and excellent curing properties, and its cured product has excellent toughness, strength, durability and chemical resistance and can be used for various anticorrosive materials, waterproof materials, floor covering materials and fiber reinforced plastics. The present invention relates to a resin composition, a coating material containing the resin composition, and a coating method using the coating material.

[0002]

2. Description of the Related Art Unsaturated polyester resins, vinyl ester resins, acrylic resins and the like have hitherto been used as curable resins which can be cured by radical polymerization at room temperature.
These resins use a styrene monomer as a polymerizable diluent as an unsaturated polyester resin and a vinyl ester resin, and a monomer such as methyl methacrylate as an acrylic resin. These monomers are highly volatile and
Due to the strong odor, it poses a problem during construction or molding, which limits its use.

In order to reduce the odor, when a low-volatile acrylic monomer is used instead of a monomer such as styrene or methyl methacrylate, the viscosity becomes high and the workability becomes poor. The amount used was large, and it was difficult to satisfy the cured product performance such as odor, toughness, strength, and durability.

[0004] In addition, as a coating material such as an anticorrosive material, a waterproof material, and a floor material, a moderate tensile force is used so as not to cause breakage due to factors such as impact, fluctuation in use temperature, and generation of hair cracks on the base material. It is important to have an elongation at break, and the tensile elongation at break of the coating material is preferably 0.5 to 100%, more preferably 0.5 to 70%. It was difficult to achieve a low odor and an appropriate tensile elongation at break by simply using a resin composition using a low volatility monomer as the polymerizable diluent.

Further, in order to prevent sagging when the coating material is applied to inclined surfaces and vertical wall surfaces, a thixotropic material is often added. However, coating materials containing volatile monomers such as styrene monomer and methyl methacrylate are often used. The fluidity of the material deteriorated due to monomer evaporation during construction, and it was difficult to obtain a good finish. Also in this case, it was difficult to develop an appropriate tensile elongation even if the resin composition contained a low volatile monomer instead of the volatile monomer.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems and contains a resin composition excellent in low odor, curability, toughness, durability and workability during construction. A coating material and a coating method using the coating material are provided.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a specific epoxy (meth)
By using a low-odor (meth) acrylate monomer as an acrylate and a polymerizable organic substance having a low-odor double bond, and further blending these in a certain ratio, preferably by further combining with a specific filler. ,
The inventors have found that this problem can be solved, and have completed the present invention. That is, the present invention relates to an epoxy obtained by reacting 1.0 mol of bisphenol with a total of 1.5 to 3.5 mol of an aliphatic diglycidyl ether type epoxy compound and / or an aromatic polyfunctional epoxy resin. With respect to 100 parts by mass of the epoxy (meth) acrylate (a) composed of the reaction product of the compound (α) and the (meth) acrylic acid (β), the polymerizable organic substance (b) having a low odor double bond and 70 to 100 parts by mass 150 parts by mass, curing agent (c) 0.6 to 10 parts by mass, and curing accelerator (d) 0.1.
A resin composition (A) containing 2 to 5 parts by mass.

The resin composition (A) according to the above (A), wherein the ratio (mol%) of the aliphatic diglycidyl ether type epoxy compound to the total amount of the aliphatic diglycidyl ether type epoxy compound and the aromatic polyfunctional epoxy resin is 0 to 100. ).

The resin composition according to (A), wherein the ratio (mol%) of the aliphatic diglycidyl ether type epoxy compound to the total amount of the aliphatic diglycidyl ether type epoxy compound and the aromatic polyfunctional epoxy resin is 40 to 100 (A) ).

A coating material containing the resin composition (A) according to any one of the above.

[0011] The coating material according to the above description, which comprises 1 to 400 parts by volume of the filler (B) based on 100 parts by volume of the resin composition (A).

The coating material according to any one of claims 1 to 3, further comprising a thixotropic agent.

[0013] The coating according to the above, wherein the thixotropic material is a polyolefin pulp-like substance.

A coating method using the coating material according to any one of the above.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy (meth) acrylate (a) used in the present invention has a total of 1.0 mol of bisphenol, an aliphatic diglycidyl ether type epoxy compound and / or an aromatic polyfunctional epoxy resin. 1.5
To 3.5 moles of the epoxy compound (α) and (meth) acrylic acid (β).

The bisphenol which can be used for preparing the epoxy (meth) acrylate (a) includes:
Bisphenol A, bisphenol S, bisphenol F, brominated bisphenol A, hydrogenated bisphenol A,
Bisphenol AF can be mentioned.

The aliphatic diglycidyl ether type epoxy compound which can be used for preparing the epoxy (meth) acrylate (a) is a diglycidyl ether type epoxy compound of an aliphatic bifunctional alcohol, and has an epoxy equivalent of It is preferably 300 or less.

Specific examples thereof include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, and (di) glycerol. (Poly) glycidyl ether, polytetramethylene glycol diglycidyl ether and the like.

The aromatic polyfunctional epoxy resin which can be used for preparing the epoxy (meth) acrylate (a) is a polyfunctional epoxy resin having an aromatic ring in a molecule and having an epoxy equivalent of 600 or less. Is preferably 3
Those having a value of 00 or less are more preferable.

Specific examples of the aromatic polyfunctional epoxy resin include a phenol novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, an alkylphenol type epoxy resin, a resorcinol type epoxy resin. Resins, N-glycidylamine type epoxy resins, brominated epoxy resins, and the like can be mentioned, and bisphenol type epoxy resins are preferable. Of these, bisphenol A epoxy resin is particularly preferred.

The epoxy compound (α) used for preparing the epoxy (meth) acrylate (a) is bisphenol and an aliphatic diglycidyl ether type epoxy compound and / or
Alternatively, it can be obtained by reacting with an aromatic polyfunctional epoxy resin.

The reaction between the bisphenol and the aliphatic diglycidyl ether type epoxy compound and / or the aromatic polyfunctional epoxy resin is carried out by reacting the phenolic hydroxyl group of bisphenol with the aliphatic diglycidyl ether type epoxy compound and / or the aromatic polyfunctional epoxy resin. This is a reaction with an epoxy group of a functional epoxy resin, and is usually performed at a temperature of 100 to 200 ° C.

In this reaction, an inorganic base such as sodium hydroxide, potassium hydroxide or lithium hydroxide, or an organic base such as triethylamine can be used as a catalyst. Particularly, an inorganic base is preferable.

In the above reaction, a total of 1.5 to 3.5 moles of the aliphatic diglycidyl ether type epoxy compound and / or the aromatic polyfunctional epoxy resin is usually reacted with 1.0 mole of bisphenol. . More preferably, it is 2.0 to 3.0 mol. When the amount is less than 1.5 mol, the viscosity of the obtained resin composition tends to increase and the workability tends to decrease, and when it exceeds 3.5 mol, the cured product of the obtained resin composition has There is a tendency for toughness to decrease.

Since the epoxy group is in excess of the phenolic hydroxyl group in the amount of the above-mentioned reagent used, the epoxy compound (α) obtained by the reaction usually contains unreacted aliphatic diglycidyl ether type epoxy compound. It contains a compound or an aromatic polyfunctional epoxy resin.

The above reaction can be carried out using 0 to 3.5 mol of an aliphatic diglycidyl ether type epoxy compound and 0 to 3.5 mol of an aromatic polyfunctional epoxy resin per 1 mol of bisphenol. Preferably, the amount of the aliphatic diglycidyl ether type epoxy compound is usually in the range of 40 to 100 mol% based on the total amount of the aliphatic diglycidyl ether type epoxy compound and the aromatic polyfunctional epoxy resin. And preferably from 60 to 100
Amounts in the mole% range can be used.

When the proportion of the aliphatic diglycidyl ether type epoxy compound used is increased, the tensile elongation at break of the cured product of the resin composition of the present invention is increased, and the amount of the aliphatic diglycidyl ether type epoxy compound used is reduced to 100 moles. %, The tensile elongation at break of the cured product can be 50% or more. Further, as the length of the aliphatic group of the aliphatic diglycidyl ether type epoxy compound increases, the tensile elongation at break of the cured product increases. On the other hand, when the use ratio of the aromatic polyfunctional epoxy resin is increased, the tendency of the cured product to decrease in tensile breakage tends to decrease, and instead of bisphenol type, novolak type and resol type aromatic compounds are present in the molecule. As the number of rings increases, the tensile elongation at break of the cured product tends to decrease.

As is evident from the above, the proportion of the aliphatic diglycidyl ether type epoxy compound and the aromatic polyfunctional epoxy resin and the type thereof are determined by the length of the aliphatic group, the number of aromatic rings and the aromatic group. By appropriately selecting according to the type of the system polyfunctional epoxy resin, the cured product of the resin composition of the present invention, the tensile elongation at break of the cured product of the coating material is adjusted according to the intended use, and the heat shrinkage of the base material, It can be designed to follow thermal expansion. Usually, the tensile elongation at break of the cured product of the resin composition (A) used for preparing the coating material is 5 to 100%, preferably 5 to 70%. The tensile elongation at break of the coating material of the present invention is preferably 0.5 to 1.
00%, and more preferably 0.5 to 70%.

The epoxy (meth) acrylate (a) used in the present invention can be obtained by reacting an epoxy compound (α) with (meth) acrylic acid (β). The above reaction is usually performed at 80 ° C to 130 ° C.

As the reaction catalyst, tertiary amines such as triethylamine and dimethylaniline, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, and inorganic salts such as lithium hydroxide and lithium chloride can be used.

In the above reaction, when the epoxy compound (α) is produced, the OH group of the bisphenol and the epoxy group of the aliphatic diglycidyl ether type epoxy compound and / or the aromatic polyfunctional epoxy resin are reacted at a ratio of 1: 1. In general, the reaction can be carried out using 0.9 to 1.1 mol of (meth) acrylic acid (β) based on 1 mol of the epoxy group remaining in the epoxy compound (α) calculated as follows. In the above reaction, a polymerization inhibitor is used as necessary. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone and methylhydroquinone, benzoquinones such as benzoquinone and methyl-P-benzoquinone, and catechols such as t-butylcatechol. And phenols such as 2,6-di-t-butyl-4-methylphenol and 4-methoxyphenol, and phenothiazine.

The polymerizable organic substance (b) having a double bond with low odor used in the present invention has a relatively large molecular weight,
Organic substance having a vapor pressure of 1 mmHg or less at 20 ° C.

Specific examples of the polymerizable organic substance (b) having a double bond having a low odor include an alkyl methacrylate having 8 or more carbon atoms, a methoxypolyethylene glycol methacrylate containing an ethylene residue having 10 or more carbon atoms, and dicyclohexane. Pentenyloxyethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate and the like can be used, and these may be used alone or in combination.

In the resin composition (A) of the present invention, the ratio of the epoxy (meth) acrylate (a), which is an essential component constituting the resin composition, and the polymerizable organic substance (b) having a low-odor double bond is such that (Meth) acrylate (a)
70 to 150 parts by mass of a polymerizable organic substance (b) having a low-odor double bond with respect to 100 parts by mass,
80 to 140 parts by mass, more preferably 90 to 130 parts by mass. When the amount of the polymerizable organic substance (b) having a low-odor double bond exceeds 150 parts by mass, the cured product of the obtained resin composition (A) tends to have poor chemical resistance and toughness, and less than 70 parts by mass. In this case, the surface properties of the cured product tend to be poor, and the workability tends to be poor due to the high viscosity.

As the curing agent (c) used in the present invention, for example, methyl ethyl ketone peroxide, acetylacetone peroxide, cumene hydroperoxide, t-butyl perbenzoate, t-butyl peroctoate, benzoyl peroxide, bis ( 4-
A polymerization initiator such as an organic peroxide such as (t-butylcyclohexyl) peroxydicarbonate and t-hexylperoxy-2-ethylhexanoate is used.

The amount of the curing agent (c) used is 0.6 to 10 parts by mass, preferably 1.3, with respect to 100 parts by mass of the epoxy (meth) acrylate (a).
To 8 parts by mass, more preferably 2 to 6 parts by mass.

Examples of the curing accelerator (d) used in the present invention include metal soaps such as cobalt naphthenate, manganese naphthenate, copper naphthenate, potassium naphthenate, calcium naphthenate, and cobalt octylate; and dimethylaniline. Amines such as N, N-dimethyltoluidine, N, N-diethylaniline, N, N-di (hydroxy) -4-methylaniline, β-diketones such as acetylacetone, ethyl acetoacetate and N, N-dimethylacetamide , Β-ketoesters, β-ketoamides and the like.

The amount of the curing accelerator (d) used is 0.2 to 5 parts by mass of the curing accelerator (d) based on 100 parts by mass of the epoxy (meth) acrylate (a).
0.4 to 4 parts by mass, more preferably 0.8 to 3 parts by mass.

The resin composition (A) of the present invention can be used by adding a solventless urethane resin for the purpose of improving the adhesion to the substrate. As the solventless urethane resin, a known urethane resin can be used as long as it does not contain a so-called solvent.

The solventless urethane resin is obtained by reacting a diisocyanate such as, for example, toluidine diisocyanate, hexamethylene diisocyanate, 4,4-diphenylmethylene diisocyanate with 1,4-butanediol, polypropylene glycol, polyethylene glycol or the like. And a urethane resin obtained by subjecting a diisocyanate and water to a Burette reaction.

Further, a wax can be added to the resin composition (A) of the present invention in order to avoid poor curing of the air contact surface. As wax, paraffin wax,
Petroleum waxes such as microcrystalline wax, olefinic waxes such as polyethylene and polypropylene, or polar waxes having a polar group introduced therein can be used. As the amount of the wax to be added, it is necessary to exhibit excellent barrier properties and curability, and to prevent the wax from being precipitated without lowering the solubility. a) 100 parts by mass of wax 0.04
To 4 parts by mass, preferably 0.2 to 3 parts by mass, more preferably 0.4 to 2 parts by mass.

The resin composition (A) of the present invention may contain a polymerization inhibitor, an antifoaming agent and the like. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone and methylhydroquinone; benzoquinones such as benzoquinone and methyl-P-benzoquinone; catechols such as t-butylcatechol; 2,6-di-t-butyl-4-methylphenol; -Phenols such as methoxyphenol, phenothiazine and the like can be used.

As the antifoaming agent, a commercially available polymer antifoaming agent and other additives can be used in addition to the silicone type and the like.

The coating material of the present invention comprises the resin composition (A)
It contains. A filler can be added to the coating material of the present invention. Usually, 1 to 400 parts by volume of the filler (B) can be added to 100 parts by volume of the resin composition (A). A coating material in which the amount of the filler (B) added is relatively small and has good fluidity, and when applied on a horizontal surface, flows even after application to obtain a flat finish, is generally called a resin paste. The coating material which does not become flat by itself when the addition amount of the material (B) is relatively large and has poor fluidity,
Generally, it may be referred to as a resin mortar, but the coating material of the present invention comprises a resin composition (A) and a filler (B) in a ratio of:
By appropriately adjusting the particle size and the particle size distribution of the filler (B), a coating material of any property can be obtained. In the coating material of the present invention, about 1 to 150 parts by volume of the resin paste and about 50 to 400 parts by volume of the resin mortar are added to 100 parts by volume of the resin composition (A).

For example, in the case of a coated floor, which is a floor coating method, a method mainly using a resin paste is called a flow-through method, and a method mainly using a resin mortar is called a mortar method. It can also be applied to construction methods.

As the filler which can be added to the coating material of the present invention, an inorganic powder or an inert powder can be mentioned. Examples of the inorganic powder include silica sand, river sand, land sand, silica sand powder, emery, corundum, silica, clay,
Bentonite, aluminum hydroxide, alumina, talc, calcium carbonate, pulverized ceramics and the like can be exemplified. Examples of the inert powder include thermoplastic resins such as polyethylene, polypropylene, polystyrene, and polymethyl methacrylate, acrylic resins, and polyesters. resin,
Examples thereof include cured products of thermosetting resins such as phenol resins and urethane resins, and powders and / or pulverized products such as rubber and wood.

The coating material of the present invention may optionally contain a pigment, a colorant such as a toner, a thixotropy-imparting material, and the like. As the pigment, any of an organic pigment and an inorganic pigment can be used.

Examples of the organic pigment include benzidine yellow, Hansa yellow, lithol red, alizarin lake, pigment scarlet 3B, brilliant carmine 6B, permanent red F-5R, permanent red 4R, rhodamine lake B, rhodamine lake Y,
Lake Red C, Para Red, Beacock Blue Lake, Phthalocyanine Blue, Phthalocyanine Green,
Examples include aniline black, permanent yellow HR, PV violet BL, quinacridone, perinone, anthraquinone, chromophtal yellow 6G, chromophtal yellow 3G, and chromophtal yellow GR.

As the inorganic pigment, for example, titanium oxide,
Zinc flower, lithobon, lead white, cadmium yellow, graphite, titanium yellow, zinc chromate, loess, chrome vermillion, red mouth pigment, amber, yellow iron oxide, red iron oxide, cadmium red, lead red, navy blue, ultramarine, cobalt blue,
Examples thereof include oxidized chrome green, mineral violet, carbon black, and iron black. These pigments are kneaded by adding a plasticizer such as a phthalate ester, an epoxy (meth) acrylate or the like as a vehicle,
It can also be used as a paste toner.

As the thixotropy-imparting material, known materials can be used. For example, organophilic compounds obtained by reacting with smectite-type clays such as montmorillonite, bentonite, beidellite, hectorite, savonite, stepensite, and organic cation compounds thereof are used. Clay, finely divided silica, pulp-like substances such as polyolefin are fisted,
Among these, a polyolefin pulp-like substance is preferred.

The polyolefin pulp-like substance has a large thixotropy-imparting effect, and is easy to handle without scattering fine powder.

Examples of the polyolefin pulp-like substance include SWP (trade name: manufactured by Mitsui Chemicals, Inc.) and Chemibest (trade name: Mitsui Chemicals, Inc.), which are formed by molding polyethylene into pulp-like multibranched fibers. ) Company).

The amount of the thixotropic material is usually
The amount is 0.5 to 10 parts by mass, preferably 1 to 7 parts by mass based on 100 parts by mass of the resin composition (A).

The coating material of the present invention can be produced by the following method.

That is, the resin composition (A) and the coating material of the present invention are generally prepared by putting the constituents of the resin composition (A) or the coating material into a container such as a metal can or a resin can and using a mixer. It can be manufactured by stirring and homogenizing.
The resin composition (A) can be produced by supplying the curable composition without adding the curing agent (c) to the construction site, adding the curing agent (c) on site, stirring, dissolving, and mixing. . In the case of a coating material as well, a curing agent (c) is added to the resin composition (A) at the construction site to stir and dissolve, and then a coloring agent and a filler (B) are sequentially added to stir and homogenize. be able to. In order to ensure the dissolution of the curing agent (c), the curing agent (c) is usually first added to the resin composition (A) and stirred. Alternatively, before the curing agent (c) is charged, it may be charged and stirred in advance to make it even.

When a hand mixer is used, generally about 3 to 30 liters of the resin composition (A) or coating material can be prepared. When a large amount of the resin composition (A) or the coating material is to be prepared, a pan-type forced mulling mixer or a tilting mixer may be used. Materials can be prepared.

To prepare a small amount of the resin composition (A) or the coating material, hand mixing or hand kneading may be used. In this case, if the coating material is a coating material that does not add the filler (B) to the resin composition (A) but only the pigment or the like (a coating material without the filler (B)), it is stirred with a spatula or the like. It is sufficient to confirm the dissolution of the curing agent (c) or the stiffness of the pigment. However, in the case of the coating material containing the filler (B) (the coating material of the type added with the filler (B)), a scoop is required. It is preferable to employ a method in which the mixture is sufficiently kneaded and uniform. The stirring time is generally
It takes about 30 to 90 seconds to dissolve the curing agent (c) and about 1 to 3 minutes to mix the pigment and the filler.

Further, a coupling agent can be added to the resin composition (A) and the coating material of the present invention, if necessary, for the purpose of improving physical properties. Examples of the coupling agent include silane coupling agents such as vinyltrimethoxysilane, vinyltriacetylsilane, vinyltriethoxysilane, and gamma-methacryloxytrimethoxysilane, isopropylpropyltriisostearoyl titanate, tetraoctylbis (didodecylphospho). Examples thereof include titanium coupling agents such as (phytate) titanate, and among them, γ-methacryloxytrimethoxysilane is preferable. The coupling agent can be added at the time of preparing the resin composition (A) or the coating material, and the filler (B) is prepared by uniformly mixing the filler (B) with a coupling agent diluted with water or alcohol and heating. May be processed in advance.

The coating method of the present invention is characterized by using the coating material of the present invention. Although the substrate to which the coating method of the present invention can be applied is not particularly limited, it is usually a cured product of Portland cement such as cement concrete or cement mortar. In addition, metal plates such as iron plates, stainless steel plates and aluminum plates, asphalt compositions such as asphalt concrete, natural stones such as granite, limestone, iron flat stone, inorganic sintered products such as clinker tiles, terracotta, bricks, terrazzos, acrylics Rubber-based, epoxy-based, polymer cement mortars such as ethylene vinyl acetate, epoxy-based, urethane-based, methacrylic-based, polyester-based, vinyl ester-based resin-based paints or coated flooring materials, polyvinyl chloride tiles and long sheets thereof , Wood flooring, cork and the like.

The following are examples of the coating method of the present invention. That is, using the coating material of the present invention, generally, a primer layer is usually applied to a substrate usually 1 to 3 times, an intermediate layer is usually applied 1 to 2 times thereon, and a top coat layer is usually applied. The substrate is coated by applying and curing once or twice. However, these three types of layers are not essential, for example, the substrate has almost no liquid permeability,
In the case of a metal, a resin tile, or the like, the primer layer may be omitted in some cases, and the top coat layer may be omitted in a case where it is not particularly required. Further, when the coating layer is made thinner from the viewpoint of economy, the primer layer and the top coat layer may be omitted from the intermediate layer in some cases.

In some cases, three or more intermediate layers are applied in order to form a stronger coating layer. For the primer layer, generally, a coating material of the present invention without a filler (B) added or a resin paste type coating material is used. When the resin paste type or resin mortar type coating material of the present invention is used for the primer layer, the resin composition (A)
A coating material containing a relatively large amount of the resin composition (A) containing 1 to 100 parts by volume of the filler (B) with respect to 100 parts by volume is used. In addition, it is preferable that a non-solvent type urethane resin is blended in the primer layer for the purpose of improving the adhesion to the substrate. The coating thickness is usually 0.05 to 0.8 mm.

For the intermediate layer, the resin paste type or resin mortar type coating material of the present invention is usually used. The coating thickness is about 1 to 10 mm when using a resin paste type coating material, and about 3 to 20 mm when using a resin mortar type coating material.

As the top coat layer, the coating material of the present invention without the filler (B) added or the coating material with the filler (B) added is used. Usually, a coating material without a filler (B) added or a coating material with a filler (B) added with a coloring agent is used. The coating thickness is about 0.1 to 0.6 mm.

In the coating method of the present invention, a glass cloth, a resin cloth such as aramid fiber, a glass mat, a surface mat, a polyolefin or polyester non-woven cloth, etc. can be provided between the respective layers for the purpose of reinforcement or the like. Alternatively, resin flakes such as glass flakes, polyvinyl chloride, acrylic resin, and polyvinyl acetate, and flake-like solids such as metal flakes may be used as the filler (B) of the present invention without a coating material, a resin paste type or a resin mortar. The coating method of the present invention can also be carried out by mixing with a type of coating material or spraying after coating. In particular, after the above-mentioned primer layer is provided on the base material, a filler (B) -free coating material or a resin paste-type coating material layer of the present invention is applied, and flake-like solid matter is sprayed before curing. After curing, by applying the above-mentioned top coat layer on it, it has excellent brittleness, strength, durability, chemical resistance,
In addition, a coating material having aesthetic properties can be applied in a low-odor environment.

In this method, the thickness of the coating layer as the intermediate layer is about 0.2 to 3 mm, preferably 0.4 to 2 mm. As the flakes, resinous colored flakes are preferable, and the thickness of the flakes is about 0.05 to 0.3 mm, the size is about 1 to 10 mm × 1 to 10 mm, and may be irregular.

When the coating material of the present invention is applied to an inclined surface or a vertical wall surface, use of the above-mentioned resin paste or resin mortar to which a thixotropy-imparting material is added reduces the workability due to evaporation. In addition, it is possible to obtain a coating material having low odor and excellent in impact resistance, temperature fluctuation resistance, and anti-corrosion resistance. In this case, the amount of the thixotropy-imparting material is usually 0.5 to 10 parts by mass, preferably about 1 to 7 parts by mass, per 100 parts by mass of the resin composition (A). Although any of the aforementioned thixotropic materials can be used, a polyolefin pulp-like substance is preferred. As a coating material for a building floor or a peripheral portion thereof, it is suitable for constructing a portion having a large water gradient on the floor surface, an R-fitting material at a corner with a wall, and a waist wall portion.

To provide the coating material layer of the present invention on a substrate,
When the coating material of the filler (B) -free type and the resin paste type coating material are applied in a thickness of 1 mm or less, a brush or a roller is usually used. In order to apply a resin paste type or resin mortar type coating material having a thickness of 1 mm or more, a metal iron, a wooden iron, a reiki or the like is usually used. The construction method of the present invention is not limited to construction tools. For example, when applying a filler (B) -free type coating material and a resin paste type coating material having a thickness of 1 mm or less, using a trowel. Or when applying a resin paste type coating material, see JP-A-11-2072.
No. 45, a coated floor in which a partition partitioning the outer space of the surface into a number of portions is disposed on the surface of the roller, and a large number of depressions are formed by the partition and the surface. A construction tool for keeping the coating thickness of the material constant may be used.

Specific examples of the use of the coating material of the present invention as a coating material such as an anticorrosion material, a waterproof material, a floor material, a wall material, etc. are, for example, concrete anticorrosion materials for sewage treatment facilities, rooftops, verandas and the like. Waterproofing materials, dam-hitting, repair materials for concrete structures such as roads, painted floor materials for various buildings, and the like can be given. INDUSTRIAL APPLICABILITY The coating material and the coating method of the present invention are particularly suitable for applications in which odor during construction is a problem, particularly as a coated flooring material for buildings. Examples include repair work for hospitals, hotel kitchens, etc., repair work for operating food factories, new or repair work for various factories located in densely populated houses, and new or repair work for stores and the like. Furthermore, since the coating material of the present invention has an appropriate tensile elongation at break, it is most suitable as a flooring material for kitchens and food factories where hot water and cold water are frequently used and temperature fluctuations often become a load.

[0069]

The present invention will be described in more detail with reference to the following examples. In the following, “%” and “parts” are based on mass unless otherwise specified.

Synthesis Example 1 Bisphenol A: 1.0 mol, bisphenol A type epoxy resin (Epomic R140, manufactured by Mitsui Chemicals, Inc.)
0.02 mass% of 20% potassium hydroxide was added to 2.5 mol, and reacted at 140 ° C. to 180 ° C. for 5 hours to obtain an epoxy compound (αl) having an epoxy equivalent of 400. The epoxy compound (αl) and 2.95 mol of methacrylic acid (β1) were mixed in an air stream in the presence of 0.2% by mass of triethylamine and 0.01% by mass of phenothiazine in an amount of 100 to 1%.
The reaction was carried out at a temperature of 20 ° C. for 3 hours to obtain an epoxy methacrylate (A1-1) having an acid value of 2. 100 parts by mass of the epoxy methacrylate (Al-1) were mixed with 74 parts by mass of dicyclopentenyloxy methacrylate, 41 parts by mass of phenoxyethyl methacrylate, and 0.02 parts by mass of a polymerization inhibitor, hiquinonone monomethyl ether. And
Resin 1 was obtained.

Synthetic Example 2 Bisphenol A: 1.0 mol, 2.5 mol of 1,6-hexanediol diglycidyl ether, 0.02 mass% of 20% potassium hydroxide were added, and the mixture was heated at 140 to 180 ° C. for 5 hours. The reaction was performed to obtain an epoxy compound (α2) having an epoxy equivalent of 345. The epoxy compound (α2) and 2.95 mol of methacrylic acid (β1) were mixed at a temperature of 100 to 120 ° C. in an air stream in the presence of 0.2% by mass of triethylamine and 0.01% by mass of phenothiazine. Reaction for 2 hours, epoxy methacrylate having an acid value of 2 (A2-1)
I got This epoxy methacrylate (A2-1) 1
Resin 2 was obtained by mixing 66 parts by mass of dicyclopentenyloxy methacrylate, 34 parts by mass of phenoxyethyl methacrylate, and 0.02 parts by mass of hyquinonone monomethyl ether in 00 parts by mass.

Synthesis Example 3 0.2 mol of maleic anhydride, 0.8 mol of phthalic anhydride,
1.06 mol of 1,6 hexanediol was added under nitrogen stream,
The mixture was reacted at 85 ° C. for 12 hours to obtain an unsaturated polyester (A3-1) having an acid value of 35. This unsaturated polyester is
After cooling to 00 ° C, unsaturated polyester (A3-1)
Resin 3 was obtained by adding and dissolving 0.01 part by mass of hydroquinone and 70 parts by mass of styrene to 100 parts by mass.

Examples 1 and 2 and Comparative Example 1 The components shown in Table 1 were mixed to prepare a resin composition (A). This resin composition is 300 mm × 300 mm × 3 mm
It was poured into a mold having a size of (length × width × thickness), cured at room temperature for 4 hours, and further post-cured in a curing oven at 80 ° C. for 2 hours to prepare a casting plate. These were subjected to a tensile test of the cast plate according to the method of JIS K7113. In addition, a sensory test for odor during the preparation and curing of the resin composition was performed. Table 2 shows the results.

[0074]

[Table 1]

[0075]

[Table 2]

Example 3 In a resin composition of Example 1, 100 parts of a mixture excluding 55% methyl ethyl ketone peroxide was added to a commercially available isocyanate prepolymer as a solventless urethane resin (manufactured by Sumitomo Bayer Urethane Co., Ltd.): Sumidule E21
-1) 30 parts were added and stirred well, and then 1.2 parts of powdery 50% benzoyl peroxide was added and further stirred to obtain a coating material. This was applied to a concrete pavement plate with a roller to form a first coating layer having a thickness of 0.2 mm. At the same time, a test piece was prepared by using the coating material according to the method of JIS K6911 and kept at 23 ° C. for 7 days, and then the tensile elongation at break was measured.

Subsequently, of the resin composition of Example 2, 55
% Silica sand (70%) silica sand powder (30%) in 100 parts by volume of the resin composition excluding the% methyl ethyl ketone peroxide.
%) Of the mixture was added and stirred with a spatula to make the mixture uniform. Further, 2 parts of 55% methyl ethyl ketone peroxide was added and stirred to obtain a resin paste type coating material. This was applied to the above-mentioned pavement board with a metal iron so as to have a thickness of 3 mm, and was cured to form a second coating layer. At the same time, using this resin paste type coating material, JISK6
A test piece was prepared by the method of Example 911 and held at 23 ° C. for 7 days, and then the tensile elongation at break was measured.

Subsequently, of the resin composition of Example 1, 5
10 parts of a phthalocyanine green-based green pigment was added to 100 parts of the resin composition except for 5% methyl ethyl ketone peroxide, and the mixture was stirred with a spatula to make the mixture uniform. 55% more
2 parts of methyl ethyl ketone peroxide was added and stirred to obtain a coating material. This was applied onto the pavement plate with a roller to obtain a third coating layer having a thickness of 0.3 mm.

A pavement board specimen coated with the above-described three layers of covering material was obtained. JIS K691 using this coating material
A test piece was prepared in the same manner as in the method 1 and kept at 23 ° C. for 7 days, and then the tensile elongation at break was measured.

Next, the obtained pavement plate specimen was heated at 23 ° C. for 7 hours.
After holding for one day, the apparatus was placed in a device where 100 ° C. steam and water at about 20 ° C. alternately contact the surface of the specimen, and after 500 cycles of 1 cycle = 30 minutes of steam / 30 minutes of water ( Hereinafter, this is referred to as a cold / hot repetition test), and the surface state was visually observed and evaluated. Tables 3 and 4 show the measurement results of the tensile elongation at break and the evaluation results of the surface condition after the cold / hot repetition test, respectively.

[0081]

[Table 3]

[0082]

[Table 4]

Example 4 In Example 3, 55% of the resin composition of Example 2 was used instead of the resin paste type coating material of the second layer.
No. 4 silica sand (30%) and No. 5 silica sand (30%) were added to 100 parts by volume of the resin composition excluding methyl ethyl ketone peroxide.
%) And No. 6 silica sand (40%), add 180 parts by volume, stir with a spatula to equalize, further add 2 parts of 55% methyl ethyl ketone peroxide and stir to use a resin mortar type coating material obtained. Except for the above, a pavement plate specimen coated with three layers was obtained in the same manner as in Example 3.

The tensile elongation at break of the resin mortar type coating material of the second layer was measured, and the surface condition of the specimen coated with the three layers after the repeated cooling / heating test was evaluated. The results are shown in Tables 3 and 4. In addition, the measurement of the tensile elongation at break of the coating materials of the first and third layers was omitted.

Example 5 Of the resin composition of Example 2, 4 parts were added to 100 parts by volume of the resin composition except for 55% methyl ethyl ketone peroxide.
No. 5 silica sand (30%) No. 5 silica sand (30%), No. 6 silica sand (40%)
%), And a polyolefin pulp-like substance (Chemibest F, manufactured by Mitsui Chemicals, Inc.)
1.5 parts of DSS-5) was added thereto, and the mixture was stirred with a spatula to make them even. Further, 2 parts of 55% methyl ethyl ketone peroxide was added and stirred to obtain a resin paste type coating material. A specimen coated with only the first layer was prepared in advance by the method of Example 3, and the coated surface was set upright so that the coating material of the resin paste type was immediately coated with a metal iron to a thickness of 2 mm. As a result of the coating having a large thickness, a coating layer having a smooth surface was obtained. Further, the same third coating layer as in Example 3 was applied with a roller and cured, so that a smoother and more glossy coating layer was obtained.

Example 6 A covering made of the resin composition of Example 2 was coated on a floor 20 m ² on which polyvinyl chloride tiles were laid with a metal iron.
It was applied to a thickness of 0.6 mm. Immediately flakes made of polyvinyl acetate (thickness 0.3 mm, size 1-10 m
m) was uniformly applied from above in an amount of 500 g / m ² . After the coating material was cured, the flakes that did not adhere to the coating material were removed, and the coating material made of the resin composition in Example 1 was applied to a thickness of 0.3 mm using a roller and cured. A coating layer having a moderate anti-slip property and a unique texture was obtained. Although no odor countermeasures such as forced exhaust were taken during the execution of this example, almost no odor was felt.

[0087]

Industrial Applicability The low odor resin composition of the present invention, a coating material containing the resin composition and a method using the coating material have no odor, are excellent in coating workability, and have good adhesion to a substrate and durability. Excellent performance.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takumi Shimizu 1900 Togo, Mobara-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Yasumasa Fujii 9 Kawarai-cho, Kuki-shi, Saitama Pref. (72) Inventor Yasushi Yamada 9 Kawarai-cho, Kuki-shi, Saitama Prefecture Mitsui Chemicals Co., Ltd.Product Research Institute Co., Ltd. (72) Inventor Shozo Hieda 3-39-10 Yushima, Bunshima-ku, Tokyo Mitsui Chemicals In-house F-term (reference) 4J027 AE02 AE04 AE05 BA07 BA10 BA11 CA02 CA04 CA06 CA14 CA18 CA24 CA25 CA36 CB03 CC02 CD08 4J036 AB01 AB10 AD08 AD09 AD21 CA08 CA21 CD10 EA01 EA04 JA01 4J038 CB002 FA121 FA131 FA141 FA171 HA251 FA 271 JA47 JA51 JA56 JA66 JB06 JB09 JB13 KA03 KA04 KA08 KA19 MA15 NA03 NA11 NA23 NA27

Claims (8)

[Claims] 1. An epoxy compound obtained by reacting 1.0 mol of bisphenol with a total of 1.5 to 3.5 mol of an aliphatic diglycidyl ether type epoxy compound and / or an aromatic polyfunctional epoxy resin. (Α) and (meta)
70 to 150 parts by weight of a polymerizable organic substance (b) having a low odor double bond and 100 parts by weight of an epoxy (meth) acrylate (a) composed of a reaction product with acrylic acid (β), ) A resin composition (A) containing 0.6 to 10 parts by mass and 0.2 to 5 parts by mass of a curing accelerator (d). 2. The ratio (mol%) of the aliphatic diglycidyl ether type epoxy compound to the total amount of the aliphatic diglycidyl ether type epoxy compound and the aromatic polyfunctional epoxy resin is from 0 to 100. Resin composition (A). 3. The ratio (mol%) of the aliphatic diglycidyl ether type epoxy compound to the total amount of the aliphatic diglycidyl ether type epoxy compound and the aromatic polyfunctional epoxy resin is 40 to 100. Resin composition (A). 4. A coating material containing the resin composition (A) according to claim 1. 5. The coating material according to claim 4, wherein 1 to 400 parts by volume of the filler (B) is contained based on 100 parts by volume of the resin composition (A). 6. The coating material according to claim 4, further comprising a thixotropy-imparting material. 7. The coating material according to claim 6, wherein the thixotropy-imparting material is a polyolefin pulp-like substance. 8. A coating method using the coating material according to claim 4. Description: