JPH11106643A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition capable of being cured at the ordinary temperature, having excellent workability, little in curing contraction and useful for obtaining resin mortars and resin concrete. SOLUTION: This curable resin composition comprises 100 pts.wt. of a binder, and an inorganic filler and an aggregate in a total amount of 100-1200 pts.wt. The binder comprises a polymerizable liquid resin produced from (A) 30-90 pts.wt. of a urethane (meth)acrylate comprising an isocyanate compound component having three or more isocyanate groups in the molecule, a polyol component and a hydroxyl group-containing (meth)acrylate component, and (B) 70-10 pts.wt. (totally 100 pts.wt.) of a vinylic monomer capable of being copolymerized with the component A.

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, and more particularly, to a curable resin composition having good workability and room-temperature curability, and having a small curing shrinkage and capable of obtaining resin mortar and resin concrete. It relates to a resin composition.

[0002]

2. Description of the Related Art Various proposals have been made as binders for obtaining resin mortar and resin concrete. For example, Japanese Patent Publication No. Sho 62-12934 and Japanese Patent Publication No. Sho 62
JP-143916 discloses that an unsaturated polyester resin is used as a binder.
No. 90 and JP-A-54-36392,
The use of a polymerizable liquid resin containing a urethane (meth) acrylate obtained from a polyisocyanate and a hydroxyl group-containing (meth) acrylate as a binder is disclosed in JP-B-1-30777 and JP-B-3-3623. The use of a polymerizable liquid resin containing a (meth) acrylic acid partial ester of a polyhydric alcohol and another vinyl monomer as a binder is further disclosed in JP-B 1-3650.
No. 8 proposes to use a polymerizable liquid resin mainly composed of a vinyl monomer and a copolymer soluble or swellable therein as a binder.

However, there are the following disadvantages in the production of conventional resin mortar and resin concrete using the above-mentioned binder.

[0004] (1) When an unsaturated polyester resin is used as a binder, the viscosity becomes very high when an aggregate or the like is blended, so that a material having good fluidity cannot be obtained. And workability is inferior. In addition, since it has poor water resistance, it is restricted when used in civil engineering and construction applications where it is exposed outdoors.

(2) As a binder, a liquid resin containing a urethane (meth) acrylate obtained from a polyisocyanate and a hydroxyl group-containing (meth) acrylate has a high melting point, so that it hardens at a temperature below room temperature. The workability is restricted due to the formation of a precipitate.

(3) A binder made of a polymerizable liquid resin containing a (meth) acrylic acid partial ester of a polyhydric alcohol and another vinyl monomer is used in the same manner as the unsaturated polyester resin. It is inferior in property, and its strength is reduced by long-time contact with water, causing deterioration.

(4) When a polymerizable liquid resin containing a vinyl monomer and a copolymer soluble or swellable therein as a main component is used as the binder, the drawbacks of the above (1) to (3) occur. Can be almost eliminated, but the shrinkage during curing is large.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to eliminate the above-mentioned disadvantages, to provide good workability and curability, and to provide weather resistance. Another object of the present invention is to develop a curable resin composition which is capable of providing a resin mortar and a resin concrete having excellent water resistance and small curing shrinkage.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result,
It has been found that the above object can be achieved by using a polymerizable liquid resin containing urethane (meth) acrylate composed of a specific component, and the present invention has been achieved.

That is, the present invention relates to a curable resin composition comprising a binder, an inorganic filler and an aggregate, wherein the binder comprises an isocyanate compound component containing three or more isocyanate groups in one molecule, A polymerizable composition comprising 30 to 90 parts by weight of a urethane (meth) acrylate (A) composed of a polyol component and a hydroxyl group-containing (meth) acrylate component, and 70 to 10 parts by weight of a vinyl monomer (B) copolymerizable therewith. A curable resin which is a liquid resin (100 parts by weight in total), and is mixed with 100 to 1200 parts by weight of the inorganic filler and the aggregate in total with respect to 100 parts by weight of the binder. Resin composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention comprises a binder, an inorganic filler and an aggregate.

The binder used in the present invention comprises a urethane (meth) acrylate (A) comprising an isocyanate compound component having three or more isocyanate groups in one molecule, a polyol component and a hydroxyl group-containing (meth) acrylate component; It is a polymerizable liquid resin composed of this and a copolymerizable vinyl monomer (B).

In the present invention, examples of the isocyanate compound having three or more isocyanate groups in one molecule used for constituting the binder include a nurate modified form of isophorone diisocyanate, a buret modified form of hexamethylene diisocyanate, and a buret modified form of hexamethylene diisocyanate. Polyisocyanates such as trimethylolpropane adduct of tolylene diisocyanate, polymethylene polyphenyl polyisocyanate, and isocyanurate trimer of hexamethylene diisocyanate.

In the present invention, an isocyanate compound having two or more isocyanate groups in one molecule such as tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the above-mentioned polyisocyanate compound are combined, and It can be used in a range where the average isocyanate group is 3 or more.

The polyols used in the present invention include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3
-Butanediol, 1,4-butanediol, polytetramethylene glycol, polyether polyol, polyester polyol, polycarbonate diol, and the like can be mentioned, and may be selected from those having an average molecular weight of 300 or more according to required performance. preferable.

The hydroxy group-containing (meth) acrylate used in the present invention includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl. (Meth) acrylates having a hydroxyalkyl group such as (meth) acrylate, γ-butyrolactone ring-opened adduct to 2-hydroxyethyl methacrylate, ε-caprolactone ring-opened adduct to 2-hydroxyethyl acrylate, methacryl Ring-opening adduct of ethylene oxide to acid, ring-opening adduct of propylene oxide to methacrylic acid, 2-
(Meth) acrylic acid esters having a hydroxyl group at a terminal such as a dimer or trimer of hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate;
Examples thereof include polyethylene glycol monomethacrylate and polypropylene glycol monomethacrylate, and among them, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable. These can be used alone or in combination of two or more.

The ratio of the polyisocyanate / polyol / hydroxyl group-containing (meth) acrylate used in synthesizing the urethane (meth) acrylate (A) is adjusted so that the molar ratio of functional groups (NCO / OH) becomes 1/1. Is preferred, but it may be carried out in the range of 1 / 0.95 to 0.95 / 1.

For these syntheses, an inert solvent is added to the polyisocyanate, a catalyst such as di-n-butyltin dilaurate is added, and the temperature is raised to 40 to 80 ° C.
A method is used in which a hydroxyl group-containing (meth) acrylate and a polyol are successively added dropwise to the mixture while maintaining the temperature.
At this time, it is possible to use a vinyl monomer such as (meth) acrylate or styrene as the inert solvent. When an intentional molecular design method of the synthesized urethane (meth) acrylate is not required, the synthesis may be performed by adding an inert solvent and a catalyst to a hydroxyl group-containing component and gradually adding a polyisocyanate.

In the present invention, the molecular weight of the urethane (meth) acrylate (A) used is preferably in the range of 500 to 50,000, more preferably in the range of 1,000 to 20,000 in terms of weight average molecular weight measured by the GPC method. If the weight average molecular weight is small, the effect of reducing shrinkage during curing is reduced, and also, there is a tendency to decrease the physical properties of the cured product.On the other hand, if the weight average molecular weight is large, the viscosity is increased, and the workability tends to be deteriorated. Absent.

The vinyl monomer (B) copolymerizable with the urethane (meth) acrylate component used in the present invention includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. Acrylate, 2-ethylhexyl (meth) acrylate,
Monofunctional polymerizable monomers such as 4-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (meth) acrylate; ethylene glycol di (meth) acrylate; Alkanediol di (meth) acrylates such as 1,3-butylene glycol di (meth) acrylate, and polyoxyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate;
Further, polyfunctional polymerizable monomers such as tri- or more-valent (meth) acrylates and partial esters such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate are exemplified. These can be used alone or in combination of two or more.

In the present invention, the ratio of the urethane (meth) acrylate (A) used as the binder and the vinyl monomer (B) copolymerizable with the urethane (meth) acrylate is 30 to 40%. 10 to 70 parts by weight of the copolymerizable vinyl monomer (B) to 90 parts by weight (total 1 part)
00 parts by weight), preferably 30 to 70 parts by weight of the copolymerizable vinyl monomer (B) with respect to 30 to 70 parts by weight of the urethane (meth) acrylate (A) (total 1).
00 parts by weight). When the amount of the urethane (meth) acrylate used in the binder is less than 30 parts by weight, the effect of reducing shrinkage tends not to be sufficiently exerted,
On the other hand, if the amount exceeds 90 parts by weight, the viscosity increases, the workability is impaired, and the curability tends to be poor.

The curable resin composition of the present invention contains an inorganic filler and an aggregate.

Examples of the inorganic filler used in the present invention include, for example, calcium carbonate, aluminum hydroxide, silica, talc and the like. The particle size, shape, particle size distribution and the like of these inorganic fillers are not particularly limited, but preferably those having an average particle size of 1 μm or more and an oil absorption of 25 cc linseed oil / 100 g or less are 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. In the curable resin composition of the present invention, it is preferable to combine the inorganic filler and the aggregate such that the particle diameters are different from the viewpoint of coating workability and self-leveling property.

In the curable resin composition of the present invention, a silica powder such as asbestos or sebiolite aerosil may be added as a filler to impart thixotropic properties to the composition. 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, red bengal, ultramarine,
Cobalt blue, phthalocyanine blue, phthalocyanine green, and the like.

The total amount of the inorganic filler and the aggregate depends on the type and particle size thereof, the required performance of the curable resin composition using them, and the like.
The range is from 0 to 1200 parts by weight. This is because there is no compounding effect when the compounding amount of the inorganic filler and the aggregate is small,
On the other hand, if the amount is too large, the viscosity increases, the fluidity decreases, and the workability deteriorates.

In the curable resin composition of the present invention, a shrinkage reducing agent comprising a thermoplastic polymer can be used for the purpose of further suppressing shrinkage upon curing and obtaining a cured product having high dimensional stability. It is.

Examples of the thermoplastic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate , A polyalkyl (meth) acrylate obtained by polymerizing 2-ethylhexyl acrylate, polystyrene, a styrene-butadiene copolymer, a styrene-acrylonitrile copolymer, or other vinyl aromatic hydrocarbon as a monomer component. Polymers.

It is preferable that such a thermoplastic polymer can be dissolved or swelled in a polymerizable resin solution used as a binder, and has a glass transition temperature of 20 to 105 ° C. The proportion of the thermoplastic polymer used is 100
The amount is preferably 100 parts by weight or less, more preferably 30 parts by weight or less based on parts by weight. These thermoplastic polymers can be added as dissolved or swollen in the resin solution as needed, or can be blended in the same manner as the aggregate.

In the curable resin composition of the present invention, a plasticizer can be added according to the required performance. Examples of the plasticizer include, for example, di-2-ethylhexyl phthalate, phthalic acid esters such as dibutyl phthalate, adipic acid esters, dibasic fatty acid esters such as sebacic acid esters, polyethylene glycol, polypropylene glycol and the like. Examples which can be generally used as a plasticizer such as glycols can be given.

The use ratio of the plasticizer in the present invention cannot be unconditionally determined because the viscosity, development characteristics, compatibility and the like differ depending on the plasticizer, but is preferably 60 parts by weight or less with respect to 100 parts by weight of the binder. Preferably it is 30 parts by weight or less.

Although the curable resin composition of the present invention uses a polymerizable liquid resin as a binder, various paraffin waxes can be used for the purpose of improving the surface curability of these cured products. It is. As the paraffin wax, those having a melting point of 40 to 80 ° C can be used, and it is preferable to use two or more kinds of paraffin waxes having different melting points.

The amount of paraffin wax used is 5% by weight or less, preferably in the range of 0.3 to 1% by weight, based on the polymerizable liquid resin. Addition of more than 5% by weight of paraffin wax is not preferred because it tends to lower the compatibility of the resin and lower the adhesiveness when repeatedly applied to the cured product.

In order to cure the curable resin composition of the present invention, a resin catalyst based on a combination of a curing agent and a curing accelerator is used. Examples of the curing agent include benzoyl peroxide, t-butylperoxy 2-ethylhexanate, bis (4-t-butylcyclohexyl) peroxydicarbonate, cumene hydroperoxide, and methyl ethyl ketone peroxide. Examples of the curing accelerator include aromatic tertiary amines such as N, N-dimethylaniline and N, N-dimethyl-p-toluidine; and organic acid metal salts such as cobalt naphthenate, manganese naphthenate and nickel octylate. Can be used. These are used alone or in combination of two or more.

The amount of the curing agent added is 0.1 to the binder.
-15% by weight, preferably 0.5-10% by weight. If the amount is less than 0.1% by weight, poor curing tends to occur. On the other hand, if the amount exceeds 15% by weight, the pot life is shortened, the workability tends to be impaired, and the required physical properties tend not to be obtained. Because there is. The addition amount of the curing accelerator is in the range of 0.1 to 10% by weight, preferably 0.3 to 5% by weight, based on the binder. If the amount of addition is less than 0.1% by weight, accelerated curing tends not to occur, while if it exceeds 10% by weight, the pot life becomes extremely short, impairing workability or obtaining required physical properties. This is because there is a tendency that it cannot be performed. For this reason, the addition amount of the curing agent and the curing accelerator depends on the pot life of 20 to 6
It is preferable to add it so as to be 0 minutes.

[0035]

The present invention will be described more specifically with reference to the following examples and comparative examples. The percentages and parts in the following examples are based on weight unless otherwise specified. The evaluation of various physical properties in the following examples was based on the following methods.

(1) Viscosity The viscosity of the polymerizable resin solution was measured at 20 ° C. using a BM type viscometer (manufactured by Tokimec Co., Ltd.).

(2) Workability ：: Good iron coatability of resin concrete (iron is light). ×: Poor troweling property (heavy trowel, poor concrete separation from trowel).

(3) Curability The curable resin composition was allowed to stand at 0 ° C. for 90 minutes and at 20 ° C. for 60 minutes, and the presence or absence of surface tack was examined. ○: no tack △: slight tack ×: tack

(4) Flexural strength The flexural strength was measured according to JIS A1184.

(5) Compressive strength Measured in accordance with JIS A1183.

(6) Linear shrinkage due to curing Measured in accordance with JIS A1129.

Example 1 442.2 parts of polymethylene polyphenyl polyisocyanate (Millionate MR-400, manufactured by Nippon Polyurethane Industry Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, a temperature controller and a condenser.
Methyl methacrylate (hereinafter abbreviated as MMA) 281.
2 parts, 0.17 part of di-n-butyltin dilaurate (hereinafter abbreviated as DBTDL) as a catalyst and 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor (Sumitomo Chemical Co., Ltd.) Made, Sumilyzer BHT-
P) (hereinafter abbreviated as BHT-P) (1.12 parts) was added, heated to 40 ° C. while stirring, and, while maintaining this temperature, 2-hydroxyethyl methacrylate (hereinafter referred to as 2-H).
286.4 parts of EMA were added dropwise over 2 hours, and then the temperature was raised to 55 ° C. and reacted for 1 hour. Next, the temperature of the reaction product was raised to 65 ° C., and polyether polyol (Adeka polyether BPX-55, manufactured by Asahi Denka Kogyo KK) 3
95.0 parts were added dropwise over 1.5 hours. This is further heated to 75 ° C., and the reaction rate of the isocyanate group becomes 97%.
At this point, the reaction was terminated, cooled, and MMA 4
68.7 parts, paraffin wax 18.7 parts and N, N-dimethyl-p-toluidine (hereinafter abbreviated as DMTP) 9.4 parts as a polymerization accelerator are added, and a urethane acrylate having an oligomer content of about 60%. A polymerizable resin solution was obtained. The viscosity of this polymerizable resin solution is 550 cp
s (20 ° C.).

Next, 2 parts of benzoyl peroxide (pure content 50% by weight) as a curing agent was added to 100 parts of the polymerizable resin solution.
Formulated aggregate KM with calcium carbonate as inorganic filler and silica sand as aggregate at a ratio of 15/85 (parts by weight)
-2 parts (manufactured by Mitsubishi Rayon Co., Ltd.) was added to obtain a curable resin composition A. Table 1 shows the evaluation results of the physical properties of the curable resin composition A.

Example 2 In a reaction vessel similar to that in Example 1, an isocyanurate trimer of hexamethylene diisocyanate (TPA-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) was placed.
3.0 parts, MMA 326.2 parts, DBTDL as catalyst
0.13 parts and BHT-P as a polymerization inhibitor
30 parts were added, the mixture was heated to 40 ° C. with stirring, and 260.4 parts of 2-HEMA was added dropwise over 2 hours while maintaining this temperature, and then the temperature was raised to 55 ° C. and reacted for 1 hour. . Next, the temperature was raised to 65 ° C., and polyether polyol (Adeka Polyether BPX- manufactured by Asahi Denka Kogyo KK) was used.
100) 500.0 parts were added dropwise over 2 hours. The mixture was further heated to 75 ° C. and maintained at this temperature. When the conversion of the isocyanate groups became 97% or more, the reaction was terminated, and the mixture was cooled to obtain 543.7 parts of MMA, 21.7 parts of paraffin wax, and polymerization. DMPT 8.7 as accelerator
To obtain a urethane acrylate polymerizable resin solution having an oligomer content of about 60%. The viscosity of this polymerizable resin solution was 330 cps (20 ° C.).

Next, the same curing agent, inorganic filler and aggregate as in Example 1 were added to 100 parts of the polymerizable resin solution to obtain a curable resin composition B. Table 1 shows the evaluation results of the physical properties of the curable resin composition B.

Comparative Example 1 A polymethylene polyphenyl polyisocyanate (Millionate MR-40, manufactured by Nippon Polyurethane Industry Co., Ltd.) was placed in the same reaction vessel as in Example 1.
0) 442.2 parts, MMA 216.6 parts, DBTDL 0.09 part as catalyst and BHT as polymerization inhibitor
0.87 parts of -P was added, and the mixture was heated to 40 ° C with stirring, and while maintaining this temperature, 2-HEMA 423.
3 parts were added dropwise over 4 hours, then the temperature was raised to 65 ° C., and the reaction was continued. When the conversion of the isocyanate group became 97% or more, the reaction was terminated, cooled, and MMA 36
1.0 part, paraffin wax 14.4 parts, and DMPT 7.0 parts as a polymerization accelerator were added to obtain a urethane acrylate polymerizable resin solution having an oligomer content of about 60%. The viscosity of this polymerizable resin solution is 200 cps
(20 ° C.).

Next, the same curing agent, inorganic filler and aggregate as in Example 1 were added to 100 parts of the polymerizable resin solution to obtain a curable resin composition C. This curable resin composition C
Are shown in Table 1.

Comparative Example 2 In a reaction vessel similar to that in Example 1, diphenylmethane-4,4'-diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.)
250.0 parts, MMA 194.0 parts, DBT as catalyst
DL 0.08 part and BHT-P as polymerization inhibitor
Add 0.78 parts, heat to 40 ° C with stirring, add 130.2 parts of 2-HEMA dropwise over 2 hours while maintaining this temperature, and then raise the temperature to 65 ° C and react for 1 hour. I let it. Next, polyether polyol (Adeka polyether BPX-55, manufactured by Asahi Denka Kogyo KK) 39
5.0 parts were added dropwise over 3 hours. Further, at 75 ° C
The reaction was terminated when the reaction rate of the isocyanate groups reached 97% or more, cooled, and cooled to 323.4 parts of MMA and 12.9 parts of paraffin wax.
Parts and 5.2 parts of DMTP as a polymerization accelerator,
A urethane acrylate polymerizable resin solution having an oligomer content of about 60% was obtained. The viscosity of this polymerizable resin solution was 220 cps (20 ° C.).

Next, the same curing agent, inorganic filler and aggregate as in Example 1 were added to 100 parts of the polymerizable resin solution to obtain a curable resin composition D. This curable resin composition D
Are shown in Table 1.

[Comparative Example 3] A polymethylene polyphenyl polyisocyanate (Millionate MR-40, manufactured by Nippon Polyurethane Industry Co., Ltd.) was placed in the same reaction vessel as in Example 1.
0) 442.2 parts, MMA 97.9 parts, D as catalyst
0.17 parts of BTDL and BHT- as a polymerization inhibitor
P was added to the mixture, and the mixture was heated to 40 ° C. with stirring, and while maintaining this temperature, 2-HEMA 286.
4 parts were added dropwise over 2 hours, and then the temperature was raised to 55 ° C.
The reaction was performed for 1 hour. Next, the temperature was raised to 65 ° C., and 395.0 parts of polyether polyol (Adeka Polyether BPX-55, manufactured by Asahi Denka Kogyo KK) was added dropwise over 1.5 hours. The mixture was further heated to 75 ° C., and the reaction was terminated when the reaction rate of the isocyanate group became 97% or more. After cooling, 12.2 parts of paraffin wax and 5.0 parts of DMTP as a polymerization accelerator were added. A urethane acrylate polymerizable resin solution having an oligomer content of about 92% was obtained. The viscosity of this polymerizable resin solution is 9000 cp.
s (20 ° C.).

Next, 100 parts of the polymerizable resin solution was added to
The same curing agent, inorganic filler and aggregate as in Example 1 were added to obtain a curable resin composition E. Table 1 shows the evaluation results of the physical properties of the curable resin composition E.

Comparative Example 4 A polymethylene polyphenyl polyisocyanate (Millionate MR-40, manufactured by Nippon Polyurethane Industry Co., Ltd.) was placed in the same reaction vessel as in Example 1.
0) 442.2 parts, MMA 281.2 parts, DBTDL 0.17 part as catalyst and BHT as polymerization inhibitor
The mixture was heated to 40 ° C. while stirring, and with the temperature maintained, 2-HEMA 286.
4 parts were added dropwise over 2 hours, and then the temperature was raised to 55 ° C.
The reaction was performed for 1 hour. Next, the temperature was raised to 65 ° C., and 395.0 parts of polyether polyol (Adeka Polyether BPX-55, manufactured by Asahi Denka Kogyo KK) was added dropwise over 1.5 hours. The mixture was further heated to 75 ° C., the reaction was terminated when the reaction rate of the isocyanate group became 97% or more, and cooled to 4218.4 parts of MMA, 56.2 parts of paraffin wax and 21.50 parts of DMTP as a polymerization accelerator.
By adding 0 parts, a urethane acrylate polymerizable resin solution having an oligomer content of about 20% was obtained. The viscosity of this polymerizable resin solution was 60 cps (20 ° C.).

Next, 100 parts of the polymerizable resin solution was added to
The same curing agent, inorganic filler and aggregate as in Example 1 were added to obtain a curable resin composition F. Table 1 shows the evaluation results of the physical properties of the curable resin composition F.

Comparative Example 5 In a reaction vessel similar to that in Example 1, 40 parts of MMA, 20 parts of 2-ethylhexyl acrylate, 2 parts of ethylene glycol dimethacrylate, 10 parts of dioctyl phthalate (DOP), and an acrylic polymer (methyl methacrylate / n-butyl acrylate =
60/40 (weight ratio) copolymer, Mw = about 4000
0) 22 parts, paraffin wax 1.0 part, DMTP 0.6 part as a curing accelerator and hydroquinone 0.003 part as a polymerization inhibitor were charged, and heated at 60 ° C. for 3 hours to obtain a viscosity of 100 cps (20 ° C.). Was obtained.

Next, 100 parts of this polymerizable resin solution was added to
The same curing agent, inorganic filler and aggregate as in Example 1 were added to obtain a curable resin composition G. Table 1 shows the evaluation results of the physical properties of the curable resin composition G.

Comparative Example 6 In a reaction vessel similar to that of Example 1, 39 parts of MMA, 21 parts of 2-ethylhexyl acrylate, 2 parts of ethylene glycol dimethacrylate, 20 parts of a polyester plasticizer, and the acrylic polymer 23
Part, paraffin wax 0.8 part, D as curing accelerator
0.4 parts of MTP and 0.006 parts of hydroquinone as a polymerization inhibitor were charged and heated at 60 ° C. for 3 hours to obtain a polymerizable resin solution having a viscosity of 300 cps (20 ° C.).

Next, 100 parts of the polymerizable resin solution was added to
The same curing agent, inorganic filler and aggregate as in Example 1 were added to obtain a curable resin composition H. Table 1 shows the evaluation results of the physical properties of the curable resin composition H.

Comparative Example 7 Diphenylmethane-4,4'-diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) was placed in the same reaction vessel as in Example 1.
250.0 parts, MMA 120.2 parts, DBT as catalyst
DL 0.08 part and BHT-P as polymerization inhibitor
Add 0.78 parts, heat to 40 ° C. with stirring, add 260.4 parts of 2-HEMA dropwise over 4 hours while maintaining this temperature, and then raise the temperature to 55 ° C. and react for 1 hour. The reaction was terminated when the reaction rate of the isocyanate group became 97% or more, and 200.2 parts of MMA, 8.3 parts of paraffin wax, and DMTP as a polymerization accelerator
4.0 parts were added to obtain a urethane acrylate polymerizable resin solution having a viscosity of 150 cps (20 ° C.).

Next, 100 parts of the polymerizable resin solution was added to
The same curing agent, inorganic filler and aggregate as in Example 1 were added to obtain a curable resin composition I. Table 1 shows the evaluation results of the physical properties of the curable resin composition I.

[0060]

[Table 1]

[0061]

As is clear from the results of the above Examples and Comparative Examples, the curable resin composition of the present invention has good workability, low-temperature curability, and low shrinkage due to curing. Therefore, it can be suitably used for civil engineering and construction as resin mortar or resin concrete.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI (C04B 26/16 14:02)

Claims (1)

[Claims] 1. A curable resin composition comprising a binder, an inorganic filler, and an aggregate, wherein the binder has 3 per molecule.
30 to 90 parts by weight of a urethane (meth) acrylate (A) comprising an isocyanate compound component having at least two isocyanate groups, a polyol component and a hydroxyl group-containing (meth) acrylate component, and a vinyl monomer copolymerizable therewith (B ) 70 to 10 parts by weight of a polymerizable liquid resin (100 parts by weight in total), and 100 to 1200 parts by weight of the inorganic filler and the aggregate in a total amount of 100 parts by weight of the binder. A curable resin composition characterized by being blended.