JP2000026558A - Hardenable resin composition, and execution of waterproof agent and resin concrete using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rapidly hardenable resin composition excellent in coating properties at a normal temperature and a low temperature, and a hardened product by hardening the composition, and further to obtain a resin mortar or a concrete composition, having small temperature dependence and excellent balance of strength and elongation by using the resin composition. SOLUTION: This liquid resin composition comprises a urethane (meth) acrylate oligomer consisting essentially of (A) a polyfunctional isocyanate component, (B) a polyester polyol component, and (C) a hydroxy-containing (meth) acrylate oligomer, and a vinyl monomer copolymerizable therewith, in the proportion regulated so that the ratio of the urethane (meth)acrylate to the vinyl monomer may be (70/30)-(20/80). The resin mortar or the concrete is obtained by using the resin composition. The construction method thereof is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition which can be rapidly cured at normal temperature and low temperature, and a method of using the same.

[0002]

2. Description of the Related Art Conventionally, in the case of road bridges, viaducts, expressways, and various buildings, waterproofing is applied to concrete floorboards for the purpose of improving the durability. In general, as a material used for a waterproof layer of a concrete floorboard, a material such as a sheet system, a coating system, and a pavement system is mainly used.

A waterproofing method using a sheet material is a method of attaching an asphalt waterproof sheet formed by impregnating a synthetic fiber non-woven fabric with special asphalt to a floor plate,
Due to the excellent adhesion between the floorboard and the pavement and the excellent followability of the floorboard against cracks, it has been used extensively. However, this waterproofing method has problems in construction, such as the necessity of heating for asphalt melting at the time of sticking the sheet. On the other hand, in the case of a pavement system, the asphalt mixture can be easily applied with a normal pavement machine, but there are problems such as poor waterproof performance.

As a waterproofing method using a coating material, there are a synthetic rubber type (solvent type) in which synthetic rubber such as chloroprene is dissolved in a volatile solvent, an asphalt type (heat type) in which synthetic rubber is added to asphalt, and a modification. An epoxy resin-based material such as an epoxy resin is used. In each case, the concrete floorboard is repeatedly coated several times to form a waterproof layer. Waterproof coatings have the advantage that they can be applied regardless of changes in the shape of the coating, but on the other hand, when using synthetic rubber materials, for example, the solvent is volatilized to evaporate. In order to obtain the film, there are problems such as a long construction time, a deterioration in the working environment, and air pollution. Further, when an asphalt-based material is used, there is a fear of an accident such as a fire or a burn due to heating and melting. When a non-solvent epoxy resin waterproofing material is used, the curing time is extremely long, the crack followability is poor, and the workability due to the high viscosity of the resin is a problem.

[0005] Materials used as waterproof lining materials for concrete floors and the like in architectural applications are mainly epoxy resins, unsaturated polyester resins, vinyl ester resins, polyurethane resins, (meth) acrylate resins, and the like. Various curable resin compositions are used. Epoxy resins have excellent mechanical strength, but have problems such as a long curing time, poor acid resistance and hot water resistance, and poor flexibility without crack followability. The unsaturated polyester resin is excellent in acid resistance, but has a large curing shrinkage of the resin, and is inferior in crack followability like an epoxy resin. Vinyl ester resin
It is a resin with excellent chemical resistance and solvent resistance, and is used for various purposes in the field of anticorrosion. However, this resin is also difficult to follow concrete cracks like the above-mentioned epoxy resin. Have the following problems.

[0006] On the other hand, polyurethane resins are excellent in elasticity and flexibility, but have a long curing time and have problems in curing at low temperatures. Further, the (meth) acrylate resin is excellent in workability, weather resistance, and load resistance, but has a problem in elasticity.

As described above, in the prior art, each material has advantages and disadvantages, and it has not been sufficiently satisfactory as a material for waterproofing a concrete floor or the like and a method of applying the same. As a method for solving this problem, a waterproof material using a specific urethane acrylate is disclosed in Japanese Patent Application Laid-Open No. H8-30195.
No. 3, JP-A-8-31805, JP-A-9-911
No. 2,27639. However,
These urethane acrylates use polyoxyalkylene glycol as a main polyol component, and cannot achieve both the curability of the resin composition and the physical properties of the cured product such as strength, elongation and temperature dependency.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional technical problems, has good water resistance, is excellent in low-temperature flexibility, is excellent in following cracks of a concrete substrate, and has a load resistance. Curable resin composition which is excellent in water resistance and weather resistance, has rapid curability at room temperature and low temperature, has good coating workability, is suitable as a waterproof material for concrete floors, etc., its application method and curable resin composition The purpose of the present invention is to provide a resin mortar or resin concrete using the same.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a curable resin comprising a urethane (meth) acrylate synthesized from specific components and a polymerizable vinyl monomer. The resin composition is excellent in coating workability, quick-curing property, and low-temperature curability, and the cured resin is excellent in strength-elongation balance, and is required to have low-temperature flexibility. It has been found that the material is excellent as a material or a waterproof lining material, and the present invention has been completed.

That is, the present invention provides (A) a polyvalent isocyanate component, (B) a polyester polyol component, (C)
It contains a urethane (meth) acrylate oligomer (I) synthesized from a hydroxyl group-containing (meth) acrylate component and a vinyl monomer (II) copolymerizable therewith, and
The weight ratio (I / II) of the urethane (meth) acrylate oligomer (I) and the vinyl monomer (II) is 70 / 30-2.
0/80, which is a curable resin composition.

The present invention also relates to a method for applying a waterproof material using the above-mentioned curable resin composition as a waterproof lining material for concrete, and an application method for using a waterproof material between a concrete floor and a road pavement layer. Further, the present invention provides a construction method characterized in that various curable resin compositions and various kinds of inorganic fillers and aggregates are blended with the curable resin composition and the resulting composition is used as a resin mortar or concrete.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention comprises
Urethane (meth) acrylate oligomer (I) synthesized from (A) a polyvalent isocyanate component, (B) a polyester polyol component, and (C) a hydroxyl group-containing (meth) acrylate component, and a vinyl monomer copolymerizable therewith. Consists of body (II). In the description, the notation (meth) acrylate indicates methacrylate and / or acrylate, and the notation (meth) acrylic acid indicates methacrylic acid and / or acrylic acid.

In the present invention, the polyvalent isocyanate component (A) used for synthesizing the urethane (meth) acrylate oligomer (I) is a compound having two or more isocyanate groups in the molecule and is a known compound. Can be used. Examples of such isocyanate compounds include aromatic isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, and diisocyanates such as aliphatic isocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.
Also, isophorone diisocyanate, buret modified form of hexamethylene diisocyanate, nurate modified form,
Examples include triisocyanate compounds such as a modified form of isophorone diisocyanate and trivalent or higher polyvalent isocyanate compounds such as polymethylene polyphenyl polyisocyanate. These polyvalent isocyanate compounds may be used alone or in combination of two or more. Can be selected and used.

Among these, a diisocyanate compound is more preferred because of ease of intentional molecular design at the time of synthesizing the urethane (meth) acrylate oligomer. When yellowing or the like becomes a problem, the use of aliphatic isocyanates is preferred.

The polyester polyol component (B) comprises an acid component and an alcohol component, and the acid component includes aromatic dibasic acids such as phthalic acid (including terephthalic acid and isophthalic acid) and esters thereof. Exchange compounds, adipic acid, aliphatic dibasic acids such as sebacic acid and its transesterified compounds, aromatic dibasic acid anhydrides such as phthalic anhydride, aliphatic dibasic acid anhydrides such as maleic anhydride, and the like. it can. Of these, adipic acid and its transesterified compound, or adipic acid-based compounds such as adipic anhydride are preferred because of their excellent strength / elongation balance after curing of the resin composition. In particular, it is more preferable that the compound based on adipic acid accounts for 50% or more of the total acid components.

As the alcohol component which is a constituent component of the polyester polyol component (B), known alcohol components having a dihydric or higher alcoholic hydroxyl group can be used. Among them, ethylene glycol, propylene glycol, Diols composed of aliphatic hydrocarbons such as 4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, and cyclohexanedimethanol are preferred. In particular, diols having a main chain having 3 to 4 carbon atoms are more preferable. These alcohol components can be used as a mixture of two or more.

This polyester polyol component (B)
Is preferably selected from those having an average molecular weight of 600 or more according to the required performance. The more preferable average molecular weight of the polyester polyol is in the range of 1,000 to 2,000. When the average molecular weight of the polyester polyol is less than 600, the strength / elongation balance after curing of the synthesized resin composition cannot be maintained, and the intended flexibility cannot be exhibited.

In the present invention, in addition to the polyester polyol component (B), ethylene glycol,
Alkylene glycols such as propylene glycol,
Polyether polyols such as polyethylene glycol and polypropylene glycol can be used in combination.
These mixing ratios are not particularly limited,
The amount of the polyols other than the polyester polyol component (B) used is preferably within 30% by weight of the total polyol components.

The hydroxy group-containing (meth) acrylate component (C) includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
(Meth) acrylates having a hydroxyalkyl group such as -hydroxybutyl (meth) acrylate, γ-butyrolactone ring-opened adduct to 2-hydroxyethyl (meth) acrylate, and ε- to 2-hydroxyethyl (meth) acrylate Caprolactone ring-opening adduct, (meth)
Ring-opening adduct of ethylene oxide to acrylic acid, ring-opening adduct of propylene oxide to (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate dimer or 3
(Meth) acrylates having a hydroxyl group at a terminal such as a monomer, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate, and other components in the curable resin composition of the present invention. 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc. are particularly preferred from the viewpoint of compatibility and various physical properties. These components are 2
It is also possible to use a mixture of more than one species.

The molecular weight of the urethane (meth) acrylate oligomer (I) is preferably such that the weight average molecular weight measured by GPC is in the range of 1,000 to 50,000, more preferably in the range of 5,000 to 20,000. If the weight average molecular weight is less than 1,000, the distance between the crosslinking points of the cured product tends to be short, and sufficient flexibility tends not to be provided. On the other hand, if the weight average molecular weight exceeds 50,000, the distance between the cross-linking points of the cured product becomes large, and it becomes difficult to maintain the strength / elongation balance, or the viscosity increases,
It tends to sacrifice workability.

When synthesizing the urethane (meth) acrylate oligomer (I), the ratio of the polyvalent isocyanate component / polyol component + hydroxyl group-containing (meth) acrylate component is 1/1 as a functional group molar ratio (NCO / OH). Although it is preferable to set it as such, it may be in the range of 1 / 0.95 to 0.95 / 1.

As a method for synthesizing the urethane (meth) acrylate oligomer (I), an inert solvent is added to polyisocyanate, and a catalyst such as di-n-dilaurate is added.
A method in which hydroxyl group-containing (meth) acrylate and polyol are successively added dropwise while maintaining the temperature at 40 to 80 ° C. while adding an inert solvent and a catalyst to the hydroxyl group-containing component. And a method of gradually adding a polyisocyanate. At this time, a vinyl-based monomer such as (meth) acrylate or styrene can be used as the inert solvent.

The vinyl monomer (II) copolymerizable with the urethane (meth) acrylate oligomer (I) used in the present invention.
As, for example, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n
-Butyl methacrylate, i-butyl methacrylate,
The glass transition temperature (T) of a homopolymer such as t-butyl methacrylate, styrene, α-methylstyrene, etc.
g) a monofunctional polymerizable monomer exceeding 0 ° C., ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl (meth) acrylate,
Glass transition temperature (Tg) of 0 ° C. in the case of a homopolymer such as methoxyethyl acrylate, 2-hydroxyethyl acrylate, or 2-hydroxypropyl acrylate
The following monofunctional polymerizable monomers are exemplified. Use of a monofunctional polymerizable monomer having a glass transition temperature (Tg) of 0 ° C. or less within a range that does not affect the curability of the resin composition (the range varies depending on the monomer used) When the amount of the urethane (meth) acrylate oligomer (I) is constant, a more flexible cured product can be obtained. When a certain level of flexibility (flexibility) is maintained, the amount of the urethane (meth) acrylate oligomer (I) can be reduced, and the viscosity of the resin composition can be reduced.

If necessary, a polymerizable monomer having two or more polymerizable double bonds in the molecule may be added.
Examples thereof include alkanediol di (meth) acrylates such as ethylene glycol di (meth) acrylate and 1,3-butylene glycol di (meth) acrylate, and polyoxyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate. ) Acrylates, and polyfunctional polymerizable monomers such as tri- or higher-valent (meth) acrylates and partial esters such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate. These can be used alone or in combination of two or more.

In the present invention, the content ratio of the urethane (meth) acrylate oligomer (I) to the vinyl monomer (II) copolymerizable with the urethane (meth) acrylate oligomer (I) / vinyl monomer Body (II) = 70/30
２０20/80 weight ratio, preferably 60
/ 40 to 30/70. When the content of the urethane (meth) acrylate oligomer (I) exceeds 70% by weight, the viscosity of the curable resin composition increases, which affects the workability, and also increases the viscosity with the vinyl monomer (II). There is a case where the balance of copolymerizability is lost and a sufficiently cured product is not obtained.
When the content of the urethane (meth) acrylate oligomer (I) is less than 20% by weight, the effect imparted by the urethane (meth) acrylate oligomer (I) may not be sufficiently exhibited, and the vinyl monomer In some cases, the balance of copolymerizability with (II) is lost, resulting in insufficient cured product.

In the curable resin composition of the present invention, a thermoplastic polymer compound can be added in addition to the above.
Such a thermoplastic polymer compound has the effect of accelerating the apparent curing of the curable resin composition, the effect of suppressing and reducing shrinkage during curing, and the effect of adjusting the solution viscosity of the curable resin composition. Is added to Examples of the thermoplastic polymer compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl. Polyalkyl (meth) obtained by polymerizing (meth) acrylate
Examples thereof include vinyl copolymers containing a vinyl aromatic hydrocarbon as a monomer component such as acrylates, polystyrene, styrene-butadiene copolymer, and styrene-acrylonitrile copolymer. Such a thermoplastic polymer compound can be dissolved or swelled in a polymerizable resin solution used as a binder, and has a glass transition temperature (Tg) of 2 or more.
Those at 0 ° C to 105 ° C are preferred.

In the present invention, the content of the thermoplastic polymer compound is not limited, but is preferably 50 parts by weight or less, more preferably 20 parts by weight or less in 100 parts by weight of the curable resin composition. Is preferred.

It is also possible to add a plasticizer according to the required performance of the curable resin composition. Examples of the plasticizer include phthalic acid esters such as di-2-ethylhexyl phthalate and dibutyl phthalate, dibasic fatty acid esters such as adipic acid esters and sebacic acid esters, and glycols such as polyethylene glycol and polypropylene glycol. What can be generally used as a plasticizer can be used.

Although the content ratio of the plasticizer is not particularly limited, the characteristics of the curable resin composition such as viscosity, compatibility, flexibility (softening property), and transferability of the plasticizer differ depending on the plasticizer. Therefore, it cannot be said unconditionally, but it is preferable to use 20 parts by weight or less, more preferably 15 parts by weight or less in 100 parts by weight of the curable resin composition.

In the present invention, various paraffin waxes can be added for the purpose of improving the surface curability of the cured product obtained from the curable resin composition. As the paraffin wax, those having a melting point of 40 to 80 ° C can be used, and it is desirable to use two or more paraffin waxes having different melting points. They are,
5 parts by weight or less based on 100 parts by weight of the curable resin composition,
It is particularly desirable to use it in the range of preferably 0.3 to 1 part by weight. Addition of more than 5 parts by weight is not preferred because it may cause a problem in the compatibility of the resin composition and may lower the adhesiveness when the composition is repeatedly applied to the cured product.

As the curing agent used for curing the curable resin composition of the present invention, various known polymerization initiators and curing accelerators capable of performing radical polymerization can be used. Examples of such a polymerization initiator include benzoyl peroxide, t-butylperoxy 2-ethylhexanate, bis (4-t-butylcyclohexyl) peroxydicarbonate, cumene hydroperoxide, methyl ethyl ketone peroxide and the like. These are used in one kind or in a mixture of two or more kinds. Further, N, N-dimethylaniline, N, N
Aromatic tertiary amines such as -dimethyl-p-toluidine and metal soaps such as cobalt naphthenate, manganese naphthenate and nickel octylate can be used.

The addition amount of the curing agent is preferably in the range of 0.1 to 15% by weight. More preferably, it is in the range of 0.5 to 10% by weight. If the content is less than 0.1% by weight, poor curing tends to occur, and if the content exceeds 15% by weight, the pot life is shortened, the workability is impaired, or the required physical properties tend not to be obtained. Further, the addition amount of the curing accelerator is preferably in the range of 0.1 to 10%, more preferably in the range of 0.3 to 5% by weight. This is 0.1% by weight
If it is less than 10%, the accelerating effect tends not to be exhibited, and if it exceeds 10% by weight, the pot life becomes extremely short, and the workability tends to be impaired or the required physical properties tend not to be obtained. Usually, it is desirable to determine the amounts of the curing agent and the polymerization initiator to be added so that the pot life is 20 to 60 minutes. After these additions, the polymerization reaction starts immediately, and the curing of the curable resin composition proceeds.

The curable resin composition of the present invention can be used as a resin mortar and concrete by blending an inorganic filler and an aggregate. Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, silica, talc and the like. In the present invention, the particle size, shape, particle size distribution and the like are not particularly limited, but preferably the average particle size is 1 μm or more and the oil absorption is 25 ml.
Linseed oil / 100 g or less is desirable. Examples of aggregates include silica sand, quartz sand, colored porcelain, fired, hardened and crushed ceramics, glass beads, fine aggregates such as mountain sand and river sand, and coarse bones such as river gravel and crushed stone. Materials.
As the resin mortar or concrete, a combination of an inorganic filler having a relatively small particle size and an aggregate having a relatively large particle size having a different particle size is desirable for improving coating workability and self-leveling property.

In order to impart thixotropic properties to the composition, a silica powder such as asbestos, sebiolite, and aerosil can be added as a filler. In addition to the above, a coloring pigment or a dye can be used as a filler to supplement the appearance. For example, titanium oxide, barium sulfate, carbon black, chrome vermillion,
Bengala, ultramarine, cobalt blue, phthalocyanine blue, phthalocyanine green and the like are used.

The total amount of the inorganic filler and the aggregate in the curable resin composition of the present invention depends on the type and particle size thereof, and the required performance of the resin mortar and concrete composition using the same. Those which are 100 to 1200 parts by weight per 100 parts by weight of the curable resin composition are preferred. In the resin mortar or concrete composition of the present invention,
Increasing the content of the inorganic filler and the aggregate in the curable resin composition inevitably increases the viscosity and decreases the fluidity. Therefore, it is necessary that the appropriate compounding ratio is determined within the above range that does not impair workability.

The curable resin composition of the present invention can be used as a waterproof lining layer on concrete floorboards and piers of road bridges in the field of roads, and on floors of factories, warehouses and parking lots in the field of construction. Available as Further, the curable resin composition of the present invention mixed with various inorganic fillers, aggregates, and the like can also be used as a resin mortar or resin concrete.
In general, concrete refers to one using fine aggregate and coarse aggregate, and mortar refers to one using only fine aggregate.

[0037]

The present invention will be described in more detail with reference to the following examples. In the description, “%” is based on weight unless otherwise specified. [Production Example] (1) Production of urethane acrylate resin composition 1 In a container equipped with a stirrer, a temperature controller, and a condenser,
6000 parts (3 mol) of a polyester polyol composed of adipic acid and propylene glycol having an average molecular weight of 2,000, and methyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.)
1500 parts of dimethylaminoethyl methacrylate (trade name of “acrylester DM” manufactured by Mitsubishi Rayon Co., Ltd .; hereinafter, the same name of “acrylester DM”), 1500 parts, polymerization inhibitor 2,6-
Di-t-butyl-4-methylphenol (manufactured by Sumitomo Chemical Co., Ltd., trade name "Sumilyzer BHT-P" and the same)
6.94 parts were added, the mixture was heated to 60 ° C. with stirring, and tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate T-65” and below) 696.0 while maintaining this temperature. Parts (4 moles) were added dropwise over 1 hour, and then 174.0 parts of MMA were added. Thereafter, the reaction was further allowed to proceed at 60 ° C. for 2 hours. Thereafter, while maintaining this temperature, 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd .;
Abbreviated as EA. ) 241.5 parts (2.08 mol)
It was added dropwise over time and then 60.4 parts of MMA were added. The temperature was raised to 85 ° C., the reaction was terminated when the reaction rate of the isocyanate group became 98% or more, and cooled to 5244.7 parts of MMA, 2-ethylhexyl acrylate (manufactured by Mitsubishi Chemical Corporation; 3489.6 parts, paraffin wax 174.5 parts, polymerization accelerator (N, N-
Dimethyl-p-toluidine) was added to obtain a urethane acrylate resin composition 1 having an oligomer content of about 40%.

(2) Production of urethane acrylate resin composition 2 In a container equipped with a stirrer, a temperature controller and a condenser,
6000 parts (3 parts) of a polyester polyol composed of adipic acid and neopentyl glycol having an average molecular weight of 2,000
Mol), 1500 parts of MMA, 34.7 parts of dimethylaminoethyl methacrylate, 2,6-di-
6.94 parts of t-butyl-4-methylphenol were added,
The mixture was heated to 60 ° C. with stirring, and while maintaining this temperature, 696.0 parts (4 mol) of tolylene diisocyanate was added dropwise over 1 hour, and then MMA 174.0.
Parts were added. Thereafter, the reaction was further allowed to proceed at 60 ° C. for 2 hours. Thereafter, while maintaining this temperature, 2-HE
A241.5 parts (2.08 mol) was added dropwise over 1 hour, and then 60.4 parts of MMA was added. This is 85
When the reaction rate of the isocyanate group became 98% or more, the reaction was terminated.
4.7 parts, 2-ethylhexyl acrylate 3489.
6 parts, 174.5 parts of paraffin wax and 104.7 parts of a polymerization accelerator (N, N-dimethyl-p-toluidine) were added to obtain a urethane acrylate resin composition 2 having an oligomer content of about 40%.

(3) Production of urethane acrylate resin composition 3 In a container equipped with a stirrer, a temperature controller and a condenser,
6000 parts (3 moles) of a polyester polyol composed of adipic acid and propylene glycol having an average molecular weight of 2,000, 1500 parts of MMA, and dilauric acid
3.56 parts of n-butyltin and 7.12 parts of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor were added, and the mixture was heated to 60 ° C. while stirring, and the temperature was maintained. Then, 889.2 parts (4 mol) of isophorone diisocyanate (manufactured by Daicel Huls Co., Ltd.) was added dropwise over 1 hour, and then 222.3 parts of MMA was added. Thereafter, the reaction was further allowed to proceed at 60 ° C. for 2 hours. Thereafter, while maintaining this temperature, 241.5 parts (2.08 mol) of 2-HEA was added dropwise over 1 hour.
A60.4 parts were added. The temperature was raised to 85 ° C., and when the reaction rate of the isocyanate group became 98% or more, the reaction was terminated. After cooling, 5358.7 parts of MMA, 3570.7 parts of 2-ethylhexyl acrylate, and 178. 5 parts, polymerization accelerator (N, N-dimethyl-
(p-toluidine) (107.1 parts) was added to obtain a urethane acrylate resin composition 3 having an oligomer content of about 40%.

(4) Production of urethane acrylate resin composition 4 In a container equipped with a stirrer, a temperature controller and a condenser,
3,600 parts of polyester polyol having an average molecular weight of 2,000 consisting of adipic acid and propylene glycol (1.
8 mol), 2400 parts (1.2 mol) of a polyether polyol having an average molecular weight of 2000 (BPX-2000 (bisphenol A propylene oxide adduct), manufactured by Asahi Denka Kogyo KK), 1500 parts of MMA, dimethylaminoethyl as a catalyst 34.7 parts of methacrylate and 6.94 parts of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor were added, and the mixture was heated to 60 ° C. while stirring, and tolylenediene was maintained at this temperature. Isocyanate 6
96.0 parts (4 moles) were added dropwise over 1 hour, then
174.0 parts of MMA were added. Thereafter, the reaction was further allowed to proceed at 60 ° C. for 2 hours. Thereafter, while maintaining this temperature, 241.5 parts (2.08 mol) of 2-HEA was added to 1
It was added dropwise over time and then 60.4 parts of MMA were added. The temperature was raised to 85 ° C., and when the reaction rate of the isocyanate group became 98% or more, the reaction was terminated, and cooled to 5244.7 parts of MMA, 3489.6 parts of 2-ethylhexyl acrylate, and 174. 5
Part, polymerization accelerator (N, N-dimethyl-p-toluidine)
By adding 104.7 parts, a urethane acrylate resin composition 4 having an oligomer content of about 40% was obtained.

(5) Production of urethane acrylate resin composition 5 In a container equipped with a stirrer, a temperature controller and a condenser,
6000 parts (3 moles) of a polyester polyol consisting of adipic acid and propylene glycol having an average molecular weight of 2,000, 3,000 parts of MMA, 34.7 parts of dimethylaminoethyl methacrylate, and 2,6-di-t as a polymerization inhibitor
-Butyl-4-methylphenol (6.94 parts) was added, the mixture was heated to 60 ° C. while stirring, and 696.0 parts (4 moles) of tolylene diisocyanate was maintained at this temperature.
Was added dropwise over 1 hour, and then 174.0 parts of MMA was added. Thereafter, the reaction was further allowed to proceed at 60 ° C. for 2 hours. Thereafter, while maintaining this temperature, 2-HEA2
41.5 parts (2.08 mol) were added dropwise over 1 hour, and then 60.4 parts of MMA were added. The temperature was raised to 85 ° C., and when the reaction rate of the isocyanate group became 98% or more, the reaction was terminated, and cooled to obtain MMA28508.5.
9305.5 parts of 2-ethylhexyl acrylate,
465.3 parts of paraffin wax, polymerization accelerator (N, N
-Dimethyl-p-toluidine) 279.2 parts was added to obtain a urethane acrylate resin composition 5 having an oligomer content of about 15%.

(6) Production of urethane acrylate resin composition 6 In a container equipped with a stirrer, a temperature controller and a condenser,
6000 parts (3 moles) of a polyester polyol consisting of adipic acid and propylene glycol having an average molecular weight of 2,000, 3,000 parts of MMA, 34.7 parts of dimethylaminoethyl methacrylate, and 2,6-di-t as a polymerization inhibitor
-Butyl-4-methylphenol (6.94 parts) was added, the mixture was heated to 60 ° C. while stirring, and 696.0 parts (4 moles) of tolylene diisocyanate was maintained at this temperature.
Was added dropwise over 1 hour, and then 174.0 parts of MMA was added. Thereafter, the reaction was further allowed to proceed at 60 ° C. for 2 hours. Thereafter, while maintaining this temperature, 2-HEA2
41.5 parts (2.08 mol) were added dropwise over 1 hour, and then 60.4 parts of MMA were added. The temperature was raised to 85 ° C., and when the reaction rate of the isocyanate group became 98% or more, the reaction was terminated, and cooled to 592.0 parts of 2-ethylhexyl acrylate and 93.1 parts of paraffin wax.
Part, polymerization accelerator (N, N-dimethyl-p-toluidine)
By adding 55.9 parts, a urethane acrylate resin composition 6 having an oligomer content of about 75% was obtained.

(7) Production of urethane acrylate resin composition 7 In a container equipped with a stirrer, a temperature controller and a condenser,
6000 parts (3 mol) of a polyether polyol having an average molecular weight of 2,000 (manufactured by Asahi Denka Kogyo KK, BPX-2000 (bisphenol A propylene oxide adduct)),
1500 parts of MMA, 34.7 parts of dimethylaminoethyl methacrylate, and 6.94 parts of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor were added, and the mixture was heated to 60 ° C. while stirring and maintained at this temperature. In this state, 696.0 parts (4 mol) of tolylene diisocyanate was added dropwise over 1 hour, and then 174.0 parts of MMA was added. Thereafter, the reaction was further allowed to proceed at 60 ° C. for 2 hours. Thereafter, while maintaining this temperature, 2-HEA24
1.5 parts (2.08 mol) were added dropwise over 1 hour, then 60.4 parts of MMA were added. The temperature was raised to 85 ° C., and when the reaction rate of the isocyanate group became 98% or more, the reaction was terminated, cooled, and MMA5244.7 parts,
3489.6 parts of 2-ethylhexyl acrylate, 174.5 parts of paraffin wax, and 104.7 parts of a polymerization accelerator (N, N-dimethyl-p-toluidine) are added, and a urethane acrylate resin composition having an oligomer content of about 40%. 7 was obtained.

(8) Production of urethane acrylate resin composition 8 In a container equipped with a stirrer, a temperature controller and a condenser,
1,800 parts of polyester polyol having an average molecular weight of 2,000 consisting of adipic acid and propylene glycol (0.
9 mol), 4200 parts (2.1 mol) of a polyether polyol having an average molecular weight of 2,000 (BPX-2000 (bisphenol A propylene oxide adduct), manufactured by Asahi Denka Kogyo KK), 1500 parts of MMA, dimethylaminoethyl as a catalyst 34.7 parts of methacrylate and 6.94 parts of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor were added, and the mixture was heated to 60 ° C. while stirring, and tolylenediene was maintained at this temperature. Isocyanate 6
96.0 parts (4 moles) were added dropwise over 1 hour, then
174.0 parts of MMA were added. Thereafter, the reaction was further allowed to proceed at 60 ° C. for 2 hours. Thereafter, while maintaining this temperature, 241.5 parts (2.08 mol) of 2-HEA was added to 1
It was added dropwise over time and then 60.4 parts of MMA were added. The temperature was raised to 85 ° C., and when the reaction rate of the isocyanate group became 98% or more, the reaction was terminated, and cooled to 5244.7 parts of MMA, 3489.6 parts of 2-ethylhexyl acrylate, and 174. 5
Part, polymerization accelerator (N, N-dimethyl-p-toluidine)
By adding 104.7 parts, a urethane acrylate resin composition 8 having an oligomer content of about 40% was obtained.

(9) Reaction-curable acrylic resin composition 9
Production of methyl methacrylate 37 parts, 2-ethylhexyl acrylate 20 parts, ethylene glycol dimethacrylate 2 parts, polyester plasticizer 19 parts, MMA / n-BM
A (n-butyl methacrylate) = 60/40, acrylic polymer 22 having an average molecular weight of 40000 (trade name: acrylic bead resin BR-599, manufactured by Mitsubishi Rayon Co., Ltd.)
Part, paraffin wax 1.0 part, curing accelerator (N, N
-Dimethyl-p-toluidine), and 0.66 parts of 2,6-di-t-butyl-4-methylphenol as a polymerization inhibitor were charged and heated at 60 ° C. for 3 hours to give a viscosity of 30.
A resin composition 9 of 0 cps (20 ° C.) was obtained.

Evaluation of coating film [Examples 1 to 4], [Comparative Examples 1 to 5] The resin compositions obtained in the above Production Examples 1 to 9 have the viscosities at 20 ° C (B-type viscometer) shown in Table 1. It has the following resin liquid properties. These resin compositions were prepared at 20 ° C. and 0 ° C.
Under an atmosphere, a primer was applied on a concrete pavement plate, using a roller, and the workability and the curability were investigated. The results are shown in Table 1. In addition,
The amount of the curing agent and the like added at this time is 20% benzoyl peroxide 50% granules based on 100 parts of the resin composition (Cadox B-CH50, manufactured by Kayaku Akzo Co., Ltd.).
At 0 ° C., and 0.5 parts of N, N-dimethyl-p-toluidine and 6 parts of 50% benzoyl peroxide granules as curing accelerators per 100 parts of the resin composition. Was added.

[0047]

[Table 1]

With respect to the resin compositions obtained in Production Examples 1 to 9, dumbbell-shaped No. 1 test pieces were prepared in accordance with JIS K6301 at 20 ° C. and -10 ° C.
The strength, elongation, and elastic modulus were measured at a tensile speed of 20 mm / min. The results are shown in Tables 2 and 3.

[0049]

[Table 2]

[0050]

[Table 3]

Next, as an evaluation of low-temperature flexibility, the following bending test was performed. Each resin composition was applied to a steel sheet having a thickness of 0.5 mm to a thickness of 0.5 mm, cured, and then cured in a -10 ° C atmosphere for 4 hours. Thereafter, the steel plate was bent at 180 ° C. for 3 seconds on a 10 mm-diameter iron bar that had been cured at the same temperature, and the state of the coating film applied on the surface was examined. Table 4 shows the results.

[0052]

[Table 4]

Evaluation of Resin Mortar Formulation A resin composition prepared by mixing a resin composition with 100 parts by weight of a resin liquid and a curing agent or the like (trade name "KM- manufactured by Mitsubishi Rayon Co., Ltd.")
2)) After mixing and stirring 750 parts by weight, the curability and strength properties of the resin mortar were measured. The amount of the curing agent added is
At 20 ° C., 2 parts with respect to 100 parts of the resin composition, and at 0 ° C., with respect to 100 parts of the resin composition, 0.5 part of N, N-dimethyl-p-toluidine as a curing accelerator, and benzoyl peroxide Six parts of 50% granules were added. For the resin mortar, a specimen having a cross section of 40 mm square and a length of 160 mm was prepared according to JIS R5201, cured for one day after molding, and measured for flexural strength and compressive strength. The results are shown in Tables 5, 6, and 7.

[0054]

[Table 5]

[0055]

[Table 6]

[0056]

[Table 7]

The resin compositions of Examples 1 to 4 were coated on a primer-coated concrete pavement plate in an atmosphere of 20 ° C. and 0 ° C. to form a waterproof layer.
The workability, the leveling property, and the curability were excellent, and the waterproof performance and the base followability were also good. It has been confirmed that the resin composition of the present invention has rapid curing properties and, when used as a waterproof material, has excellent features.

In a 20 ° C. atmosphere, a resin mortar using the resin compositions of Example 1 and Comparative Example 5 was applied on a primer-coated concrete pavement plate to a thickness of 40 mm, and then applied at −10 ° C. (15 ° C.). Time) / + 40 ° C (9 hours)
When three cycles of cooling and heating were performed, the resin mortar of the comparative example caused cracks in the concrete pavement board, whereas the resin mortar of the present invention did not cause cracks in any of the base concrete pavement board and the resin mortar. I was not able to admit. This resin mortar was small in temperature dependency, and did not show a sharp increase in strength at the time of temperature decrease or a sharp decrease in strength at the time of temperature increase, and was confirmed to be excellent in crack resistance.

[0059]

The curable resin composition of the present invention is excellent in coating workability, rapid curability, and low-temperature curability, and the cured resin is excellent in the balance between strong and elongation, and can be used at low temperatures. It is possible to provide materials with excellent flexibility, waterproof roads and road bridges,
It can be used as resin mortar or resin concrete for waterproofing of construction fields such as factories and warehouses, parking lots, etc., which is very useful.

Continued on the front page F term (reference) 4J027 AG03 AG12 AG23 AG24 AG25 AJ01 BA05 BA07 BA08 BA10 BA19 BA24 BA26 CA11 CB03 CC01 CD08 4J038 DG111 DG112 DG261 DG262 FA121 FA122 FA151 FA152 FA281 FA282 KA08 NA04 NA11 NA12 NA23 PA18 PB05 PC04

Claims (7)

[Claims] 1. A polyvalent isocyanate component (A), (B)
It contains a urethane (meth) acrylate oligomer (I) synthesized from a polyester polyol component, (C) a hydroxyl group-containing (meth) acrylate component, and a vinyl monomer (II) copolymerizable therewith, and Urethane (meth) acrylate oligomer (I) and vinyl monomer (I
The weight ratio (I / II) with I) is 70/30 to 20/80.
A curable resin composition, characterized in that: 2. A copolymerizable vinyl monomer comprising: at least one vinyl monomer having a glass transition temperature of a homopolymer exceeding 0 ° C .;
The curable resin composition according to claim 1, comprising at least one kind of vinyl monomer having a temperature of not higher than 0C. 3. The curable resin composition according to claim 1, wherein 50% or more of the acid component constituting the polyester polyol (B) is an acid based on adipic acid. 4. The curable resin composition according to claim 1, wherein the number average molecular weight of (B) the polyester polyol is 600 or more. 5. A resin mortar or resin concrete comprising the curable resin composition according to claim 1 and an inorganic filler and / or an aggregate. 6. A method for constructing a waterproof material, comprising using the curable resin composition according to claim 1 as a waterproof lining material for concrete. 7. A construction method comprising using the curable resin composition according to claim 1 as a waterproof material for a road floor plate between a concrete floor plate and a road pavement material layer.