JP2002234921A - Odor-less acrylic syrup composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a odor-less acrylic syrup composition excellent in a curing property at room and lower temperatures, and in short-term workability. SOLUTION: This acrylic syrup composition comprises 20-90 pts.mass (meth) acrylate monomer (A), having a boiling point not lower than 75 deg.C at 6.67 kPa, 10-80 pts.mass polymer or a radical polymerizable oligomer (B), and a wax (C) in dispersed condition (wherein total of component (A) and component (B) is 100 pts.mass).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-odor acrylic syrup composition having a low odor during construction, and more particularly to a flooring material having a low odor, excellent curability and excellent adhesion to concrete. The present invention relates to a low-odor acrylic syrup composition useful as a binder resin for concrete reinforcement using reinforcing fibers and wall materials, and further, reinforcing fibers and the like.

[0002]

2. Description of the Related Art Conventionally, there has been known a method of using a synthetic resin such as an unsaturated polyester resin, an epoxy resin, or a polyurethane resin to coat a floor surface or a wall surface. However, unsaturated polyester resins are excellent in solvent resistance, but inferior in weather resistance and poor in low-temperature workability. Epoxy resins have excellent adhesion to the substrate, but are poor in weather resistance, long in curing time, and inferior in low-temperature curability. Polyurethane resin has excellent elasticity and flexibility, but has a long curing time.

Therefore, instead of these resins, acrylic resins having a short curing time, excellent low-temperature curability, excellent weather resistance and chemical resistance are generally used.

[0004]

However, the acrylic resin has a peculiar odor due to the (meth) acrylate monomer.

For the purpose of suppressing this odor, for example, Japanese Patent No. 2512036 proposes an acrylic resin concrete composition containing a (meth) acrylate having an alkylcyclohexyl skeleton as a main component. However, this composition tends to have poor curability on the surface of the cured film.

Further, Japanese Patent Application Laid-Open No. Hei 5-186538 proposes a composition containing isobornyl methacrylate and hydroxypropyl methacrylate as monomers. Further, JP-A-6-329456
In Japanese Patent Laid-Open Publication No. H11-264, a synthetic resin composition for polymer concrete containing an alkyl (meth) acrylate having 6 to 16 carbon atoms is proposed. However, all the compositions have insufficient effects on odor reduction, and the curability of the coating surface tends to be poor.

Further, Japanese Patent Application Laid-Open No. Hei 10-87770 discloses polyethylene glycol di (meth) acrylate,
Curable resin compositions containing polypropylene glycol di (meth) acrylate have been proposed. Further, JP-A-10-158364 proposes a resin composition containing dicyclopentenyloxyalkyl (meth) acrylate. However, all the compositions have insufficient curability on the surface of the coating film.

On the other hand, as a method of repairing and reinforcing an existing structure made of concrete, such as a pier, a bridge, or a pillar of a building, a method using a fiber-reinforced resin is generally known. Patent 25
Japanese Patent No. 62704 discloses that a prepreg obtained by impregnating a sheet-like material or a woven fabric of a high-strength fiber such as carbon fiber, glass fiber, and organic fiber with an uncured epoxy resin as a reinforcing material is used as a reinforcing material. A method has been proposed in which an epoxy resin is attached to the surface of a structure and cured at room temperature.

However, epoxy resins have no peculiar odor like acrylic resins, but retain the odor of the amine compound used as a curing agent, and are inferior in curability at 10 ° C. or lower, especially 5 ° C. or lower. Further, since a long time is required for curing and curing, there is a problem that the construction period is lengthened. In addition, there is a possibility that the curing may be inhibited by moisture, and there is also a problem in the construction management that the concrete base surface and the construction surface need to be sufficiently managed.

The present invention has been made to solve the above-mentioned problems, and has a low odor, excellent curability at room temperature and low temperature, excellent short-term workability, and a primer, flooring material and top coat. An object of the present invention is to provide an acrylic syrup composition which is suitably used, and which exhibits an excellent reinforcing effect when used as a binder resin for a reinforcing method of an existing structure using reinforcing fibers.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the above-mentioned problems, and as a result, have found that 6.67 kPa (50 mm
By using a (meth) acrylate monomer having a boiling point of 75 ° C. or higher in Hg), a low-odor syrup composition can be obtained with little volatilization of the monomer into the air, and a polymer or a specific radical polymerizable The inventors have found that by combining oligomers, they cure in a short time and even at a low temperature, and can be suitably used as floor materials and wall materials, and have completed the present invention.

That is, the present invention relates to 20 to 90 parts by mass of a (meth) acrylate monomer (A) having a boiling point at 6.67 kPa of 75 ° C. or more, 10 to 80 parts by mass of a polymer or radically polymerizable oligomer (B), and An acrylic syrup composition comprising the wax (C) [100 parts by mass in total of the components (A) and (B)] in a state.

In the present invention, "(meth) acrylate" means "acrylate and / or methacrylate".

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The (meth) acrylate monomer (A) having a boiling point of at least 75 ° C. at 6.67 kPa, which is used in the present invention, has a low odor at ordinary temperature, is a curing component, and has a viscosity and a curing property of a syrup composition. It is also a component that adjusts properties such as mechanical strength of an object.

Specific examples of the (meth) acrylate monomer (A) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Hydroxy group-containing (meth) acrylates such as 2-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate and the like Tetrahydrofurfuryl group-containing (meth) acrylate; fluorine atom-containing (meth) such as trifluoroethyl (meth) acrylate
Acrylate; di- or trialkylcyclohexyl group-containing (meth) acrylate such as dimethylcyclohexyl (meth) acrylate and trimethylcyclohexyl (meth) acrylate; di- or trialkylphenyl group such as dimethylphenyl (meth) acrylate and trimethylphenyl (meth) acrylate Containing (meth) acrylate; stearyl (meth) acrylate, cetyl (meth)
Alkyl (meth) acrylate such as acrylate; 3-
Compounds having one (meth) acryloyl group in one molecule, such as (meth) acrylate having an ether bond, such as methoxybutyl (meth) acrylate and ethoxydiethylene glycol (meth) acrylate.

Further, ethylene glycol di (meth)
Acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butanediol di (meth)
Acrylate, 1,6-hexanediol (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether (meth) Acrylic acid adduct, neopentyl glycol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, tris (2-
Compounds having two or more (meth) acryloyl groups in one molecule, such as (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are also included.

One of these various (meth) acrylate monomers may be used alone, or two or more thereof may be used in combination. Among these, it is particularly preferable to use tetrahydrofurfuryl methacrylate as a main component.

The amount of the component (A) used is 20 parts by mass based on a total of 100 parts by mass of the components (A) and (B).
９０90 parts by mass. When the amount is less than 10 parts by mass, the viscosity of the syrup composition becomes high, the impregnation into the reinforcing fiber is poor, and the workability at the time of coating is poor. On the other hand, when this amount exceeds 90 parts by mass, the curability of the syrup composition is inferior, the viscosity thereof becomes too low, and sagging occurs during coating. This amount is preferably 30 to 85 parts by mass,
0 to 85 parts by mass is more preferred. When two or more compounds having a (meth) acryloyl group are used together in one molecule, the amount used is preferably 20 parts by mass or less. If this amount is suppressed to 20 parts by mass or less, the pot life of the syrup composition becomes good.

Among the polymers or radical polymerizable oligomers (B) used in the present invention, the polymer includes
From the viewpoint of solubility in the component (A), a homopolymer or a copolymer of an acrylic monomer is preferred.

Specific examples of the acrylic monomer used for the homopolymer or copolymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i- Butyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-
Octyl (meth) acrylate, isooctyl (meth)
Acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate,
Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) ) Acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, (meth) acryloylmorpholine and the like.

These monomers are polymerized by various conventionally known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method, whereby an acrylic homopolymer as the component (B) or A copolymer can be obtained. Its weight average molecular weight is 5,000-100,0
00 is preferred.

In addition to the acrylic monomers,
Other monomers may be used as long as the solubility in the component (A) is not impaired. Other monomers include styrene, vinyl toluene, vinyl acetate and the like.

Among the polymers or radically polymerizable oligomers (B) used in the present invention, examples of the radically polymerizable oligomer include urethane (meth) acrylate obtained by reacting polyol, polyisocyanate and hydroxyl group-containing (meth) acrylate. Oligomers; (meta)
By reacting acrylic acid or a dibasic acid such as maleic acid or phthalic acid with a hydroxy group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, a (meth) acrylate-terminated monocarboxylic acid is synthesized. )
Epoxy (meth) acrylate oligomer obtained by the reaction of an acrylate-terminated monocarboxylic acid with an epoxy resin; obtained by the reaction of a polybasic acid such as phthalic acid and adipic acid with a polyhydric alcohol such as ethylene glycol and butanediol. Polyester (meth) acrylate-based oligomers in which an acryloyl group, a methacryloyl group, or the like is introduced into the terminal of the oligomer by reaction with acrylic acid, methacrylic acid, or the like; However, it is not limited to these. Among these, from the viewpoint of curability, urethane (meth) acrylate oligomers, that is, urethane (meth) acrylate oligomers composed of a polyol having a carbonate bond in the molecule are particularly preferable.

The polyol used for synthesizing the urethane (meth) acrylate oligomer is a compound having two or more hydroxyl groups in one molecule. Examples of the polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polyhexamethylene glycol;
Addition reaction products of dihydric phenols such as bisphenol A, bisphenol F and bisphenol S with alkylene oxides such as ethylene oxide and propylene oxide; ethylene glycol, propylene glycol,
Polyhydric alcohols such as butanediol, butylene glycol, and methylpentanediol; and polybasic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, and trimellitic acid; Polyester polyols obtained by reaction with anhydrides; polylactone diols obtained from alkylene glycol and lactone; butanediol, pentanediol, hexanediol, heptanediol,
Polycarbonate diols containing a carbonate bond obtained by reacting a diol such as octanediol, nonanediol or cyclohexanedimethanol with a carbonate agent such as phosgene or dimethyl carbonate; and the like. These polyols may be used alone or in combination of two or more.

Among these polyols, polycarbonate diols are particularly preferable from the viewpoint of curability, and polycarbonate diols obtained using butanediol, pentanediol or hexanediol are more preferable.

The polyisocyanate used for synthesizing the urethane (meth) acrylate oligomer is a compound having two or more isocyanate groups in one molecule. As the polyisocyanate, for example, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethyl Xylylene diisocyanate, isophorone diisocyanate and the like. Adduct compounds of these compounds with water, trimethylolpropane and the like, trimer cyclized compounds, and the like can also be used as polyisocyanates. These polyisocyanates may be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate used for synthesizing the urethane (meth) acrylate oligomer, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 4
-Hydroxybutyl (meth) acrylate, adducts of ε-caprolactone and 2-hydroxyethyl (meth) acrylate, and the like. One of these hydroxyl group-containing (meth) acrylates may be used alone,
Two or more kinds may be used in combination.

If necessary, an allyl group-containing alcohol may be used in place of the hydroxyl group-containing (meth) acrylate. As the allyl group-containing alcohol, for example, allyl alcohol, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether,
Polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, glycerin monoallyl ether, glycerin diallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, pentaerythritol mono Allyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether and the like can be mentioned.

As the epoxy resin used for synthesizing the epoxy (meth) acrylate oligomer, for example, bisphenol type epoxy resin, novolak type epoxy resin and the like can be mentioned.

The molecular weight of the radically polymerizable oligomer is not particularly limited, but from the viewpoint of workability at the time of coating, the weight average molecular weight is preferably 30,000 or less.

Component (B) is used in an amount of 10 to 8 based on a total of 100 parts by mass of components (A) and (B).
0 parts by mass. Further, the amount is preferably 15 to 70 parts by mass, more preferably 15 to 50 parts by mass.

The wax (C) in a dispersed state used in the present invention
Is a component having an effect of improving the surface curability utilizing the air blocking effect. The wax is in a dispersed state and is finely divided, so that the air blocking effect is effectively exhibited. The wax (C) in a dispersed state is commercially available, for example, as a wax dispersed in an organic solvent. Examples of commercially available products of such a wax include BYK-LP-S6665 (trade name, manufactured by Big Chemie). The composition of the present invention can be prepared by directly adding the wax dispersed in the organic solvent. In this case, the composition of the present invention also contains an organic solvent, but the present invention is not limited to this, and contains no organic solvent, for example, a wax (A) in a (meth) acrylate monomer (A). The composition in which C) is dispersed may be used.

Component (C) is used in an amount of 0.01 based on a total of 100 parts by mass of components (A) and (B).
-0.5 parts by mass is preferred. When the wax dispersed in the organic solvent is added as it is, the total amount of the organic solvent and the wax (C) is 0.1 to 5 parts by mass based on 100 parts by mass of the components (A) and (B) in total. Parts are preferred.

Wax (C) dispersed in this organic solvent
In addition, it is also preferable to add a solid wax for the purpose of further improving the surface curability. Examples of the solid wax include paraffins, polyethylenes, higher fatty acids such as stearic acid, and the like.
Particularly, paraffin wax is preferable. The amount of the solid wax to be added is 100% in total from the component (A) and the component (B) from the viewpoint of the balance between the air curability and the physical properties of the cured product.
The amount is preferably from 0.1 to 5 parts by mass on the basis of parts by mass.

The acrylic syrup composition of the present invention may further contain, for example, a silane coupling agent, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, and a lubricant for the purpose of improving various properties. Various additives such as a release agent, a dye, a pigment, an antifoaming agent, a polymerization inhibitor, and a filler may be added.

As a method for curing the acrylic syrup composition of the present invention, a method of curing using a conventionally known redox catalyst system is preferable. Examples of the curing agent used here include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide and cumene hydroperoxide; and azo compounds such as diazobisisobutyronitrile. In particular, benzoyl peroxide is preferred from the viewpoint of low-temperature curability and short-time curability. This benzoyl peroxide is preferably used as an inert liquid or solid in the form of a solution, paste or powder diluted to a concentration of about 25 to 50% in order to avoid danger in handling.

The curing agent may be added before the syrup composition is cured. The addition amount of the curing agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the syrup composition from the viewpoint of the balance between curability, pot life and workability.

For the purpose of accelerating the curing reaction, a curing accelerator can be used if necessary. As the curing accelerator, N, N-dimethyl-p-toluidine, N,
N-di (2-hydroxypropyl) -p-toluidine,
Amines such as tri-n-butylamine, N-ethyl-N-hydroxyethylaniline, N, N-dimethylaniline; polyvalent metal catalysts such as cobalt naphthenate, cobalt octylate and cobalt acetoacetylate; and the like. . These may be used alone or in combination of two or more.

The curing accelerator may be added before the syrup composition is cured, or may be added to the syrup composition in advance. The amount of the curing accelerator added is preferably 0.1 to 100 parts by mass of the syrup composition from the viewpoint of the balance between curability, pot life and workability.
The amount is preferably from 05 to 10 parts by mass.

In curing the acrylic syrup composition of the present invention, it is particularly preferable to add benzoyl peroxide as a curing agent and amines as a curing accelerator.

Although the use of the acrylic syrup composition of the present invention is not particularly limited, it is suitable for uses such as a primer, a top coat, a flooring material, and a resin mortar. It is also preferable to use in combination with a reinforcing fiber for use as a reinforcing material for reinforcing / repairing materials for concrete structures.

For example, if a coating material is produced using the acrylic syrup composition of the present invention, the coating material has excellent low-temperature curability, weather resistance, and chemical resistance in addition to the inherent properties of the acrylic resin. It has low odor, excellent curability at normal and low temperatures, and excellent short-term workability. Such coatings are very useful for floors, walls and other various coatings.

Further, for example, the acrylic syrup composition of the present invention has excellent impregnation into reinforcing fibers, and therefore works very well as a matrix resin of a fiber reinforced material. Examples of the reinforcing fibers include carbon fibers, glass fibers, and organic fibers. Mixing and use of different types of reinforcing fibers is possible.

[0044]

The present invention will be described in more detail with reference to the following examples. In the following description, “parts” means “parts by weight” unless otherwise specified.
Means The evaluation of the examples and comparative examples was performed according to the following method.

<Evaluation Method> Odor: The odor at the time of blending the curing agent and the curing accelerator and at the time of construction was judged, and those with little monomer odor were marked with “○”, and those with large monomer odor were marked with “x”.

Impregnation: A carbon fiber sheet is placed on a 50 μm-thick polyethylene terephthalate film, and the syrup composition is reciprocated by two rollers from above the carbon fiber sheet and cured, and is the syrup composition permeating the film? Please observe from the film side, if the syrup composition has fully penetrated to the film side as `` ○ '',
A sample in which the penetration of the syrup composition into the film was not sufficient was rated "x".

Curability: 50 μm thickness at room temperature (20 ° C.)
The syrup composition is applied to a thickness of 300 μm on a polyethylene terephthalate film having a thickness of 300 μm using a wool roller (manufactured by Otsuka Brush Co., Ltd., trade name B-23), cured, and after 2 hours, the surface is tacky. , Observing the tackiness, and mark those without tackiness or tackiness as "○",
If there is a slight sticky or tacky feeling, it is called "△"
Those having stickiness or tackiness were rated "x".

Adhesive strength: A syrup composition was applied on a concrete plate from which latency was removed, and after curing, a carbon fiber sheet was stuck and cured using the same syrup composition. As the carbon fiber sheet, a carbon fiber sheet having a basis weight of 300 g / m ² using carbon fibers (manufactured by Mitsubishi Rayon Co., Ltd., trade name Pyrofil TR-30W) as warps and glass fibers and nylon as wefts at 5 mm intervals is used. did. The bonded sample was subjected to an adhesion test between concrete and a carbon fiber sheet in accordance with the Kenken-type tensile test method, and the adhesion strength (MPa) was determined. At the same time, a destruction state was also observed.

<Synthesis Example 1: Synthesis of urethane methacrylate oligomer (UM-1)> Stirrer, temperature controller,
In a container equipped with a condenser, carbonate diol (UH-CARB50, manufactured by Ube Industries, Ltd.) 50
2.7 parts, dimethylaminoethyl methacrylate 5.62
Part, 2,6-di-t-butyl-4-methylphenol (trade name Sumilyzer BHT, manufactured by Sumitomo Chemical Co., Ltd.)
1.12 parts, tetrahydrofurfuryl methacrylate 9
75.2 parts were added, and the mixture was heated to 50 ° C. with stirring. At a reaction temperature of 50 ° C., tolylene diisocyanate (trade name: Coronate T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) 34
8 parts were added dropwise over 3 hours, and 87 parts of tetrahydrofurfuryl methacrylate were further added and reacted for 1 hour. Then, 2-hydroxyethyl methacrylate 27
3 parts were added dropwise over 60 minutes, and 68.3 parts of tetrahydrofurfuryl methacrylate was further added. Then 95
When the reaction rate of the isocyanate group became 98% or more, the reaction was terminated and cooled. As a result, a urethane methacrylate oligomer (UM-1) containing 50% by mass of tetrahydrofurfuryl methacrylate was obtained.

<Synthesis Example 2: Synthesis of urethane methacrylate oligomer (UM-2)> In a container similar to that of Synthesis Example 1, 986.8 parts of carbonate diol (trade name: Kuraray polyol C-1090, manufactured by Kuraray Co., Ltd.) 8.04 parts of dimethylaminoethyl methacrylate, 2,6-di-t
-Butyl-4-methylphenol (Sumilyzer BH
T) 1.61 parts and 1395.4 parts of tetrahydrofurfuryl methacrylate were added, the mixture was heated to 50 ° C. while stirring, and 348 parts of tolylene diisocyanate (Coronate T-80) was added dropwise at a reaction temperature of 50 ° C. over 3 hours. Further, 87 parts of tetrahydrofurfuryl methacrylate were added and reacted for 1 hour. Next, 273 parts of 2-hydroxyethyl methacrylate was added dropwise over 60 minutes, and 68.3 parts of tetrahydrofurfuryl methacrylate was further added. Thereafter, the temperature was raised to 95 ° C., and when the reaction rate of the isocyanate group became 98% or more, the reaction was terminated. Further, 66.8 parts of tetrahydrofurfuryl methacrylate was added and cooled. As a result, a urethane methacrylate oligomer (UM-2) containing 50% by mass of tetrahydrofurfuryl methacrylate was obtained.

<Synthesis Example 3: Synthesis of urethane acrylate oligomer (UA-3)> In the same container as in Synthesis Example 1,
Polyisocyanate (Sumitomo Bayer Urethane Co., Ltd.)
331.6 parts of trade name Sumidur N3200), 0.132 part of dibutyltin dilaurate, 2,6-di-t-butyl-4-methylphenol (Sumilyzer BHT)
0.882 parts and 176.2 parts of 2-ethylhexyloxydiethylene glycol acrylate (trade name: Aronix M120, manufactured by Toagosei Co., Ltd.)
The mixture was heated to 0 ° C., 69.7 parts of 2-hydroxyethyl acrylate was added dropwise at a reaction temperature of 40 ° C. over 3 hours, and the reaction was further performed at 50 ° C. for 1 hour. Then 6
The mixture was heated to 5 ° C., and 303.4 parts of pentaerythritol triallyl ether (manufactured by Daiso, trade name Neoallyl P-30) was added dropwise over 2 hours at a reaction temperature of 65 ° C., and the reaction rate of the isocyanate group became 98% or more. At this point, the reaction was terminated and cooled. As a result, a urethane acrylate oligomer (UA-3) containing 20% by mass of 2-ethylhexyloxy polyethylene glycol acrylate was obtained.

<Synthesis Example 4: Synthesis of urethane methacrylate oligomer (UM-4)> In a container similar to Synthesis Example 1, hexamethylene diisocyanate trimer (Duranate TPA-100 manufactured by Asahi Kasei Kogyo Co., Ltd.) 10
86 parts, tetrahydrofurfuryl methacrylate 564
Parts, 0.47 parts of dibutyltin dilaurate, and 3.13 parts of 2,6-di-n-butyl-4-methylphenol (trade name Sumilyzer BHT-P, manufactured by Sumitomo Chemical Co., Ltd.), and with stirring. Heat to 40 ° C, and react at a reaction temperature of 40 ° C.
At ° C., 520 parts of 2-hydroxyethyl methacrylate were added dropwise over 3 hours. Thereafter, the temperature was raised to 65 ° C., and 587 parts of polyether polyol (trade name: Adeka polyether BPX-33, manufactured by Asahi Denka Kogyo KK) and 376 parts of tetrahydrofurfuryl methacrylate were added dropwise over 2 hours. When the temperature was raised, the reaction rate of the isocyanate group was 9
The reaction was terminated when the concentration reached 7% or more, followed by cooling. As a result, a urethane methacrylate oligomer containing 30% by mass of tetrahydrofurfuryl methacrylate (UM-
4) was obtained.

<Synthesis Example 5: Synthesis of Epoxy Methacrylate Oligomer (EM-5)> In a container similar to that of Synthesis Example 1, bisphenol A type epoxy resin (trade name: Epicoat 1055, manufactured by Yuka Shell Epoxy Co., Ltd.) 850 Department,
86 parts of methacrylic acid, 9.4 parts of dimethylaminoethyl methacrylate, 0.9 part of hydroquinone monomethyl ether
4 parts and 631 parts of tetrahydrofurfuryl methacrylate were added, and the mixture was heated to 90 ° C. and reacted until the acid value became 5 mgKOH / g or less. Then, 315 parts of tetrahydrofurfuryl methacrylate was added. As a result, an epoxy methacrylate oligomer (EM-5) containing 50% by mass of tetrahydrofurfuryl methacrylate was obtained.

<Synthesis Example 6: Synthesis of urethane methacrylate oligomer (UM-6)> Carbonate diol (UH-CARB50) 50 was placed in the same container as in Synthesis Example 1.
2.7 parts, dimethylaminoethyl methacrylate 5.62
, 2,6-di-t-butyl-4-methylphenol (Sumilyzer BHT) (1.12 parts) and 975.2 parts of methyl methacrylate were added, and the mixture was heated to 50 ° C with stirring, and tolylene was added at a reaction temperature of 50 ° C. 348 parts of isocyanate (Coronate T-80) were added dropwise over 3 hours, and 87 parts of methyl methacrylate were further added and reacted for 1 hour. Then, 2-hydroxyethyl methacrylate 27
3 parts were added dropwise over 60 minutes, and 68.3 parts of methyl methacrylate were further added. Thereafter, the temperature was raised to 95 ° C., and when the reaction rate of the isocyanate group became 98% or more, the reaction was terminated and cooled. As a result, a urethane methacrylate oligomer (UM-6) containing 50% by mass of methyl methacrylate was obtained.

<Examples 1 to 7 and Comparative Examples 1 to 4>
The components (A) to (C) and various other components were prepared at the compounding amounts shown in Table 2 and the odor, impregnation, and curability were evaluated. Furthermore, for those having good impregnation and hardening properties, a carbon fiber sheet was attached to a concrete plate, and the adhesion between the concrete and the carbon fiber sheet was evaluated. The results are shown in Tables 1 and 2. Since the oligomer obtained in each of the synthesis examples contains an acrylic monomer, the mass of the oligomer alone is shown in the column of the component (B) in Tables 1 and 2, and the acrylic contained in the oligomer is included. The mass of the monomer is shown in the column of the component (A).

[0056]

[Table 1]

[0057]

[Table 2]

The abbreviations in Tables 1 and 2 indicate the following compounds.・ THFMA: tetrahydrofurfuryl methacrylate [° C./kPa=75/0.4] ・ 2-HPMA: 2-hydroxypropyl methacrylate [° C./kPa=87/0.67] ・ 2-HBMA: 2-hydroxybutyl methacrylate DPHA: dipentaerythritol hexaacrylate ・ TMPTMA: trimethylolpropane trimethacrylate [° C./kPa=185/0.67] ・ acrylic ester PBOM: polybutylene glycol dimethacrylate (manufactured by Mitsubishi Rayon Co., Ltd.) ・ Aronix M111: nonylphenoxy Ethylene glycol acrylate (Toagosei Co., Ltd.) Aronix M120: 2-ethylhexyloxydiethylene glycol acrylate (Toagosei Co., Ltd.) BR-541: Acrylic resin (III Rayon Co., Ltd.
・ BR-599: Acrylic resin (Mitsubishi Rayon Co., Ltd.)
MMA: methyl methacrylate [° C / kPa = 29
/6.67]-BYK-LP-S6665: wax dispersed in an organic solvent (manufactured by BYK-Chemie, wax content 10%)-paraffin wax 115: paraffin wax (melting point 47 ° C, manufactured by Nippon Seiro Co., Ltd.) -Paraffin wax 130: Paraffin wax (melting point 55C, manufactured by Nippon Seiro Co., Ltd.)-Paraffin wax 150: paraffin wax (melting point 66C, manufactured by Nippon Seiro Co., Ltd.)-BHT: 2,6-di-t -Butyl-4-methylphenol (Sumitomo Chemical Co., Ltd.)-KBM-403: Silane coupling agent (Shin-Etsu Chemical Co., Ltd.)-Nipper NS: Benzoyl peroxide-containing emulsion (Nippon Oil & Fat Co., Ltd.) ) DIPT: N, N-di (hydroxypropyl) -p
-Toluidine-Naphtex Co8% T: Cobalt naphthenate (manufactured by Nippon Chemical Industry Co., Ltd.)-UM-1-2, 4, 6: Urethane methacrylate obtained in Synthesis Examples 1-2, 4, 6-UA-3: Urethane acrylate obtained in Synthesis Example 3 EM-5: Epoxy methacrylate obtained in Synthesis Example 5.

<Embodiment 8> At an ambient temperature of 23 ° C, Embodiment 1 was performed.
For 100 parts of the syrup composition, 2 parts of a benzoyl peroxide 40% product (manufactured by Nippon Oil & Fat Co., Ltd., trade name: Niiper NS) as a curing agent, and cobalt naphthenate (manufactured by Nippon Chemical Industry Co., Ltd.) Product name Naphtex C
o8% T) was added, and the concrete from which the latency was removed was coated with a wool roller (trade name: B-23, manufactured by Otsuka Brush Co., Ltd.) and left for 1 hour. The coating film after 1 hour had no tackiness. In addition, there was no problem of odor during blending and painting.

Next, the syrup composition 100 of Example 2
Parts, green pigment 3 parts, aggregate (Mitsubishi Rayon Co., Ltd.
400 parts of KM-17A (trade name), 2 parts of benzoyl peroxide 40% product (Niper NS), and 1 part of cobalt naphthenate (Naphtex Co 8% T) were added to prepare a flooring material. Coating was performed so as to have a thickness of 5 mm. There was no problem of odor at the time of mixing and construction, and there was no problem of curability 1 hour after coating.

Next, the syrup composition 100 of Example 3
Parts, green pigment 5 parts, benzoyl peroxide 4
2 parts of a 0% product (Niper NS) and 1 part of cobalt naphthenate (Naphtex Co 8% T) are added, and a wool roller (trade name: B-23, manufactured by Otsuka Brush Co., Ltd.) is placed on the floor material.
And left for 2 hours. The coating film after 2 hours had no tackiness. In addition, there was no problem of odor during blending and painting.

Example 9 At an environmental temperature of 0 ° C., the amount of benzoyl peroxide 40% (Niper NS) added to the syrup compositions of Examples 1 and 2 was 4 parts (Example 1), 3.5. (Example 2)
3 together with 1 part of cobalt naphthenate (Naphtex Co 8% T) as a curing accelerator to be added to the syrup composition of No. 3
1 part of N, N-dimethyl-p-toluidine (Example 1,
2), except that 0.75 parts (Example 3) were used in combination.
The blending and coating operations were performed in the same manner as in Example 8. In each operation, the same good results as in Example 8 were obtained.

[0063]

As described above, the acrylic syrup composition of the present invention has a low odor, cures in a short time even at a low temperature, has excellent workability, and has excellent mechanical properties. Is also excellent.

The coating material using the acrylic syrup composition has a low odor and a curability at room temperature and low temperature in addition to the inherent properties of an acrylic resin such as excellent low-temperature curability, weather resistance and chemical resistance. Excellent short-term workability.
Such coatings are very useful for floors, walls and other various coatings.

The reinforcing material for concrete using the acrylic syrup composition and the reinforcing fiber has excellent impregnating property of the acrylic syrup composition into the reinforcing fiber. Appears well in materials.

 ──────────────────────────────────────────────────続 き Continuing on the front page F-term (reference) 4G028 CA01 CB04 CC03 CD02 4J002 AE032 CD19W CH05W CK02W EF046 EH076 EK007 ET007 FD010 FD147 FD150 4J011 AA05 AA10 PA56 PA69 PA86 PA90 PA95 PB30 PB40 BA08 AG01BA02 BA11 CA10 CA31 CB04 CB09 CD02 4J100 AL08P AL08Q AL10P AL11P AL62P BA03P BA05P BA22Q BA39Q BB17P BC04P BC53P CA04 JA67

Claims (4)

[Claims] 1. 20 to 90 parts by mass of a (meth) acrylate monomer (A) having a boiling point of at least 75 ° C. at 6.67 kPa, 10 to 10 parts by weight of a polymer or radically polymerizable oligomer (B)
An acrylic syrup composition comprising 80 parts by mass and a wax (C) [100 parts by mass in total of the components (A) and (B)] in a dispersed state. 2. A (meth) acrylate monomer (A)
2. The acrylic syrup composition according to claim 1, wherein the main component is tetrahydrofurfuryl methacrylate. 3. The acrylic syrup composition according to claim 1, wherein the oligomer of the polymer or the radical polymerizable oligomer (B) is a urethane (meth) acrylate oligomer. 4. The acrylic syrup composition according to claim 4, wherein the urethane (meth) acrylate oligomer is a urethane (meth) acrylate oligomer comprising a polyol having a carbonate bond in the molecule.