JPS6410024B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to primer compositions for floor and wall coatings.

There are a variety of solvent-based and emulsion-based paints as well-known resins used for coating floors and walls of concrete, asphalt, metal, etc., but these are difficult to apply thickly and have limited durability. be. Therefore, for applications with particularly strong demands for durability and chemical resistance, synthetic resin flooring materials have been used that are made from liquid resins such as epoxy resins, unsaturated polyester resins, and polyurethane resins that are hardened after application. In addition, acrylic liquid resins have been developed for the same purpose in recent years, and they have good durability, chemical resistance, and weather resistance, as well as short curing times and can be used within 1 to 2 hours after application. A major feature is that it has good curing properties and can be applied even at low temperatures of 5°C or lower.

When applying these synthetic resin flooring materials to a base such as concrete, asphalt, or metal, a primer is applied in advance and the synthetic resin is applied on top of the primer in order to improve adhesion to the base and suppress the effects of the base. A construction method in which the flooring material is coated over and over again is generally used. Epoxy resin as a primer,
There are types in which unsaturated polyester resins, polyurethane resins, or acrylic resins are dissolved in solvents, those in which they are dispersed in water, and types in which these liquid resins are hardened after application. These primers are used appropriately depending on the type of base material and the type of synthetic resin coated flooring material for top coating. However, all of the conventional primers for acrylic curable liquid resins that have been developed in recent years have drawbacks, and there is no suitable primer.

The acrylic curable liquid resin for coatings is characterized by its short curing time, and its excellent curability even at low temperatures of 5° C. or lower is a major feature. However, conventional curing type primers take a long time to cure and have extremely poor curing properties, especially at low temperatures.
The characteristics of acrylic curable liquid resin, which has a short curing time, cannot be fully utilized.

Curable acrylic liquid resins are generally cured by radical polymerization using a redox catalyst consisting of a combination of a curing agent and an accelerator. However, for example, when applying an epoxy primer in a low-temperature atmosphere and then topcoating it with a curable acrylic liquid resin, unreacted amines in the epoxy primer inhibit the radical polymerization of the acrylic resin, resulting in This is undesirable as it may hinder curing.

When using a solvent-based primer in which various polymers are dissolved in a solvent, it is necessary to evaporate the solvent sufficiently before applying a topcoat, but it takes a long time for the solvent to evaporate in a low-temperature atmosphere in winter. If the top coat is applied with the solvent remaining, blistering may occur in the top coated film, which is not preferable. Even when using emulsion-type primers in which various polymers are dispersed in water, it is necessary to sufficiently evaporate the water and dry the primer coating before applying a topcoat, but if the temperature is low, it may take a long time to dry. In short,
Remaining moisture may cause blistering in the top coat and may also cause poor adhesion, which is undesirable.

The present invention provides a novel primer composition that improves the drawbacks of conventional primers as described above.

The first feature of the primer composition of the present invention is that it cures in a short time and can be overcoated.

The primer composition of the present invention is particularly preferred as a primer for overcoating with an acrylic curable liquid resin, but it can also be used as a primer for overcoating with epoxy resins other than acrylic resins, unsaturated polyester resins, polyurethane resins, etc. Since the curing time of the primer is short, the construction time can be shortened.

The second feature of the primer composition of the present invention is that the primer composition of the present invention
It has excellent curability even at low temperatures below. Therefore, it can exhibit excellent characteristics in winter construction, and is particularly preferred as a primer when overcoating with an acrylic curable liquid resin.

The present invention provides a primer composition for floor and wall coatings comprising the following (A) to (D).

(A) Based on bisphenol A and epichlorohydrin, molecular weight 800-3000 and epoxide equivalent
400-2500 a) methacrylic acid and/or acrylic acid 74-64 mol%
and b) 100-80 mol% of at least one saturated monocarboxylic acid having 8-20 carbon atoms and 8
Unsaturated β- obtained by reacting a mixture of 0 to 20 mol % of at least one unsaturated monocarboxylic acid having ~20 carbon atoms with 26 to 36 mol % of a monocarboxylic acid Hydroxy ester 30-60% by weight (B) Methyl methacrylate or a polymerizable unsaturated monomer containing 80% by weight or more of methyl methacrylate 70-40% by weight (C) Paraffin and/or having a melting point of 40°C or higher For 100 parts by weight of wax, (A) and (B)
0.1 to 5 parts by weight (D) Tertiary amine, 0.1 to 5 parts by weight per 100 parts by weight of the total amount of (A) and (B) The primer composition of the present invention is prepared by adding and mixing a curing agent, and then spraying. It is applied to the base using a roller, brush, trowel, etc. The applied primer is cured by the action of a redox catalyst consisting of a combination of a curing agent and an accelerator in the primer composition, whereby the polymerizable unsaturated compound in the primer composition is polymerized.

Component (A) is an unsaturated β-hydroxy ester and constitutes one component of the polymerizable unsaturated compound. Component (A) is an epoxy resin based on bisphenol A and epichlorohydrin, i.e.
800 to 3000 and an epoxide equivalent weight of 400 to 2500. Particularly preferred are epoxy resins or mixtures thereof having an average molecular weight of 1300 to 1800 and an epoxide equivalent weight of 750 to 1000. The epoxy resin contains a) 74 to 64 mol% of methacrylic acid and/or acrylic acid.
and b) at least one long chain monocarboxylic acid26
~36 mol % of the mixture to form an unsaturated β-hydroxy ester. Preference is given to using as component a) a mixture having at least 50 mol % of methacrylic acid, in particular only methacrylic acid. Saturated monocarboxylic acids having 8 to 20 carbon atoms, such as caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid or stearic acid, and mixtures thereof are used as component b). It is also possible to mix at least one unsaturated monocarboxylic acid having 8 to 20 carbon atoms in an amount of 20 mol % or less.
Such unsaturated monocarboxylic acids include, for example, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, lintinolic acid or mixtures thereof.

Component (B), together with component (A), constitutes one component of the polymerizable unsaturated compound in the primer composition of the present invention, and is a polymerizable unsaturated compound containing methyl methacrylate or 80% by weight or more of methyl methacrylate. Consists of unsaturated monomers. Such monomers include
For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, n- methacrylate.
Examples include acrylic acid or methacrylic acid esters such as butyl, 2-ethylhexyl methacrylate, and lauryl methacrylate. Component (B) can also contain a known crosslinking agent. As a crosslinking agent, at least two vinyl groups and/or
or compounds containing allyl groups, such as ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neo diacrylate Mention may be made of polyfunctional esters of acrylic acid or methacrylic acid such as pentyl glycol, diethylene glycol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate, or triallyl compounds such as triallyl cyanurate.

Component (C) includes paraffin wax, polyethylene wax, and higher fatty acids such as stearic acid and 1,2-hydroxystearic acid.
Preferably paraffin wax is used. Component (C) is added for the purpose of blocking air during the curing reaction on the surface of the primer coating film. It may be preferable to use two or more types with different melting points in combination. Adding a large amount of component (C) will impair the adhesion between the primer composition and the topcoat resin.
The amount used is 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the total amount of (A) and (B).

Component (D) is a promoter of the redox catalyst system. As a tertiary amine, at least one
Preferably, aromatic residues of
In particular, N,N'-dimethylaniline, N,N'-dimethyl-p-toluidine, N,N'-di(hydroxyethyl)-p-toluidine, N,N'-di(2
-Hydroxypropyl)-p-toluidine or a combination of two or more thereof is preferred. Adding a large amount of component (D) will extremely shorten the curing time and impair coating workability, so it should be added in the range of 0.1 to 5 parts by weight per 100 parts by weight of the total amount of components (A) and (B). added.

The primer composition of the present invention is applied to a base using a roller, brush, trowel, etc. to an appropriate thickness, for example, 0.1 to 1 mm, but the primer composition is applied to a base using a roller, brush, trowel, etc. It is preferable that Lowering the viscosity improves the permeability to the substrate and improves the adhesion to the substrate, but the curability deteriorates and it takes a long time to cure. If the viscosity is too high, the adhesion to the base will decrease and the coating workability will also deteriorate. The appropriate viscosity range determined from these factors is 50 to 1000 cps. To obtain this viscosity range, component (A) in the composition of the present invention must be
It is necessary to use component (B) in a proportion of 70 to 40% by weight.

The primer composition of the present invention can be advantageously produced by the following method.

That is, some or all of methyl methacrylate or a polymerizable unsaturated monomer (B) containing 80% by weight or more of methyl methacrylate contains bisphenol A and epichlorohydrin as a base, and has a molecular weight of 800 to 800%.
3000 and an epoxy resin having an epoxide equivalent of 400 to 2500 is dissolved to form a solution (), in which a) 74 to 64 mol% of methacrylic acid and/or acrylic acid, and b) 8 to 20 At least one saturated monocarboxylic acid having carbon atoms 100 to 80
and 26 to 36 mol % of a monocarboxylic acid consisting of 0 to 20 mol % of at least one unsaturated monocarboxylic acid having 8 to 20 carbon atoms, and in the presence of a suitable catalyst. Unsaturated β- produced by reacting the epoxy resin with acid
A solution () containing a hydroxyester (A), a tertiary amine (D) in the solution (), and a paraffin and/or wax (C) having a melting point of 40°C or higher.
By dissolving or dispersing the following (A) to (D)
A primer composition of the present invention is produced. Note that when part of the unsaturated monomer (B) is used when preparing the solution (), the remainder of (B) is added, for example, at the same time as (D) and/or (C) are added.

(A) 30-60% by weight of unsaturated β-hydroxy ester (B) 70-40% by weight of methyl methacrylate or a polymerizable unsaturated monomer containing 80% or more of methyl methacrylate (C) 40°C or higher Paraffin and/or wax having a melting point, 0.1 to 5 parts by weight per 100 parts by weight of the total amount of (A) and (B) (D) Tertiary amine, 100 parts by weight of the total amount of (A) and (B) The reaction between the epoxy resin and the acid mixture is carried out in the presence of a known catalyst. Suitable catalysts include, for example, primary amines such as ethylenediamine, trimethylamine, dimethylpenzylamine, triethylamine, dimethyl-p-toluidine, etc.
Inorganic salts such as SnO ₂ , SnCl ₂ , LiF; Tertiary phosphines such as triphenylphosphine; Acid addition salts of secondary amines such as diethyluane hydrochloride; or nitrogen-containing heterocyclic compounds such as pyridine and morpholine.

The reaction between the epoxy resin and the acid mixture can be carried out in the absence of a solvent or in the presence of an inert solvent, but as described above, the reaction between the monomers constituting component (B) of the primer composition of the present invention It is advantageous to react in part or in total.

In order to prevent polymerization during the reaction of the epoxy resin and the acid mixture, it is preferable to add a radical polymerization inhibitor. Suitable inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether,
Mention may be made of 2,4-dimethyl-6-t-butylphenol.

The reaction between epoxy resin and acid mixture is 50-100℃
It is advantageously carried out at a temperature of . This reaction is approximately stoichiometric, i.e. 0.8 to 1.2
It is carried out using 1 mol of acid per equivalent.

A preferred manufacturing method is as follows. That is, a polymerization inhibitor is added to part or all of component (B), an epoxy resin is mixed therein, and the whole is heated to dissolve the epoxy resin to form a solution (). A catalyst for the reaction between the epoxy resin and the acid is added to the solution (2). The acid is fed into the solution continuously or batchwise over a period of about 30 minutes to 4 hours. The reaction mixture is maintained at the reaction temperature for 2 to 10 hours to ensure sufficient reaction. Add the remaining amount of component (B) as necessary to the solution () containing the generated unsaturated β-hydroxy ester, and add a tertiary amine and paraffin and/or wax having a melting point of 40°C or higher. By doing so, the primer composition of the present invention is obtained.

By adding a known organic peroxide as a curing agent to the primer composition of the present invention,
It can be cured within 2 hours at a temperature range of . A preferred example of the organic peroxide is benzoyl peroxide. In order to avoid handling hazards, it is preferable to use benzoyl peroxide in the form of a paste or powder diluted with an inert liquid or solid to a concentration of about 50%. In order to obtain a preferable curing time of 10 to 60 minutes in consideration of coating workability, it is necessary to adjust the amount of curing agent depending on the temperature of the primer or the temperature at the time of coating. ) is preferably used in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the composition of the present invention.

The composition of the present invention is usually coated with only a curing agent added, but a coloring agent may be added to clearly mark the area to be coated, or thixotropy may be imparted to the composition when applied to a wall surface. For this purpose, thixotropic agents such as asbestos, sepiolite, and aerosil can be added. In addition, silica sand, silica sand powder,
It is also possible to mix aggregates and fillers such as calcium carbonate with the composition of the present invention for coating.

The composition of the present invention has excellent adhesion to the substrate, but in order to further stabilize the adhesion, γ-methacryloxypropyltrimethoxysilane, γ- A silane coupling agent such as glycidoxypropyltrimethoxysilane can be added.

Although the composition of the present invention has a curing mechanism by radical polymerization using a redox catalyst system, it has the characteristic that it is not easily influenced by air and other polymerization inhibiting factors. These characteristics make it highly desirable as a primer. In other words, substrates generally have various stains on their surfaces, and there is a high possibility that these stains include factors that inhibit radical polymerization, but the composition of the present invention can be used with confidence on any substrate. can do.

The compositions of the invention can be used as highly preferred primers, especially when the substrate is concrete. That is, when a primer is applied to a concrete base, air is trapped in small pores existing on the concrete surface, and this air can become a factor in inhibiting radical polymerization. However, even in such cases, the polymerization of the primer composition of the present invention is not inhibited and can be cured in a short time.

All parts in the following examples indicate parts by weight, and the curing time starts from the point at which the curing agent is added to the primer composition.

Example 1 975 parts of methyl methacrylate and 5 parts of 2,4-dimethyl-6-t-butylphenol were charged at room temperature into a reaction vessel equipped with a stirrer and a heating jacket, and bisphenol A and epichlorohydrin were added while stirring at room temperature. 2000 parts of an epoxy resin having a molecular weight of 1600 and an epoxide equivalent weight of 925 based on the following were added in portions. The reaction vessel was heated to an internal temperature of 70°C to dissolve the epoxy resin in methyl methacrylate, and then 27 parts of triethylamine was added. Next, the temperature inside the reaction vessel was
Raised to 80℃, 112 parts of methacrylic acid and lauric acid
130 parts of the mixture were added dropwise over 2 hours. Internal temperature 80℃
Stirring was continued for 8 hours while the temperature was maintained at 100° C. to allow reaction, and then the mixture was cooled. Next, 250 parts of methyl methacrylate was added and mixed, and the acid value and epoxide equivalent of the reaction mixture were measured, and an acid value of 4.5 and an epoxide equivalent of 5,600 were obtained.

68 parts of the reaction mixture containing the unsaturated β-hydroxy ester produced in this way was charged into a melting vessel equipped with a stirrer and a heating jacket, and 31 parts of methyl methacrylate was mixed and stirred. Then set this to 50
0.5 part of paraffin with a melting point of 50-52°C and N,N'-di(2-hydroxypropyl)-
1 part of p-toluidine was added and dissolved. By cooling this, a primer composition having a viscosity of 300 cps at 20°C was obtained.

When 3 parts of benzoyl peroxide powder (hereinafter referred to as BPO powder) with a concentration of 50% was added as a curing agent to 100 parts of this primer composition, and the mixture was thoroughly mixed and cured, it was cured in 26 minutes at 20°C. When this cured product was subjected to a tensile test based on JISK6301, it showed a breaking strength of 560 Kg/cm ² and an elongation rate of 3%.

Also, add 3 parts of BPO powder to 100 parts of this primer composition, mix well, and use a roller to apply approximately 3 parts of BPO powder onto a concrete block (5 x 20 x 20 cm).
When applied to a thickness of 0.5 mm, it cured in 18 minutes at room temperature (24°C) to form a strong coating. Two days later, the adhesive strength was measured using a Kenken type adhesive testing machine, and the concrete block part broke at 23.8 kg/cm ² , indicating good adhesiveness.

Example 2 Add 2 parts of BPO powder to 100 parts of the primer composition produced in Example 1, mix well, and use a spatula to spread about 0.3 mm onto an asphalt block (manufactured by Nippon Test Panel, 5 x 20 x 20 cm). When applied to a thickness of , it cured in 18 minutes at a temperature of 30°C, forming a strong coating. When the adhesive strength was measured using a Kenken type adhesive testing machine, it broke from the asphalt at 7.6 kg/cm ² , indicating that the adhesive strength was high.

Example 3 5 parts of BPO powder was added to 100 parts of the primer composition produced in Example 1, mixed well and applied to a mild steel plate (6 x 300 x 300 mm) with a powder of about 0.4 parts using a brush.
When applied to a thickness of 35 mm at a temperature of 10°C,
It cured in minutes and formed a strong coating. When the adhesive strength was measured using a Kenken type adhesive testing machine, it was 8.3Kg/
It was warm in ^cm2 .

Example 4 One part of N,N'-di(2-hydroxypropyl)-p-toluidine and N,
The viscosity at 20°C was obtained in the same manner as in Example 1 except that 2 parts of N'-dimethyl-p-toluidine was used in combination.
A 300 cps primer composition was produced.

100g of this primer composition and 55g of BPO powder
When the mixture was mixed well and cured at low temperature, it showed good curability as shown in Table 1.

Table-1 Curing temperature Curing time (°C) (minutes) 0 18 -10 37 -20 90 Example 5 Using the same method as Example 1, methyl methacrylate
984 parts of 2,4-dimethyl-6-t-butylphenol and 5 parts of 2,4-dimethyl-6-tert-butylphenol were charged, and 2000 parts of an epoxy resin based on bisphenol A and epichlorohydrin having a molecular weight of 1350 and an epoxide equivalent weight of 850 were added.
With heating to 70°C 27 parts of triethylamine were added. 86 parts of methacrylic acid, acrylic acid at internal temperature of 80℃
A mixture of 30 parts of lauric acid and 141 parts of lauric acid was added dropwise over 2 hours, and the mixture was reacted at 80°C for 8 hours. After cooling this, 252 parts of methyl methacrylate was added, and the acid value and epoxide equivalent of the reaction mixture were measured, and an acid value of 4.9 and an epoxide equivalent of 6,500 were obtained.

The reaction mixture containing the unsaturated β-hydroxy ester thus produced was treated in the same manner as in Example 1 to obtain a primer composition having a viscosity of 270 cps at 20°C.

100 parts of this primer composition plus 6 parts of BPO powder
When applied with a spatula to a thickness of 0.4 mm on a concrete floor with an air temperature of 3°C and a surface temperature of 4°C, it cured in 44 minutes to form a strong coating film.

Example 6 A reaction was carried out according to the method of Example 1, except that 136 parts of industrial coconut oil fatty acid having the following composition was used instead of 130 parts of lauric acid, and a reaction mixture containing an unsaturated β-hydroxy ester was obtained. was manufactured.

Industrial coconut oil fatty acid: C ₈ C ₁₀ C ₁₂ C ₁₄ C ₁₆ C ₁₈ C ₁₈ (contains double bond) 8 7 48 18 8 2 9 (% by weight) 70 parts of the unsaturated β-hydroxy ester-containing reaction mixture was charged into a melting pot equipped with a stirrer and a heating jacket, and 29 parts of methyl methacrylate was mixed and stirred. This was then heated to 50°C, and 0.5 part of paraffin with a melting point of 54-56°C and N,N'-dimethyl-p-
1 part of toluidine was added and dissolved. By cooling this, a primer composition having a viscosity of 350 cps at 20°C was obtained.

5 parts of BPO powder to 100 parts of this primer composition
When applied to a concrete floor at a temperature of 5°C to a thickness of 0.3mm using a roller,
It cured in 50 minutes to form a strong coating.

Example 7 70 parts of the same unsaturated β-hydroxy ester-containing reaction mixture as used in Example 6 was charged into a dissolution vessel, and 23 parts of methyl methacrylate, 5 parts of 2-ethylhexyl acrylate, and 1 part of ethylene glycol dimethacrylate were added. The mixture was mixed and stirred. Then set this to 50
0.5 part of paraffin having a melting point of 54 to 56°C and part of N,N'-dimethyl-p-toluidine were added and dissolved. By cooling this, a primer composition having a viscosity of 350 cps at 20°C was obtained.

5 parts of BPO powder to 100 parts of this primer composition
When applied to a concrete floor at a temperature of 5°C to a thickness of 0.4 mm using a brush, it hardened in about 45 minutes to form a strong coating film.

Claims (1)

[Scope of Claims] 1. A primer composition for floor and wall coatings comprising the following (A) to (D). (A) Based on bisphenol A and epichlorohydrin, molecular weight 800-3000 and epoxide equivalent
400-2500 a) methacrylic acid and/or acrylic acid 74-64 mol%
and b) 100-80 mol% of at least one saturated monocarboxylic acid having 8-20 carbon atoms and 8
Unsaturated β- obtained by reacting a mixture of 0 to 20 mol % of at least one unsaturated monocarboxylic acid having ~20 carbon atoms with 26 to 36 mol % of a monocarboxylic acid Hydroxy ester 30-60% by weight (B) Methyl methacrylate or a polymerizable unsaturated monomer containing 80% by weight or more of methyl methacrylate 70-40% by weight (C) Paraffin and/or having a melting point of 40°C or higher For 100 parts by weight of wax, (A) and (B)
0.1 to 5 parts by weight (D) Tertiary amine, 0.1 to 5 parts by weight per 100 parts by weight of the total amount of (A) and (B)