JPH11181035A - Hardening resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hardening resin composition capable of giving resin mortal or resin concrete excellent in workability, hardening properties and weather resistance, and having little or no hardening shrinkage. SOLUTION: This hardening resin composition is obtained by compounding a binding material, a shrinkage-lowering material, an inorganic filter and an aggregate. As the binding material, a polymerizing liquid resin comprising at least one kind of monomer component A selected from (meth)acrylic acid, (meth)acrylic esters and other vinyl monomers, and a resin B soluble in the monomer component A is used. As the shrinkage-lowering material, a polymer insoluble in the monomer component A and dilatable is used.

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 resin mortar or resin concrete which has good workability and room temperature curability and has small or no cure shrinkage. The present invention relates to a curable resin composition which can be used.

[0002]

2. Description of the Related Art Epoxy resins and urethane resins are widely used as civil engineering and architectural resins. However, these generally have problems such as a long curing time and a long working time, and they do not cure at low temperatures. On the other hand, Japanese Patent Publication No. 1-36508 discloses a polymerizable syrup using a vinyl-based monomer, which is characterized by being excellent in fast-curing property and low-temperature curability.

[0003] A resin mortar or resin concrete composition obtained by blending such a resin as a binder with an aggregate can be cured even at a low temperature of 0 ° C or less.
In addition, since it is superior in weather resistance and the like as compared with other resins, in recent years, it has been widely used not only in flooring materials but also in the field of civil engineering such as roads.

However, the composition for resin mortar or resin concrete has the above advantages,
Due to the large shrinkage of the resin itself during curing, the resin mortar or resin concrete has a disadvantage of lacking dimensional stability.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above circumstances, and has as its object to provide excellent workability, curability, weather resistance, and shrinkage during curing. It is an object of the present invention to provide a curable resin composition capable of obtaining a resin mortar and a resin concrete having a small or no curing shrinkage.

[0006]

Means for Solving the Problems As a result of extensive studies to achieve the above object, the present inventors have used a polymerizable liquid resin having a specific composition as a binder, It has been found that the above objects can be achieved by blending a low-shrink material, and the present invention has been achieved.

That is, the present invention provides a binder, a low-shrink material,
A curable resin composition containing an inorganic filler and an aggregate, wherein the binder is at least one kind of monomer selected from (meth) acrylic acid, (meth) acrylate and other vinyl monomers. A polymerizable liquid resin comprising a body component (A) and a resin (B) soluble in the monomer component (A), wherein the low-shrink material is insoluble and swellable in the monomer component (A) And a curable resin composition characterized by being a polymer.

[0008]

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

The binder used in the present invention comprises at least one monomer component (A) selected from (meth) acrylic acid, (meth) acrylic acid ester and another vinyl monomer, and the monomer Resin (B) possible for component (A)
And a polymerizable liquid resin.

In the present invention, the (meth) acrylic acid and (meth) acrylic acid ester used for constituting the monomer component (A) of the binder include, for example,
Acrylic acid, methacrylic acid, methyl (meth) acrylate (meaning acrylate or methacrylate, the same applies hereinafter), ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) Acrylate, alkyl (meth) acrylate such as t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-
Monofunctional polymerizable monomers such as hydroxybutyl (meth) acrylate; alkanediol di (meth) acrylates such as ethylene glycol di (meth) acrylate and 1,3-butylene glycol di (meth) acrylate; and diethylene glycol di ( Polyoxyalkylene glycol di (meth) acrylates such as meth) acrylates, and trivalent or higher (meth) acrylates and partial esters such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate. A polyfunctional polymerizable monomer is exemplified. Further, as other vinyl monomers, styrene, α-methylstyrene, vinyl ketone, t-butylstyrene, p-chlorostyrene,
Vinyl naphthalene and the like. These can be used alone or in combination of two or more.

In the present invention, examples of the resin (B) soluble in the monomer component (A) used for forming the binder include various vinyl polymers and other polymers. . Examples of the vinyl polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate,
Polyalkyl (meth) acrylate and alkyl (meth) acrylate copolymer obtained by polymerizing 2-ethylhexyl acrylate, etc., polystyrene, styrene-
Butadiene copolymers, vinyl copolymers having a vinyl aromatic hydrocarbon as a monomer component such as styrene-acrylonitrile copolymers, and further vinyl chloride- or vinyl acetate-based copolymers can be exemplified. . Such polymers preferably have a glass transition temperature (Tg) of 20 to 105 ° C. In the present invention, the content ratio of the resin (B) is not particularly limited, but is preferably 50 parts by weight or less, more preferably 30 parts by weight or less based on 100 parts by weight of the binder.

Examples of other polymers other than the above include unsaturated polyesters, epoxy (meth)
Various examples include reactive oligomers such as acrylates and urethane (meth) acrylates, macromonomers, and the like. In addition to these, if the monomer component (A) can be dissolved, the type is not particularly limited. Absent. In the present invention, the content ratio of such oligomers is not particularly limited, but is preferably 80 parts by weight or less, more preferably 60 parts by weight or less based on 100 parts by weight of the binder. These components (B) are factors that mainly affect various physical properties such as the viscosity and strength of the binder.

As the low-shrink material used in the present invention, a thermoplastic resin which is insoluble and swells in the monomer component (A) of the binder is used. Among thermoplastic resins, those generally referred to as thermoplastic elastomers and crosslinked vinyl polymers exhibit good shrinkage-reducing effects.

As the thermoplastic elastomer, for example,
Various types such as styrene type, vinyl chloride type, olefin type, polyester type, polyamide type, urethane type, etc. are listed, and they are used depending on the monomer component (A) of the binder used, the use situation and other required performance. Can be Monomer component (A)
It is desirable that the elastomer which is insoluble in water and swells has high flexibility in order to alleviate shrinkage. For example, when its physical property value is shown as an index, the flexural modulus (ASTM D790)
Is less than 980 MPa (1 × 10 ⁴ kg / cm ² ) or Izod (with a notch at 23 ° C.) impact strength (AS
Those satisfying either one of which does not break TM D256) are particularly effective in reducing shrinkage. Of these, polyester-based and olefin-based ones are particularly preferred.

The crosslinked vinyl polymer includes a styrene and / or acrylic monomer having one vinyl group in one molecule and a monomer having two or more vinyl groups in one molecule (crosslinked monomer). Agent) as a main component. Examples of the monomer having one vinyl group in one molecule include styrene, α-methylstyrene, vinyltoluene, pt-
Styrene monomer such as butylstyrene, methyl (meth)
Acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth)
Acrylate, i-butyl (meth) acrylate, t-
Monofunctional vinyls such as alkyl (meth) acrylates such as butyl (meth) acrylate, (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, and (meth) acrylic acid Examples include, but are not limited to, polymerizable monomers.

Examples of the monomer having two vinyl groups in one molecule include divinylbenzene, a reaction product of glycol and (meth) acrylic acid, for example, ethylene glycol di (meth) acrylate, 1,3- Alkanediol di (meth) acrylates such as butylene glycol di (meth) acrylate, polyoxyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin triacrylate Examples thereof include, but are not particularly limited to, trifunctional or higher valent (meth) acrylates such as (meth) acrylates and polyfunctional vinyl polymerizable monomers such as partial esters.

In order for the crosslinked vinyl polymer to be insoluble and swellable in the monomer component (A) of the binder, it is necessary to set an appropriate crosslink density. The amount of the cross-linking agent varies depending on the composition of the copolymer and the type of the cross-linking agent, but 0.1 to 100 parts by weight of the monomer having one vinyl group.
The addition of up to 5 parts by weight of a crosslinking agent is preferred. This is because when the amount of the crosslinking agent is less than 0.1 part by weight, a sufficient crosslinking effect is not exhibited and there is a tendency to dissolve, so that not only the low shrinkage effect cannot be sufficiently exhibited but also the workability tends to be reduced. On the other hand, the use of a crosslinking agent exceeding 5 parts by weight tends to reduce the swelling effect and fail to exert a sufficient shrinkage reduction effect.

The crosslinked vinyl polymer containing these as components is
It can be obtained using a usual known polymerization method. For example, there is no particular limitation on the production method, such as a method of pulverizing a polymer obtained by an emulsion polymerization method by an appropriate method, a method of obtaining a polymer by a suspension polymerization method, and the like.

The amount of the low-shrinkage material depends on the type and particle size, but is 1 to 40 parts by weight per 100 parts by weight of the binder.
More preferably, it is 2 to 20 parts by weight. If the compounding amount is less than 1 part by weight, the effect of reducing shrinkage in resin mortar or resin concrete is not sufficiently exhibited, and if it exceeds 40 parts by weight, there is a balance with a filler and an aggregate. It is not preferable because the physical properties of mortar and resin concrete tend to decrease.

Further, the low-shrinkage material has various particle sizes depending on the kind, and when it is used for resin mortar or resin concrete, the particle size is not particularly limited. However, due to the balance between the filler and the particle size of the aggregate,
The maximum particle size is preferably 2 mm or less, and more preferably those having an appropriate particle size distribution.

When these low-shrinkage materials are used as a composition for resin mortar and resin concrete, they may be already blended with the binder or may be blended with the binder at the work site. Further, it may be blended with an aggregate or a filler, and the method of blending the low shrinkage material is not particularly limited.

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 coloring pigment or a dye may be used as a filler, in addition to the above, to supplement the appearance. For example, titanium oxide, barium sulfate, carbon black, chrome vermillion, red iron, ultramarine, cobalt blue, phthalocyanine blue, phthalocyanine green, and the like can be given.

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 1500 parts by weight. This is because there is no compounding effect that the compounding amount of the inorganic filler and the aggregate is small, while if too large, the viscosity increases and the fluidity decreases,
This is because workability deteriorates.

Further, in the curable resin composition of the present invention, a plasticizer can be added in order to impart flexibility according to 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. Glycols, tricresyl phosphate, tributyl acetyl citrate and the like, as well as various butadiene and derivatives thereof, which can be generally used as a plasticizer, can be mentioned.

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 50 parts by weight or less based on 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 not more than 5% by weight, 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 the curable resin composition of the present invention, a silane coupling agent conventionally used can be added for the purpose of increasing the adhesiveness between the aggregate and the binder. As the silane coupling agent, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetylsilane, γ-methacryloxypropyltrimethoxysilane, and the like are preferable, and vinyltrichlorosilane and the like are also used. Is possible.

Further, in the curable resin composition of the present invention, an antifoaming agent for improving foam removal, a leveling agent for improving surface finish, and a thixotropic property for imparting thixotropic properties to the composition. , Sepiolite, silica powder such as Aerosil, etc. can also be used as an additive.

The addition of these additives varies depending on the type and required performance, and thus cannot be unconditionally determined. However, it is desirable to add 5 parts by weight or less based on 100 parts by weight of the binder.

As the curing agent for curing the curable resin composition of the present invention, various known curing agents and curing accelerators capable of performing radical polymerization are used. Examples of such a curing agent include benzoyl peroxide, t-butylperoxy 2-ethylhexanate, bis (4-t-butylcyclohexyl) peroxydicarbonate, cumene hydroperoxide, methyl ethyl ketone peroxide and the like. In addition, as a curing accelerator,
N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-di (hydroxyethyl) -p-toluidine and N, N-di (hydroxypropyl) -p-
Organic acid metal salts such as aromatic tertiary amines such as toluidine, 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 amount of the curing accelerator added is 0.1 to 10% by weight based on the binder,
Preferably it is in the range of 0.3 to 5% by weight. If the amount of addition is less than 0.1% by weight, the accelerating effect tends to be not exhibited, while if it exceeds 10% by weight, the pot life becomes extremely short, impairing workability or obtaining required physical properties. This is because it will not be possible. For this reason, it is preferable to add the curing agent and the curing accelerator so that the pot life is 20 to 60 minutes.

[0034]

EXAMPLES Hereinafter, Production Examples, Examples and Comparative Examples will be described.
The present invention will be described more specifically. The percentages and parts in the following examples are based on weight unless otherwise specified. Also,
Various physical property evaluations in the following examples were based on the following methods.

(1) Workability ：: There is no trace of the iron, and the iron is light. Δ: No trace of iron, but iron is heavy. ×: Irregularity of the iron occurred, and the iron separation was poor.

(2) Curability After the curable resin composition was left at 20 ° C. for 60 minutes, the presence or absence of surface tack was examined. ：: no tack. Δ: slightly tacky but hardened. ×: Tack or insufficient curing.

(3) Bending strength Measured according to JIS R5201.

(4) Compressive strength Measured according to JIS R5201.

(5) Linear shrinkage due to curing Measured according to JIS A1129.

[Production Example 1] Production of binder 1 In a reaction vessel equipped with a cooler, 975 parts of methyl methacrylate (hereinafter abbreviated as MMA), 4-dimethyl 6-
Five parts of t-butylphenol were charged, and 2,000 parts of an epoxy resin having a molecular weight of 1600 and an epoxy equivalent of 925 based on bisphenol A and epichlorohydrin was added little by little with stirring. After the reaction vessel was heated and the epoxy resin was completely dissolved in MMA at an internal temperature of 70 ° C., 27 parts of triethylamine was added. Next, the temperature of the reaction vessel was raised to 80 ° C., and a mixture of 112 parts of methacrylic acid and 130 parts of lauric acid was dropped over 2 hours. The reaction was carried out for 8 hours while maintaining the internal temperature at 80 ° C., followed by cooling. To this was added 250 parts of MMA to obtain an epoxy methacrylate-containing resin having an acid value of 4. 68 parts of this resin, MMA31
Parts, paraffin wax having melting points of 47 ° C. and 55 ° C.
5 parts and 1 part of N, N-dimethyl-p-toluidine (hereinafter abbreviated as DMPT) as a polymerization accelerator were charged into a vessel equipped with a cooler and dissolved at 60 ° C. for 2 hours. This was cooled to obtain a binder 1 composed of a polymerizable liquid resin having a viscosity of 270 cps (20 ° C.).

[Production Example 2] Production of binder 2 35 parts of MMA, 2-ethylhexyl acrylate 23
Parts, ethylene glycol dimethacrylate 2 parts, dioctyl phthalate 10 parts, acrylic polymer [methyl methacrylate / n-butyl methacrylate (MMA / n
-BMA) = 70/30, Mw = 30000] 30 parts,
Melting point 47 ° C and 55 ° C paraffin wax total 0.8
Parts, 0.6 parts of DMPT as a curing accelerator and 0.004 parts of hydroquinone as a polymerization inhibitor were charged into a reaction vessel equipped with a cooler, and heated at 60 ° C. for 3 hours to give a viscosity of 200 cp.
A binder 2 made of a polymerizable liquid resin having a s (20 ° C.) was obtained.

[Production Example 3] Production of binder 3 84 parts of MMA, 0.5 parts of butylene glycol dimethacrylate, 0.5 parts of dioctyl phthalate, acrylic polymer [methyl methacrylate / methyl acrylate (MMA / MA) = 99/1] , Mw = 100000] 5
Parts, 10 parts of tricresyl phosphate, 0.3 parts of paraffin wax having a melting point of 47 ° C. and 55 ° C., and D as a curing accelerator
1.5 parts of MPT, 0.1 part of hydroquinone as a polymerization inhibitor.
005 parts was charged into a reaction vessel and heated at 60 ° C. for 3 hours to obtain a binder 3 composed of a polymerizable liquid resin having a viscosity of 20 cps (20 ° C.).

[Production Example 4] Low shrinkage material Production of crosslinked vinyl polymer T-3 80 parts of styrene, 2-ethylhexyl acrylate 20
Part, 1,3-butylene glycol dimethacrylate 1
Parts, water 200 parts, benzoyl peroxide (pure content 75%) 1
Parts, polyvinyl alcohol (degree of saponification 80
%, Degree of polymerization 1700) was charged into a reaction vessel having a cooling tube and stirred at 85 ° C for 3 hours, and then further stirred at 95 ° C.
The mixture was stirred for 2 hours and cooled. The obtained product was dehydrated and dried in a dryer at 50 ° C. for 24 hours to obtain a crosslinked vinyl polymer T-3. The particle size of this polymer was 300 μm, which was insoluble in MMA and swelled.

[Examples 1 to 3 and Comparative Examples 1 to 3] To 100 parts of the binder 1 obtained in the above Production Example 1, 2 parts of benzoyl peroxide (50% pure content) was mixed as a curing agent, and then A mixed aggregate K obtained by mixing calcium carbonate as an inorganic filler and silica sand as an aggregate in a ratio of 15/85 (parts) to this mixture.
746 parts of M-2 (manufactured by Mitsubishi Rayon Co., Ltd.) and 4 parts of a resin component shown in Table 1 and a low-shrink material having physical properties are added, mixed and stirred to obtain a curable resin composition for resin mortar. Obtained. Table 2 shows the evaluation results of the physical properties of the curable resin composition.

[Comparative Example 4] Binder 11 obtained in Production Example 1
To 2 parts of the curing agent of Example 1, 2 parts of the curing agent of Example 1 are mixed. Then, 750 parts of the mixed aggregate of Example 1 is added to the mixture, mixed, stirred, and cured for a resin mortar not containing a low-shrink material. A resin composition was obtained. Table 2 shows the evaluation results of the physical properties of the curable resin composition.

[0046]

[Table 1]

[0047]

[Table 2]

[Examples 4 and 6, Comparative Examples 5 and 7] Production Example 2
2 parts of the curing agent of Example 1 were mixed with 100 parts of the binder 2 obtained in the above, and then the mixed aggregate 74 of Example 1 was added to the mixture.
6 parts and 4 parts of the resin component shown in Table 1 and the low-shrink material having physical properties were added, mixed and stirred to obtain a curable resin composition for resin mortar. Table 3 shows the evaluation results of the physical properties of the curable resin composition.

[Comparative Example 8] Binder 2 obtained in Production Example 2
To 100 parts, 2 parts of the curing agent of Example 1 are mixed. Then, 750 parts of the mixed aggregate of Example 1 is added to the mixture, and the mixture is mixed and stirred to obtain a resin mortar containing no shrinkage reducing material. A curable resin composition was obtained. Table 3 shows the evaluation of the physical properties of the curable resin composition.

[0050]

[Table 3]

[Examples 7 to 9 and Comparative examples 9 to 11] To 100 parts of the binder 2 obtained in Production example 2, 2 parts of the curing agent of Example 1 were mixed. Mixed aggregate 7
42 parts and the resin components shown in Table 1 and 8 parts of a low-shrink material having physical properties were added, mixed and stirred to obtain a curable resin composition for resin mortar. Table 4 shows the evaluation results of the physical properties of the curable resin composition.

[0052]

[Table 4]

Examples 10 to 12 and Comparative Examples 12 to 14
To 120 parts of the binder 3 obtained in Production Example 3, 6 parts of the curing agent of Example 1 were mixed, and then the mixture was mixed with a mixed aggregate (calcium carbonate / silica sand / = 20/80 (%)) 875.
Parts and a resin component shown in Table 1 and 5 parts of a low-shrink material having physical properties were added, mixed and stirred to obtain a curable resin composition for resin concrete. Table 5 shows the evaluation results of the physical properties of the curable resin composition.

[Comparative Example 15] Binder 3 obtained in Production Example 3
To 120 parts, 6 parts of the curing agent of Example 1 were mixed.
To this mixture was added 880 parts of the mixed aggregate of Example 10,
By mixing and stirring, a curable resin composition for resin concrete containing no shrinkage reducing material was obtained. Table 5 shows the evaluation results of the curable resin composition.

[0055]

[Table 5]

[0056]

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. Alternatively, since there is no shrinkage due to curing, a resin mortar and resin concrete having excellent dimensional stability can be provided.

Claims (3)

[Claims] 1. A curable resin composition containing a binder, a low-shrinkage material, an inorganic filler and an aggregate, wherein the binder is (meth) acrylic acid, (meth) acrylate and another vinyl. A polymerizable liquid resin comprising at least one monomer component (A) selected from a series of monomers and a resin (B) soluble in the monomer component (A); A curable resin composition, which is a polymer that is insoluble and swellable in the monomer component (A). 2. The resin (B) soluble in the monomer component (A) is at least one selected from unsaturated polyesters, urethane (meth) acrylates, epoxy (meth) acrylates and vinyl polymers. The curable resin composition according to claim 1, wherein: 3. The curable resin according to claim 1, wherein the polymer insoluble and swellable in the monomer component (A) is at least one selected from a thermoplastic elastomer and a crosslinked vinyl polymer. Composition.