JP2000007467A - Primer application method and primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively form a primer layer excellent in adhesiveness in a short time by coating a concrete structure with an epoxy base primer and coating the top of the base primer with a finishing primer contg. a radical polymerizable unsatd. compd. while the base primer is in a semi-cured state. SOLUTION: A concrete structure is coated with a base primer contg. an epoxy resin and an epoxy curing agent or further contg. a radical polymerizable unsatd. compd. and a photopolymn. initiator if necessary and the base primer is cured optionally by irradiation with light. At the time when the base primer is semi-cured, the top of the base primer is coated with a finishing primer contg. a radical polymerizable unsatd. compd. and a photopolymn. initiator. The unsatd. compd. is then photopolymerized by irradiation with light to cure the finishing primer. The photopolymn. is preferably accelerated by coating the top of the base primer with the finishing primer under irradiation with light. Lining is enabled on the concrete having a high water content in a short time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for applying a primer used for lining or coating inorganic surfaces such as concrete and cement mortar of buildings and structures in the field of civil engineering and construction. The present invention relates to a method for applying a primer having good adhesiveness to an inorganic surface, having no adverse effect on a coating layer or a lining layer provided thereon, and having good adhesiveness, and a base primer composition therefor.

[0002]

2. Description of the Related Art When lining or coating an inorganic surface such as concrete with an unsaturated polyester resin, vinyl ester resin, epoxy resin, etc., a primer is applied before the lining material is applied, and these are bonded. Technology for improving the performance is widely used. As the primer, an unsaturated polyester resin primer, a vinyl ester resin primer, a one-component urethane resin primer, or an epoxy resin primer is used.

[0003] Unsaturated polyester resin-based or vinyl ester resin-based primers are usually made of a low-viscosity composition to increase the permeability of concrete. Requires a long period of time, so not only can lining materials and other surface materials not be applied, resulting in reduced workability, but also when the curing takes too long, the resin composition penetrates into the concrete layer. Too thin, the coating film becomes thin, and the adhesiveness at the interface with the lining material or the like deteriorates, or the performance as a primer deteriorates, such as poor curing at the interface portion of concrete having a high water content. In addition, volatile reactive monomers (such as styrene monomer) volatilize, causing air pollution at the work site, or reducing the primer performance due to a change in the mixing ratio of the resin composition, causing a risk of loss of resin and ignition. And other problems.

[0004] Urethane resin-based primers are also generally of the solvent type, and therefore pose a risk of contamination of the working environment and ignition. Also, if the construction surface becomes high temperature, sufficient adhesive strength may not be obtained due to the foaming phenomenon of the primer,
There are problems such as difficult timing of applying the primer and the lining material. It is known that a cold-setting two-pack type epoxy resin primer generally has a high adhesiveness to an inorganic base such as concrete, and also has a high adhesiveness even when the base has a high water content. In particular, the room temperature curing type is greatly affected by the ambient temperature and the base temperature, and it takes a long time to complete curing, so that the working efficiency is reduced. When unsaturated polyester resin, vinyl ester resin, etc. are used for the lining material or coating material and curing is performed at room temperature using a peroxide catalyst, the lining layer is formed using an amine-based curing agent that is widely used as a room temperature curing agent for epoxy primer. Suffers from curing inhibition, resulting in poor curing at the interface between the primer layer and the lining layer, thereby failing to obtain sufficient adhesiveness.

Among these drawbacks, as one means for solving environmental pollution due to volatilization of reactive monomers and the like, in a room temperature curing system using a peroxide catalyst of an unsaturated polyester resin or a vinyl ester resin, volatilization in the resin is considered. Attempts have been made to reduce environmental pollution and odors by replacing the styrene monomer with other high-boiling compounds from styrene, etc., but it takes a long time to completely cure, and peroxides on site Problems such as the danger of using the catalyst and the problem of pot life cannot be solved.

Further, in order to solve the curing failure at the interface between the primer and the lining material due to the combination of the epoxy resin-based amine curing type primer and the unsaturated polyester resin or vinyl ester resin-based lining material, an epoxy resin primer and a lining material are used. JP-A-5-163803 has proposed a method of providing a urethane resin layer between them, but the problem that it takes a long time to completely cure the primer has not been solved.

[0007]

SUMMARY OF THE INVENTION In view of the above situation, the present invention relates to a method of lining an inorganic base such as concrete, which has a high adhesiveness similar to that of an epoxy resin primer even at a high water content, and has a high volatility. It is an object of the present invention to develop a primer application method which is small in size and can be applied in a short time and a primer composition used for the method.

[0008]

Means for Solving the Problems The present invention relates to [1] A radical polymerizable unsaturated compound when a concrete structure is coated with a base primer containing an epoxy resin and an epoxy curing agent, and cured to a semi-cured state. And a method of applying a primer to a concrete structure, comprising applying a finishing primer containing a photopolymerization initiator and irradiating light to cure the finishing primer, [2] a semi-cured state containing an epoxy resin and an epoxy curing agent. The primer application method for a concrete structure according to the above [1], wherein a finish primer containing a radical polymerizable unsaturated compound and a photopolymerization initiator is applied to the base primer while irradiating light.

[3] A concrete structure is coated with a base primer (A) of 5 to 95 parts by weight of a radically polymerizable unsaturated compound and 95 to 5 parts by weight of an epoxy compound (total 100 parts by weight). Composition: 100 parts by weight, (B) photopolymerization initiator: 0.01 to 10 parts by weight, and (C) epoxy curing agent: 0.01 to 300 parts by weight After the curing has progressed to a semi-cured state by applying light, apply a finishing primer containing a radically polymerizable unsaturated compound and a photopolymerization initiator, and then apply light to cure the finishing primer. A method for applying a primer to a concrete structure, characterized by [4]
A base primer having the following composition while irradiating a concrete structure with light (A) A polymerizable composition in which 5 to 95% of epoxy groups contained in an epoxy compound are (meth) acryloylated. 100 parts by weight, (B) photopolymerization initiator 0.01 to 10 parts by weight, and (C) epoxy curing agent 0.01 to 300 parts by weight Then, applying a finishing primer composed of a radically polymerizable unsaturated compound and a photopolymerization initiator when the curing has progressed to a semi-cured state by light irradiation, and then curing the finishing primer by further light irradiation. Primer construction method for concrete structures, [5]
The concrete according to [3] or [4], wherein a base primer is applied to the concrete structure while irradiating the concrete structure, and then a finish primer containing a radically polymerizable unsaturated compound and a photopolymerization initiator is applied while irradiating light. Primer installation method for structures,

[6] The method for applying a primer to a concrete structure according to any one of [1] to [4], wherein the epoxy curing agent is an amine-based curing agent, [7]
The method for applying a primer to a concrete structure according to any one of the above [1] to [4], wherein the photopolymerization initiator is an acylphosphine oxide-based compound, [8] a wavelength of at least a visible light region as a light source for light irradiation. The method for applying a primer to a concrete structure according to any one of the above [1] to [5] using a light source that emits light or sunlight, [9] a radically polymerizable unsaturated compound is an unsaturated polyester resin, vinyl ester The primer composition for a concrete structure according to any one of the above [1] to [4], which is at least one of a resin and a urethane acrylate resin,

[10] (A) A polymerizable composition comprising 5-95 parts by weight of a radical polymerizable unsaturated compound and 95-5 parts by weight of an epoxy compound (100 parts by weight in total) 100 parts by weight, (B) a photopolymerization initiator: 0.01 to 10 parts by weight, and (C) an epoxy curing agent: 0.01 to 300 parts by weight. [11] (A) a polymerizable composition in which 5-95% of the epoxy groups contained in the epoxy compound have been converted to (meth) acryloyl .... 100 parts by weight (B) a photopolymerization initiator: 0.01 to 10 parts by weight; and (C) an epoxy curing agent: 0.01 to 300 parts by weight. Base primer composition for constructs It has solved the above problems by developing.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to an epoxy-based primer (a primer composition comprising an epoxy component containing an epoxy group and an epoxy curing agent), which has an excellent adhesion to concrete, but has a slow curing and is coated. In order to improve the shortcoming that the layer or lining layer (both of which may be referred to as a finishing layer) cannot be applied immediately, an epoxy primer is used as a base primer (a primer applied directly to a concrete structure). This can be cured in a short time in a semi-cured state (in the present invention, a state in which the applied layer has been cured to some extent and another primer or lining or the like can be applied to the upper layer). Amine-based, which has excellent adhesion to the base primer and epoxy primer, and prevents the curing of the finished layer By using as a finishing primer consisting of a radical polymerizable unsaturated compound not containing an agent and a photopolymerization initiator (a primer for applying on a base primer and applying a finishing layer thereon) in a short time This is a method for forming an effective primer layer.

In the present invention, the epoxy base primer used as the base primer composition includes:
An epoxy primer consisting of an epoxy resin and an epoxy curing agent, a radical polymerizable unsaturated compound, an epoxy resin, an epoxy primer consisting of a photopolymerization initiator and an epoxy curing agent, and a part of the epoxy resin contained in the epoxy compound (meta There is an epoxy primer comprising an acryloylated polymerizable composition, a photopolymerization initiator and an epoxy curing agent.

The epoxy resin may be one produced by a commonly known method, and is a thermosetting epoxy resin having at least two or more epoxy groups in one molecule. Examples of the epoxy resin include an ether type bisphenol type epoxy resin, a novolak type epoxy resin, a polyphenol type epoxy resin, an aliphatic type epoxy resin, an ester type aromatic epoxy resin, a cyclic aliphatic epoxy resin, and an ether / ester type epoxy resin. Such epoxy resins may be used alone or in combination of two or more. As the epoxy resin curing agent to be added to the epoxy primer composition, an amine curing agent is generally used, and examples thereof include aliphatic amines, aromatic amines, polyamides, and heterocyclic amines. Known combinations can also be used.

These epoxy resins can be diluted with a solvent, a reactive diluent or the like in order to enhance the impregnation property on the construction surface. Known reactive diluents may be used, such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, diglycidyl ether of 1,4-butanediol, diglycidyl ether of neopentyl glycol, and trimethylolpropane triglycidyl. alcohols polyglycols glycidyl ethers such as glycidyl ether or alkyl _{(C 12} ~C ₁₄₎ glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ethers such as ether, p-te
Examples thereof include phenol glycidyl ethers such as rt-butylphenyl glycidyl ether, glycidyl carboxylate, and alicyclic and other non-glycidyl epoxies.
If necessary, a silane coupling agent such as epoxy silane or amino silane may be added for the purpose of increasing the adhesion to a wet surface and preventing flipping, and may be added as an adhesion-imparting agent.

In the present invention, the radically polymerizable unsaturated compound used as a constituent component of the base primer composition and as the finished primer composition is an unsaturated polyester resin, a vinyl ester resin (hereinafter referred to as “resin etc. ), Or at least one of urethane acrylate resins. The unsaturated polyester resin used in the present invention is obtained by subjecting a condensation product (unsaturated polyester) obtained by an esterification reaction between a polyhydric alcohol and an unsaturated polybasic acid (and optionally a saturated polybasic acid) to styrene. Resins dissolved in polymerizable monomers such as those described in "Polyester Resin Handbook" (published by Nikkan Kogyo Shimbun, 1988) or "Paint Glossary Dictionary" (edited by The Coloring Materials Association, published in 1993). It is.

A vinyl ester resin is also called an epoxy acrylate resin, and is generally formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. The resulting compound having a polymerizable unsaturated bond (vinyl ester) dissolved in a polymerizable monomer such as styrene, and is called "Polyester Handbook" (published by Nikkan Kogyo Shimbun, 1988) or "Glossary of Paint Terms". (Edited by The Color Material Association, published in 1993).

The unsaturated polyester used as a raw material of the unsaturated polyester resin may be one produced by a known method, and specifically, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid A polybasic acid or an anhydride thereof having no polymerizable unsaturated bond, and a polymerizable unsaturated polybasic acid or an anhydride thereof such as fumaric acid, maleic acid, and itaconic acid as an acid component; Glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2
Manufactured by reacting a polyhydric alcohol such as -dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A as an alcohol component. It is.

The vinyl ester as a raw material of the vinyl ester resin (epoxy acrylate resin) is produced by a known method, and is obtained by reacting an unsaturated monobasic acid such as acrylic acid or methacrylic acid with the epoxy resin. Α, β-unsaturated epoxy (meth) acrylates, or saturated or unsaturated polyesters having terminal carboxyl groups obtained from saturated dicarboxylic acids and / or unsaturated dicarboxylic acids and polyhydric alcohols. It is a saturated polyester or unsaturated polyester (meth) acrylate obtained by reacting a saturated carboxylic acid ester. Examples of the epoxy resin as a raw material include bisphenol A glycidyl ether, its high molecular weight homologues, and novolak type polyglycidyl ethers.

As the saturated dicarboxylic acid used for the polyester having a terminal carboxyl group, a dicarboxylic acid having no active unsaturated group, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, etc. Is mentioned. As unsaturated dicarboxylic acids, dicarboxylic acids having an active unsaturated group,
For example, fumaric acid, maleic acid, maleic anhydride, itaconic acid and the like can be mentioned. As the polyhydric alcohol component,
For example, ethylene glycol, propylene glycol,
Diethylene glycol, dipropylene glycol, 1,
2-butanediol, 1,3-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 2-
Methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4
And polyhydric alcohols such as dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide of bisphenol A. Glycidyl methacrylate is a typical example of the α, β-unsaturated carboxylic acid ester having an epoxy group used in the production of polyester (meth) acrylate.

As the unsaturated polyester or vinyl ester used for the resin or the like, those having a relatively high degree of unsaturation are preferable, and those having an unsaturated group equivalent (molecular weight per unsaturated group) of about 100 to 800 are used. . Those having an unsaturated group equivalent of less than 100 cannot be synthesized. However, if the unsaturated group equivalent exceeds 800, a cured product having high hardness cannot be obtained.

The unsaturated polyester resin or vinyl ester resin used in the present invention is usually a mixture of the above unsaturated polyester or vinyl ester with a reactive monomer such as a styrene monomer.
The reactive monomer blended in the resin or the like of the present invention reduces the viscosity of the resin or the like, increases permeability to concrete or the like, and improves the hardness, strength, chemical resistance, water resistance, etc. of the cured film. It is important to add 10 to 250 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of the unsaturated polyester or vinyl ester. The amount is 10
If the amount is less than part by weight, workability due to high viscosity, impregnation deteriorates, and if the amount exceeds 250 parts by weight, sufficient coating film hardness is not obtained, chemical resistance, water resistance, etc. are insufficient, and it is preferable as a primer. Absent. In this case, part or all of the styrene monomer may be replaced with a styrene-based monomer such as chlorostyrene, vinyltoluene, or divinylbenzene, or another polymerizable monomer such as methyl (meth) acrylate or ethylene glycol dimethacrylate. It is also possible to substitute and use within a range that does not impair.

The urethane acrylate used as the radical polymerizable component is a known oligomer resin obtained by reacting a polyisocyanate with a polyol such as polyether polyol, polyester polyol, polyacryl polyol and hydroxyalkyl acrylate.

The resin composition comprising the radically polymerizable unsaturated compound and the epoxy compound used in the present invention may be a thermosetting epoxy compound having at least two epoxy groups in one molecule produced by a known method. It is a resin composition obtained by mixing a resin composition obtained by combining a resin and an epoxy curing agent for room temperature curing with an unsaturated polyester resin or a vinyl ester resin produced by a known method, and the mixing ratio is 10/90 to 90 /. 10 parts by weight.
Preferably, it is 20/80 to 70/30 parts by weight. The epoxy resin used may be used alone or in combination of two or more, and the unsaturated polyester resin or the vinyl ester resin may be used alone or in combination.
Both may be used in combination of two or more. In addition, the reactive diluent used in this case may be a diluent having an epoxy group used in an epoxy resin or a diluent having a radical polymerizable unsaturated group. Further, a diluent having a structure having both an epoxy group and a radically polymerizable unsaturated group in a molecule such as glycidyl methacrylate or allyl glycidyl ether may be used.

The polymerizable compound in which 5-95% of the epoxy groups in the epoxy compound used as one of the epoxy primers of the base primer in the present invention are (meth) acryloylated is produced by a known method. 1
In a thermosetting epoxy resin having at least two or more epoxy groups in the molecule, an unsaturated monobasic acid such as acrylic acid or methacrylic acid is added to the epoxy group by a known method,
An epoxy (meth) acrylate obtained by reacting 5 to 95%, preferably 10 to 90% of epoxy groups,
Epoxy resins may be used alone or in combination of two or more. In addition, the reactive diluent used in this case may be a diluent having an epoxy group used in an epoxy resin or a diluent having a radical polymerizable unsaturated group. Further, a diluent having a structure having both an epoxy group and a radically polymerizable unsaturated group in a molecule such as glycidyl methacrylate or allyl glycidyl ether may be used. As the epoxy resin curing agent to be added to the epoxy primer composition, a common amine curing agent is used as in the case of the epoxy resin, and examples thereof include aliphatic amines, aromatic amines, polyamides, and heterocyclic amines. And a combination of known ones such as these modified amines. Compounds other than aliphatic amines that can be cured at room temperature, such as a combination of an aromatic amine and salicylic acid and a mercaptan compound, can also be used.

In the present invention, visible light is 380 to 780.
The visible light polymerization initiator used in the present invention refers to a compound having photosensitivity in the visible light region. Examples of visible light polymerization initiators having photosensitivity in the visible light region include “surface”, 27, (7),
548 (1989), Sato et al., "Summary of the 3rd Polymer Material Forum", camphorquinone, benzyl, trimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, bispentadienyltitanium-di (pentane) described in IBP18 (1994). Single visible light polymerization initiator such as fluorophenyl), organic peroxide / dye system, diphenyliodonium salt / dye,
Biimidazole / keto compound, hexaarylbiimidazole compound / hydrogen donating compound, mercaptobenzothiazole / thiopyrylium salt, metal arene / cyanine dye, and hexaarylbiimidazole / radical generator described in JP-B-45-37377. And other known composite initiator systems.

The acylphosphine oxide used in the present invention is represented by the general formula (1) or (2).

Embedded image (Wherein, R ^{1 to} R ³ each independently represent an alkyl group,
Represents an aryl group, an aralkyl group, an alkenyl group or an alkynyl group. )

[0028]

Embedded image (Wherein, R ^{4 to} R ⁶ are each independently an alkyl group,
It represents an aryl group, an aralkyl group, an alkenyl group, an alkynyl group or a heterocyclic group. These polymerization initiators are more photosensitive in the longer wavelength region than the conventionally used UV initiator (visible light region of 400 nm or more), have excellent light transmittance, and are cleaved by light irradiation. As a result, an acyl radical and a phosphino radical are generated, so that the polymerization initiation efficiency is higher than that of a conventionally used UV initiator.

Specific examples of the bisacylphosphine oxide compound of the general formula (1) used in the present invention include bis (2,6-dichlorobenzoyl) phenylphosphine oxide and bis (2,6-dichlorobenzoyl) -2. ,
5-dimethylphenylphosphine oxide, bis (2
6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl)
-4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,2-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -dodecylphosphine oxide, bis (2,6-di Chlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5 -Dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl)
-2,5-phenylphosphine oxide, bis (2-
Methyl-1-naphthoyl) -4-biphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4
-Ethoxybiphenylphosphine oxide, bis (2
-Methyl-1-naphthoyl) -2-ethoxybiphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide,
Bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-
1-naphthoyl) -4-methoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-
2,4,4-trimethylpentylphosphine oxide and the like can be mentioned.

Specific examples of the acylphosphine oxide compound of the general formula (2) used in the present invention include 2,2.
4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-diphenylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,3,5,6
-Tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2-phenyl-6
-Methylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,8-dimethylnaphthalene-1-carbonyl-diphenylphosphine oxide, 1,3-dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl-phenylphosphinic acid methyl ester and the like can be mentioned.

Specifically, for example, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one (trade name: D
arocur-1173, Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide (Ciba Specialty Chemicals Co., Ltd.) 75
% / 25% trade name “IRGACURE 1700” (Ciba Specialty Chemicals Co., Ltd.)
1-hydroxy-cyclohexyl-phenyl ketone (trade name: "Irgacure 184", manufactured by Ciba Specialty Chemicals Co., Ltd.), and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine "IRGACURE 1800" (manufactured by Ciba Specialty Chemicals Co., Ltd.) mixed with oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) at a ratio of 75% / 25%, and mixed at a ratio of 50% / 50%. Trade name "Irgacure 1850" (manufactured by Ciba Specialty Chemicals Co., Ltd.), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name "Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2,4,6-trimethylbenzoyl-
Diphenylphosphine oxide (trade name: Lucir)
in TPO BASF Co., Ltd.), 2-hydroxy-
2-Methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxyoxide (trade name: L
ucirin TPO BASF) 50% /
Trade name mixed at a ratio of 50%: "Darocur4
265 ". 380 as a visible light polymerization initiator
Any photopolymerization initiator having photosensitivity in the wavelength range of nm to 780 nm may be used, and these may be used in combination.

The amount of the photopolymerization initiator having photosensitivity in the visible light range is generally 0.0
It is 1 to 20 parts by weight, preferably 0.05 to 15 parts by weight. If the amount of the visible light polymerization initiator composition is less than 0.01 part by weight, the polymerization tends to be insufficient, while if it exceeds 20 parts by weight, it is economically disadvantageous and the physical properties of the cured product are deteriorated. Known radical polymerization inhibitors such as quinones and tertiary amines may be added in order to adjust the curing time of the resin to which the photopolymerization initiator is added and to ensure surface drying properties.

In the primer composition of the present invention, if necessary, a nonionic surfactant may be added to adjust the hydrophilic / lipophilic balance (HLB) to increase the permeability to concrete. . The addition amount is 0.1 to 5 parts by weight based on 100 parts by weight, and examples of the nonionic surfactant include an alkyl phenyl ether type, an alkyl ester type, an alkyl amine type and a sorbitan derivative.
A detailed description is given in JP-A-55-62970.

Further, in the present invention, if necessary, thixotropicity may be imparted by a known method, and a silane coupling agent may be added in order to prevent flipping on the wet concrete surface and improve the adhesiveness. . For the thixotropic addition, for example, there is a method of adding 0.1 to 50 parts by weight of silica powder (aerosil type), mica powder, calcium carbonate powder, etc. to 100 parts by weight of the resin. If necessary, a moisture absorbent such as molecular sieve is used in combination, and 3-methacryloxypropyltrimethoxysilane, vinylmethoxysilane,
0.1 parts by weight of vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, etc.
There is a method of adding ２０20 parts by weight. In the present invention,
In order to solve the swelling of the primer due to the vapor pressure of the water vapor inside the concrete, if necessary, an inorganic filler, an organic filler or a few mm of organic or inorganic short fibers may be added to such an extent that the hardening is not affected. Such a method is described in detail in JP-A-6-271373 and JP-A-57-10656.

The light source used in the molding method of the present invention is a light source that emits light in a wavelength region of 380 to 780 nm, and a light source that emits heat such as near-infrared light or infrared light of 780 nm or more. It may be a light source having a combination, such as a metal halide lamp, a xenon lamp, a near infrared lamp, a sodium lamp, a halogen lamp, an incandescent lamp, a sun lamp,
Sunlight or the like can be used. Further, various lamps can be used in combination. For outdoor work, sunlight is particularly effective. In order to obtain a faster curing speed, light in a short wavelength region having a high energy order is effective, but it is difficult to completely cure the primer composition when the thickness of the primer composition is large. In order to accelerate the curing of the epoxy / amine cold curing primer, the wavelength distribution is long in the long wavelength region at a wavelength of 380 nm or more, and light that emits heat is effective. Metal halide lamps, halogen lamps, near infrared lamps, An infrared lamp or the like is effective.

Although the light irradiation time varies depending on the effective wavelength of the light source, the output, the irradiation distance, the thickness of the primer composition, the amount of the filler, or the blending amount of the polymerization initiator, it cannot be specified unconditionally. 01 hours or more, preferably 0.1 hour.
It may be adjusted so as to be at least 05 hours. The primer application method of the present invention includes an epoxy primer composition as a base primer having high adhesion to an inorganic base such as a concrete structure [(epoxy component having epoxy group) / amine epoxy curing agent].
Is applied, and when this is in a semi-cured state, a photo-radical-curable finishing primer composition is applied and photo-cured. Since the photocurable primer cures in a short time, the primer application is completed in a short time. The base primer, which requires a long time to cure, cures slowly after application of the primer and adheres firmly to concrete structures.

As the base primer, an epoxy primer composed of a radically polymerizable unsaturated compound, an epoxy resin, a photopolymerization initiator and an epoxy curing agent, or a polymerizable polymer obtained by converting a part of epoxy groups in an epoxy compound into (meth) acryloyl. An epoxy primer comprising a composition, a photopolymerization initiator, and an epoxy curing agent contains a photopolymerization initiator and becomes semi-cured in a short time when irradiated with light. A light-curing primer composition that does not contain an amine-based epoxy curing agent is applied on top of this, and by irradiating light, the entire primer application process can be completed in a very short time, and finished. Does not interfere with the curing of the layer. In the case of the base primer in a semi-cured state, the epoxy group reacts slowly on the lower surface of the finished primer composition and becomes completely cured after several days.

In the method of applying a primer according to the present invention, a photocurable polymerizable unsaturated compound layer (finish primer layer) is provided between the base primer layer and the finish layer, so that an epoxy compound / amine cold-setting epoxy system can be used. Prevents poor curing due to the action of the amine-based epoxy curing agent at the interface between the primer and the unsaturated polyester resin or vinyl ester resin lining layer of the finishing layer. The mild heat from the light source allows the epoxy compound / amine-based room temperature Since the curing of the curing primer is promoted, the workability can be improved safely without any trouble, the economy is excellent, and the light used is safe.

[0039]

The present invention will be described in detail with reference to the following examples and comparative examples. In each example, "parts" and "%" are based on weight. [Preparation of Primer Composition] (Primer Composition-1) Epoxy resin [trade name: Epicoat 828 (manufactured by Yuka Shell Co., Ltd.): 60 parts, Epicoat 834: 20 parts] 80 parts, neopentyl glycol diglycidyl ether [ Trade name SR-NGP (manufactured by Sakamoto Pharmaceutical Co., Ltd.)]: 10 parts, butyl glycidyl ether [reactive diluent BGE]: 10 parts, and an epoxy curing agent [trade name Epicure S-005P (oilification) Shell Co.)]: 80 parts was added to obtain a cold-setting epoxy resin composition, Primer-1. (Primer composition-2) vinyl ester resin [trade name: Lipoxy R-802 (manufactured by Showa Polymer Co., Ltd.)]: 100
Acylphosphine oxide-based photopolymerization initiator having photosensitivity in the visible light region in its part [IRGACURE 1800
(Ciba Specialty Chemicals Co., Ltd.): I
-1800]: 2.0 parts were mixed to obtain a primer composition-2 which was a photo-radical polymerizable vinyl ester resin composition.

(Primer composition-3) Urethane acrylate resin (trade name: Lipoxy FM-1600 (manufactured by Showa Polymer Co., Ltd.)): 100 parts and I-1800: 2.0 parts were mixed, and photo-radical polymerizable A primer composition-3 which was a urethane acrylate resin composition was obtained. (Primer composition-4) Unsaturated polyester resin [trade name: Rigolac FK-2000 (Showa Polymer Co., Ltd.)
)]: 100 parts and I-1800: 1.0 part,
A primer composition-4 which was a photo-radical polymerizable unsaturated polyester resin composition was obtained. (Primer composition-5) Primer composition-1: 50
To 50 parts by weight of primer composition-2:
A primer composition-5 containing a cold-setting epoxy resin component and a photo-radical polymerizable vinyl ester resin component was obtained.

(Primer Composition-6) Epicoat 828 (epoxy equivalent: 189): 1 equivalent (189 equivalents) was added to a reactor equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer.
g), Epicoat 834 (epoxy equivalent 250): 1 equivalent (250 g), chromium naphthenate: 1.57 g, and methacrylic acid in which 0.026 g of hydroquinone was dissolved while stirring at 110 ° C. while blowing air. : 1 equivalent (86 g) was charged, and 3 at 110 to 130 ° C.
When the acid value was reduced to 0 for 4 hours, the reaction was terminated, and styrene monomer: 283 parts was added to obtain a vinyl ester resin having an epoxy group. Next, I-180 was added to 100 parts of the vinyl ester resin having an epoxy group.
0: 1.0 part, epoxy curing agent [trade name Epicure S-
002 (manufactured by Yuka Shell Co., Ltd.)]: 80 parts by weight were added to obtain a primer composition-6 which is a photo-radical polymerizable vinyl ester resin composition having a room temperature-curable epoxy group.

(Example 1) (Coating and curing conditions of primer) Primer composition
5 was applied to the upper surface (30 cm × 30 cm) of a 30 cm × 30 cm × 6 cm concrete sidewalk board with a brush so as to be 0.2 kg / m ^2, and left for 5 minutes to allow the primer composition to penetrate into the concrete. 380-780
1 m using a 2KW metal halide lamp [trade name: Dynabeam 2: manufactured by Toshiba Lighting & Technology Corp .: hereinafter referred to as lamp 1], which is a light source including a wavelength region of visible light region of nm.
Irradiation at a distance of 5 minutes lost fluidity. Next, the primer composition-2 was applied thereon with a brush so as to have a concentration of 0.1 kg / m ^2, and light irradiation was performed using a lamp 1 at a distance of 1 m for 5 minutes to eliminate the surface tack and harden.

(FRP lining) Next, 3.0 parts of benzoyl peroxide-based peroxide catalyst Cadox B-40E [manufactured by Kayaku Akzo Co., Ltd.] was added to adjust unevenness of the cured primer surface. Lipoxypate FM [manufactured by Showa Polymer Co., Ltd.] was thinly applied to a concentration of 0.2 kg / m ² and allowed to stand for one day. After curing, carbon fiber cloth [trade name: Torayca Cloth, T-300, CF weight 193g
/ M ² (manufactured by Toray Industries, Inc.)] To 2 ply, room temperature curing catalyst Permec-N [manufactured by NOF Corporation / cobalt naphthenate (cobalt: 6%) = 1.5 / 0.5] was added. A vinyl ester resin [trade name: Lipoxy R-804 (manufactured by Showa Polymer Co., Ltd.)] has a carbon content of about 60 V.
ol%, and laminated on the putty cured surface,
Allowed one day to cure.

(Adhesion test) In order to confirm the performance of the primer, ADHESION TESTER elco was used.
Using a meter and measuring the adhesive strength and the state of destruction three days after the application of the primer with an adhesive area of 4.9 cm ² , the concrete was peeled off by about 10 mm due to the destruction of the concrete base material. The adhesion was good, and it was confirmed that the performance as a primer was sufficiently satisfied. Table 1 shows the adhesive strength.

Example 2 (Conditions for Applying and Curing Primer) Primer Composition
6 was applied to the upper surface (30 cm × 30 cm) of a 30 cm × 30 cm × 6 cm concrete sidewalk board with a brush so as to have a concentration of 0.2 kg / m ² and left for 5 minutes to allow the primer composition to penetrate into the concrete. When light irradiation was performed for 5 minutes at a distance of 1 m using the lamp 1, the fluidity disappeared. Next, Primer Composition-3 was placed thereon with 0.1K
g / m ² was applied with a brush, and light irradiation was performed using a lamp 1 at a distance of 1 m for 5 minutes using a lamp 1.

(FRP lining) In the same manner as in Example 1, unevenness was adjusted with Lipoxy Putty FM, and "Treca" cloth 2ply was laminated on the putty hardened surface using Lipoxy R-804. (Adhesion test) ADHESI by the same operation as in Example 1.
Using the ON TESTER elmeter,
When the adhesive strength and the state of destruction of the three days after the application of the primer were examined, about 10 mm of the concrete was peeled off when the concrete base material was broken. The adhesion was good, and it was confirmed that the performance as a primer was sufficiently satisfied. Table 1 shows the adhesive strength.

(Example 3) Primer composition-1 was treated with 30
It was applied to the upper surface (30 cm × 30 cm) of a concrete side board (cm × 30 cm × 6 cm) with a brush so as to have a concentration of 0.2 kg / m ^2, and was left at room temperature to lose fluidity after 3 hours. Next, the primer composition-4 was applied thereon with a brush so as to have a concentration of 0.1 kg / m ^2, and light irradiation was performed for 5 minutes at a distance of 1 m using a lamp 1. .

(FRP lining) In the same manner as in Example 1, the lipoxy putty FM was used to adjust the unevenness, and "Treca" cloth 2ply was laminated on the putty hardened surface using Lipoxy R-804. (Adhesion test) ADHESI by the same operation as in Example 1.
Using the ON TESTER elmeter,
When the adhesive strength and the state of destruction of the three days after the application of the primer were examined, about 10 mm of the concrete was peeled off when the concrete base material was broken. The adhesion was good, and it was confirmed that the performance as a primer was sufficiently satisfied. Table 1 shows the adhesive strength.

(Example 4) (Conditions for applying and curing the primer) The primer composition-6 was spray-up molded on the upper surface (30 cm x 30 cm) of a concrete sidewalk board of 30 cm x 30 cm x 6 cm in direct sunlight. 0.2 kg / m by spraying using Super Slave (Binks, USA)
^{When the} composition was applied with a brush so as to obtain No. ² , the fluidity disappeared when light irradiation was performed for 3 minutes. Next, the primer composition
When No. ² was applied thereon by spraying so as to be 0.1 kg / m ² , the surface tack disappeared and hardened in 3.5 minutes under sunlight.

(FRP lining) In the same manner as in Example 1, the unevenness was adjusted with Lipoxy Putty FM, and "Treca" cloth 2ply was laminated on the putty hardened surface using Lipoxy R-804. (Adhesion test) ADHESI by the same operation as in Example 1.
Using the ON TESTER elmeter,
When the adhesive strength and the state of destruction of the three days after the application of the primer were examined, about 10 mm of the concrete was peeled off when the concrete base material was broken. The adhesion was good, and it was confirmed that the performance as a primer was sufficiently satisfied. Table 1 shows the adhesive strength.

Comparative Example 1 (Conditions for Applying and Curing Primer) Primer Composition
1 was applied to the upper surface (30 cm × 30 cm) of a 30 cm × 30 cm × 6 cm concrete sideboard (30 cm × 30 cm) with a brush so as to be 0.2 kg / m ^2, and was left at room temperature. Dried. Eight hours were spent in the primer application process. (FRP lining) In the same manner as in Example 1, the lipoxy putty FM was used to adjust the unevenness, and "Treca" cloth 2ply
Was laminated on the putty cured surface using Lipoxy R-804. (Adhesion test) ADHESI by the same operation as in Example 1.
Using the ON TESTER elmeter,
Examination of the adhesive strength and the state of breaking three days after the application of the primer revealed that the vinyl ester resin-based putty had low adhesiveness on the epoxy primer. Table 1 shows the adhesive strength.

(Comparative Example 2) (Conditions for coating and curing of primer) Vinyl ester resin [trade name, Lipoxy R-806, Showa Kogaku Co., Ltd.]
100 parts of a mixture consisting of 100 parts, lipoxy R-803AT: 40 parts, and styrene monomer: 70 parts.
A mixture of room temperature curing agent Permec N [manufactured by NOF CORPORATION] / cobalt naphthenate 1.2: 0.5 part was used as a room temperature primer, and the upper surface (30 cm × 30 cm) of a 30 cm × 30 cm × 6 cm concrete sidewalk plate was used. ) To 0.2K
g / m ² was applied with a brush and allowed to dry at room temperature after 3 hours. Three hours were spent in the primer application process. (FRP lining) In the same manner as in Example 1, the lipoxy putty FM was used to adjust the unevenness, and "Treca" cloth 2ply
Was laminated on the putty cured surface using Lipoxy R-804. (Adhesion test) ADHESI by the same operation as in Example 1.
Using the ON TESTER elmeter,
When the adhesive strength and the state of destruction of the three days after the application of the primer were examined, about 2 mm of the concrete was peeled off due to the destruction of the concrete base material. The bonding strength was also slightly lower. The results are shown in Table 1.

[0053]

[Table 1]

[0054]

Industrial Applicability The present invention relates to a method of applying a primer to a concrete structure used for coating or lining an inorganic surface such as concrete or cement mortar of a building or a structure in the field of construction and civil engineering, and a base primer for the method. It relates to a primer composition. According to this construction method, since the epoxy primer is used as the base primer, it is firmly adhered to the concrete structure, and the finishing primer is composed of a radical polymerizable unsaturated compound and a photopolymerization initiator. The use of a curable primer not only cures in a very short time only by irradiation, but also has a strong adhesion to the base primer, and the primer contains no amine epoxy curing agent at all. Therefore, even when an unsaturated polyester resin or a vinyl ester resin is used for the finishing layer, the curing is not hindered. Therefore, the application of the next finishing layer after the start of the primer application can be started in a short time. The primer application method of the present invention applies a finish primer when the base primer is semi-cured, and since this can be cured in a very short time by light irradiation, it is possible to move to a finish layer application step. . In addition, the base primer layer in a semi-cured state gradually cures thereafter, and after a few days is completely cured, there is no hindrance in the process, and although the performance is excellent as a primer process, Time was greatly reduced.

Claims (11)

[Claims] 1. A base primer containing an epoxy resin and an epoxy curing agent is applied to a concrete structure, and when curing has progressed to a semi-cured state, a finish primer containing a radically polymerizable unsaturated compound and a photopolymerization initiator is applied. And irradiating with light to cure the finishing primer. 2. A finish primer containing a radically polymerizable unsaturated compound and a photopolymerization initiator is applied to a semi-cured base primer containing an epoxy resin and an epoxy curing agent while irradiating light. Method for applying primer to concrete structures. 3. A polymerizable composition comprising a base primer (A) of 5 to 95 parts by weight of a radical polymerizable unsaturated compound and 95 to 5 parts by weight of an epoxy compound (100 parts by weight in total) in a concrete structure. 100 parts by weight, (B) photopolymerization initiator 0.01 to 10 parts by weight, and (C) epoxy curing agent 0.01 to 300 parts by weight After the curing has progressed to a semi-cured state by irradiation with light, a finishing primer containing a radically polymerizable unsaturated compound and a photopolymerization initiator is applied, and the light is further irradiated to cure the finishing primer. A method for applying primer to a concrete structure. 4. A polymerizable composition in which 5 to 95% of epoxy groups contained in an epoxy compound is (meth) acrylolylized in a concrete structure with a base primer having the following composition: 100 parts by weight, (B) photopolymerization initiator 0.01 to 10 parts by weight and (C) epoxy curing agent 0.01 to 300 parts by weight Then, when the curing has progressed to a semi-cured state by light irradiation, a finishing primer composed of a radically polymerizable unsaturated compound and a photopolymerization initiator is applied, and the finishing primer is cured by further light irradiation. Method for applying primer to concrete structures. 5. The concrete structure according to claim 3, wherein a base primer is applied to the concrete structure while irradiating light, and then a finish primer containing a radically polymerizable unsaturated compound and a photopolymerization initiator is applied to the concrete structure while irradiating light. Method for applying primer to concrete structures. 6. The method for applying a primer to a concrete structure according to claim 1, wherein the epoxy curing agent is an amine curing agent. 7. The method for applying a primer to a concrete structure according to claim 1, wherein the photopolymerization initiator is an acylphosphine oxide-based compound. 8. The method for applying a primer to a concrete structure according to claim 1, wherein a light source that emits light having a wavelength of at least a visible light region or sunlight is used as a light source for light irradiation. 9. The radical polymerizable unsaturated compound is at least one of unsaturated polyester resin, vinyl ester resin and urethane acrylate resin.
4. The primer composition for a concrete structure according to any one of 4. 10. A polymerizable composition comprising (A) 5 to 95 parts by weight of a radical polymerizable unsaturated compound and 95 to 5 parts by weight of an epoxy compound (100 parts by weight in total). 100 parts by weight, (B) a photopolymerization initiator: 0.01 to 10 parts by weight, and (C) an epoxy curing agent: 0.01 to 300 parts by weight. Base primer composition for concrete constructions. 11. A polymerizable composition in which (A) 5 to 95% of epoxy groups contained in an epoxy compound has been converted to (meth) acryloyl 100 parts by weight, (B) a photopolymerization initiator ... 0.01 to 10 parts by weight and (C) an epoxy curing agent ... 0.01 to 300 parts by weight.