JP5128379B2 - Formulation and cured product thereof - Google Patents

Description

  The present invention relates to a low-temperature sensitive composition suitable for resin mortar or resin concrete for civil engineering and construction, and a cured product thereof.

Conventionally, a curable composition containing a vinyl monomer having an alicyclic structure and a methacrylic polymer having a number average molecular weight of 1,000 to 20,000 in a civil engineering building coating (see, for example, Patent Document 1). ) And a resin composition containing a (meth) acrylic polymer having a polymerizable double bond and a polymerizable monomer (for example, see Patent Document 2).
JP 2002-114830 A JP 2002-020440 A

Specifically, in Production Example 1 of Patent Document 1, methyl methacrylate, n-butyl acrylate, and acrylic acid are polymerized to obtain vinyl polymer B-1, and the vinyl polymer B-1 and glycidyl methacrylate are obtained. To obtain a methacryloyl group-containing vinyl polymer C-1, and a mixture of the methacryloyl group-containing vinyl polymer C-1, dicyclopentenyloxyethyl methacrylate, trimethylolpropane triacrylate, and paraffin wax. Although D-1 is described, since the composition has a high viscosity, the coating workability is poor, and the strength of the cured product is inferior.
In Synthesis Example 1 of Patent Document 2, a polymer is obtained by polymerizing methyl methacrylate and methacrylic acid, and a polymer is obtained by esterifying glycidyl methacrylate to the obtained polymer. Although methacrylic syrup (1) to which tert-butyl methacrylate and a wax are added is described, the methacrylic syrup has a high viscosity, so that the coating workability is poor. In addition, when the viscosity of syrup is high, the coating workability of a blend in which aggregate is blended with syrup is also poor.

  The object of the present invention is that the viscosity of the syrup is low, the coating workability when the aggregate is mixed with the syrup is good, the strength when the cured product is high, and the strength change of the cured product from low temperature to high temperature Is in a formulation with a small and a cured product thereof.

The present invention includes the following aspects.
[1] Methyl methacrylate monomer (A) 60 to 85% by mass and an alkyl (meth) acrylate unit or cycloalkyl (meth) acrylate unit having an alkyl group having 2 or more carbon atoms and a double bond 100 parts by mass of syrup (X) containing 15-40% by mass of polymer (B) and 100 parts by mass of syrup composition (L) containing 0.1-5 parts by mass of wax (C), A blend comprising 400 to 1500 parts by mass of aggregate.
[2] The blend according to [1], wherein the polymer (B) has an alkyl methacrylate unit having 2 to 4 carbon atoms or an isobornyl (meth) acrylate unit.
[3] Addition of 0.5 to 10 parts by mass of organic peroxide to 100 parts by mass of the syrup (X) in the compound described in [1] to [2] and curing. The strength at 20 ° C. is a bending strength: 10 N / mm ² or more, compressive strength: 15 N / mm ² or more, and (strength at 20 ° C.−strength at 80 ° C.) / 20 ° C. Hardened | cured material which is below 0.5.

The blend of the present invention has a low viscosity of syrup (X), good kneadability when mixing aggregates, and is excellent in coating workability and material uniformity in a state where aggregates are blended.
The cured product of the blend of the present invention has high strength, high strength even from low temperature to high temperature, small strength change due to temperature, and stable physical properties.
When the composition of the present invention is applied, a cured product having high strength, high strength from low temperature to high temperature, small fluctuation in strength due to temperature change, and excellent strength stability can be obtained in a short time. .

  The syrup (X) in the present invention has a methyl methacrylate monomer (A) and an alkyl (meth) acrylate unit or cycloalkyl (meth) acrylate unit having an alkyl group having 2 or more carbon atoms and a double bond. A polymer (B).

<Methyl methacrylate monomer (A)>
By using the methyl methacrylate monomer (A), the viscosity of the syrup (X) becomes sufficiently low, not only the kneading property with the aggregate is improved, but also the coating workability is improved.
The content of the methyl methacrylate monomer (A) in the syrup (X) is 60 to 85% by mass. When the content is 60% by mass or more, the viscosity is sufficiently low, and the kneadability with the aggregate and the coating workability of the blend are improved. When the content is 85% by mass or less, good curability can be obtained. A more preferable range of the content of the methyl methacrylate monomer (A) is 65 to 85% by mass, and 70 to 82% by mass is more preferable.

<Acrylic monomer (D) other than monomer (A)>
The syrup (X) can contain an acrylic monomer (D) other than methyl methacrylate as long as the low viscosity of the syrup and the physical property stability of the cured product are not impaired. The acrylic monomer (D) is one or both of a monofunctional acrylic monomer (D1) and a polyfunctional acrylic monomer (D2).
The monofunctional acrylic monomer (D1) here is a (meth) acrylate (excluding methyl methacrylate) having only one (meth) acryloyl group, and a polyfunctional acrylic monomer (D2). Is a (meth) acrylate having two or more (meth) acryloyl groups. In the present invention, “(meth) acrylate” means “acrylate” and / or “methacrylate”, and “(meth) acryloyl group” means “acryloyl group” and / or “methacryloyl group”.

  Specific examples of the monofunctional acrylic monomer (D1) include ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylic acid alkyl esters such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Hydroxyl group-containing (meth) acrylates; nitrogen-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meta) such as tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate Acu Rate and the like. These may be used alone or in combination of two or more.

  Specific examples of the polyfunctional acrylic monomer (D2) include alkanes such as ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. Diol di (meth) acrylate; polyoxyalkylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate; neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid tris [ethyloxy (meth) Acrylate, trifunctional or more (meth) acrylic acid ester or a partial ester of such glycerin tri (meth) acrylate; and the like. These may be used alone or in combination of two or more.

  When syrup (X) contains acrylic monomers (D) other than methyl methacrylate, the content is preferably more than 0 to 15% by mass, more preferably more than 0 to 10% by mass.

<Polymer (B)>
The polymer (B) is a polymer having an alkyl (meth) acrylate unit or a cycloalkyl (meth) acrylate unit having an alkyl group having 2 or more carbon atoms and having a double bond. The polymer (B) is a component that imparts curability and imparts strength to the cured product. The double bond in the polymer (B) is a double bond involved in a radical polymerization reaction, and examples of the functional group having such a double bond include a vinyl group, an allyl group, and a (meth) acryloyl group. .
Both the alkyl (meth) acrylate unit and cycloalkyl (meth) acrylate unit having an alkyl group having 2 or more carbon atoms contribute to the low viscosity of syrup (X) and the high strength of the cured product at high temperature. This is considered to be involved in the effects of the present invention.

As a monomer constituting the polymer (B), at least one of alkyl (meth) acrylate (B1) or cycloalkyl (meth) acrylate (B2) having an alkyl group having 2 or more carbon atoms is essential, Other examples include the aforementioned methyl methacrylate, other monofunctional acrylic monomers, polyfunctional acrylic monomers, (meth) acrylic acid, and the like.
As the monomer (B1), ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate etc. are mentioned. Among these, an alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms is preferable in that the glass transition temperature of the polymer (B) is high and the viscosity when the syrup (X) is reduced. In particular, i-butyl methacrylate, t-butyl methacrylate, and sec-butyl methacrylate are preferable. The monomer (B1) may be used alone or in combination of two or more.
Examples of the monomer (B2) include isobornyl (meth) acrylate and cyclohexyl (meth) acrylate. In particular, isobornyl (meth) acrylate is preferred in that the polymer (B) has a high glass transition temperature and can reduce the viscosity when it is made into syrup (X). The monomer (B2) may be used alone or in combination of two or more.

As the monomer constituting the polymer (B), it is preferable to use another acrylic monomer (B3) not included in any of the above (B1) and (B2). That is, the polymer (B) preferably has an acrylic unit that is not included in any of the alkyl (meth) acrylate unit having an alkyl group having 2 or more carbon atoms and the cycloalkyl (meth) acrylate unit. . As another acrylic monomer (B3), methyl methacrylate, glycidyl (meth) acrylate, or (meth) acrylic acid is preferable.
As monomers constituting the polymer (B), alkyl methacrylate having 2 to 4 carbon atoms and / or isobornyl (meth) acrylate, methyl methacrylate, glycidyl (meth) acrylate, and (meth) acrylic It is more preferable to use an acid.
The alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms is preferably n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, or sec-butyl methacrylate, and particularly preferably n-butyl methacrylate.

Although the manufacturing method of a polymer (B) is not specifically limited, First, as reaction of the 1st step, the alkyl (meth) acrylate (B1) or cycloalkyl (meth) acrylate (B2) which has an alkyl group with 2 or more carbon atoms Any one or more of the above and a monomer having a first functional group involved in the esterification reaction are copolymerized to obtain a first copolymer having the first functional group. Then, as a second stage reaction, the second functional group and the second monomer having a double bond that are esterified with the first functional group are esterified with the first copolymer. The method of obtaining the polymer (B) which has a double bond by making it react is preferable.
As a combination of the first functional group and the second functional group, a carboxyl group and a glycidyl group, a hydroxyl group and an isocyanate group, and the like are preferable.

The specific polymerization method is not particularly limited. First, in the first stage reaction, either alkyl (meth) acrylate (B1) or cycloalkyl (meth) acrylate (B2) having an alkyl group having 2 or more carbon atoms is used. 1 type or 2 types or more and methyl methacrylate and (meth) acrylic acid are subjected to suspension polymerization to obtain a first copolymer having a carboxyl group, and in the second stage reaction, the first copolymer obtained A method in which the polymer is dissolved in a methyl methacrylate monomer and glycidyl (meth) acrylate is added to the first copolymer by an esterification reaction in the solution to obtain the polymer (B) is preferable.
The polymerization temperature for suspension polymerization in the first stage reaction is preferably in the range of 70 to 98 ° C., and the polymerization time is preferably about 2 to 5 hours. The reaction temperature in the second stage reaction is preferably 90 to 95 ° C., and the reaction time is preferably about 1 to 4 hours.

  The preferred composition ratio of the monomer used in the first stage reaction is either one of alkyl (meth) acrylate (B1) or cycloalkyl (meth) acrylate (B2) having an alkyl group having 2 or more carbon atoms, or The total of 2 or more types is preferably 5 to 40% by mass, methyl methacrylate is 53 to 94.5% by mass, and (meth) acrylic acid is preferably 0.5 to 7% by mass, and an alkyl group having 2 or more carbon atoms. The alkyl (meth) acrylate (B1) or cycloalkyl (meth) acrylate (B2) having 15 to 40% by mass, methyl methacrylate 59 to 81% by mass, and (meth) acrylic acid 1 to 4% by mass. preferable.

  In the second stage reaction, 100 parts by mass of the first stage copolymer was dissolved in 70 to 150 parts by mass of methyl methacrylate monomer, and 1 of the (meth) acrylic acid used in the first stage reaction. It is preferable to react 0.9-1.2 mol of glycidyl (meth) acrylate with respect to mol, and it is more preferable to react 1.0-1.1 mol.

The suspension in which suspension polymerization is performed in the first stage reaction is preferably an aqueous suspension. It is preferable to add a dispersant to the aqueous suspension. The dispersant is not particularly limited, and examples thereof include poorly water-soluble inorganic compounds such as calcium phosphate, aluminum hydroxide, and starch silica; nonionic polymer compounds such as polyvinyl alcohol, polyethylene oxide, and cellulose derivatives; alkali poly (meth) acrylates Examples thereof include metal salts and anionic polymer compounds such as alkali metal salts of (meth) acrylic acid and methyl (meth) acrylate copolymer. The amount of the dispersant used is preferably in the range of 0.005 to 5 mass%, more preferably in the range of 0.01 to 1 mass% with respect to the suspension.
Moreover, it is preferable to contain electrolytes, such as sodium carbonate, sodium sulfate, manganese sulfate, in the suspension at the time of the suspension polymerization. By containing an electrolyte, dispersion stability can be improved. The amount of electrolyte used is not particularly limited as long as it is set appropriately.

In the suspension polymerization, a polymerization initiator is used. The polymerization initiator is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, bis (4-tert Organic peroxides such as -butylcyclohexyl) peroxydicarbonate; azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis-2-methylbutyronitrile. These may be used alone or in combination of two or more. The addition amount and addition method of the polymerization initiator may be set as appropriate and are not particularly limited.
It is preferable to use a chain transfer agent in the suspension polymerization. When a chain transfer agent is used, the polymerization reaction of the monofunctional acrylic monomer can be easily controlled.
A thiol compound is preferably used as the chain transfer agent. The thiol compound is not particularly limited, and examples thereof include alkyl mercaptans such as t-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan; aromatic mercaptans such as thiophenol thionaphthol: thioglycolic acid, thioglycolic acid thiol And alkyl glycolate. The addition amount and addition method of the chain transfer agent may be appropriately set and are not particularly limited.

In the second stage reaction, an esterification catalyst can be used to advance the reaction between the first functional group and the second functional group. Examples of the esterification catalyst include amines such as triethylamine; quaternary ammonium salts such as tetraethylammonium chloride and tetrabutylammonium bromide; and phosphorus compounds such as triphenylphosphine. These may be used alone or in combination of two or more. The addition amount of the esterification catalyst may be set as appropriate and is not particularly limited.
A polymerization inhibitor may be added in the second stage reaction. When a polymerization inhibitor is added, the second stage reaction can be performed more stably. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl 4-methylphenol, and the like. These may be used alone or in combination of two or more. The addition amount of the polymerization inhibitor may be set as appropriate and is not particularly limited.

The weight average molecular weight of the first copolymer obtained by the first stage reaction is preferably in the range of 10,000 to 150,000, more preferably in the range of 15,000 to 80,000. preferable. When the weight average molecular weight is 10,000 or more, the strength of the cured product tends to be sufficiently high. When the weight average molecular weight is 150,000 or less, the viscosity tends to be sufficiently low.
The weight average molecular weight in the present specification is obtained by dissolving the resin in a solvent (tetrahydrofuran) and converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) into polystyrene.
The acid value (unit: mgKOH / g) of the polymer (B) obtained by the second stage reaction is preferably 1 or less, and more preferably 0.5 or less.
The acid value in this specification is a value obtained by dissolving a polymer in toluene and titrating with 0.1N KOH ethanol solution using phenolphthalein as an indicator.

  Content of the polymer (B) in syrup (X) is 15-40 mass%, 15-35 mass% is preferable, and the range of 18-30 mass% is more preferable. When the content is 15% by mass or more, good curability is easily obtained, and when it is 40% by mass or less, syrup (X) tends to have a sufficiently low viscosity.

<Wax (C)>
The syrup composition (L) in the present invention contains wax (C) in addition to syrup (X). Wax (C) exhibits an effect such as an improvement in surface curability utilizing an air blocking effect.
Examples of the wax (C) include solid waxes. Examples of solid waxes include higher fatty acids such as paraffins, polyethylenes, and stearic acid. Of these, paraffin wax is preferred.
It is preferable to use two or more paraffin waxes having different melting points. The melting point of the paraffin wax is preferably 40 to 80 ° C. When the melting point is 40 ° C. or higher, a sufficient air barrier action is obtained when the compound is cured, and the surface curability tends to be good. When the melting point is 80 ° C. or lower, the solubility in syrup (X) tends to be good. In addition, when two or more paraffin waxes having different melting points are used in combination, a sufficient air barrier action can be obtained and the surface curability can be improved even when the base temperature changes when the composition is paint-cured. . When using 2 or more types together, it is preferable to use the thing of the difference of melting | fusing point about 5 to 20 degreeC together.

As the wax (C), a wax dispersed in an organic solvent may be used in terms of further improving the surface curability. When the wax is dispersed in the organic solvent and is finely divided, the air blocking action is more effectively exhibited. Such a wax dispersion is commercially available, and the wax dispersion can be added as it is when preparing the syrup composition (L). In this case, the syrup composition (L) will also contain an organic solvent.
Alternatively, the wax (C) may be used in which the wax (C) is previously dispersed in the methyl methacrylate monomer (A) without containing any organic solvent.

The addition amount of the wax (C) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the syrup (X) in terms of the balance between the surface curability and the physical properties of the cured product. ˜2 parts by mass are preferred.
In the present invention, 100 parts by mass of syrup (X) serving as a reference is composed of methyl methacrylate monomer (A), polymer (B), and acrylic monomer (D) other than monomer (A). The total mass of
When the added amount of the wax (C) is 0.1 parts by mass or more, an air barrier action when cured is sufficiently obtained, and good surface curability is obtained. When the added amount of the wax (C) is 5 parts by mass or less, good storage stability of the syrup composition (L) and good dispersibility of the wax are easily obtained.

<Tertiary amine>
It is preferable to add a tertiary amine to the syrup composition (L) in the present invention. A tertiary amine is a curing accelerator that accelerates the curing reaction.
Tertiary amines include aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p- Toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N -Bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, N, N-substituted anilines such as diethanolaniline, N, N-substituted-p-toluidi , 4- (N, N- disubstituted amino) benzaldehyde, and the like.

As the tertiary amine, an aromatic tertiary amine is more preferable. As the aromatic tertiary amine, those in which at least one aromatic residue is directly bonded to the nitrogen atom are preferable. Examples of the aromatic tertiary amine include N, N-dimethyl-p-toluidine, N, N-diethylaniline, N, N-diethyl-p-toluidine, N- (2-hydroxyethyl) N-methyl-p-. Toluidine, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-di (2-hydroxypropyl) -p-toluidine; N, N-di (2-hydroxyethyl) -p-toluidine or Examples thereof include ethylene oxide or propylene oxide adducts of N, N-di (2-hydroxypropyl) -p-toluidine. Moreover, these are not limited to p (para) body, o (ortho) body and m (meta) body may be sufficient.
Examples of the aromatic tertiary amine include N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di () from the viewpoint of reactivity and curability of the syrup composition (L). 2-hydroxyethyl) -p-toluidine and N, N-di (2-hydroxypropyl) -p-toluidine are preferred.
A tertiary amine may be used individually by 1 type, and may be used in combination of 2 or more type.
The tertiary amine may be added immediately before the compound is cured (simultaneously added with the aggregate or after the aggregate is added), or may be added to the syrup composition in advance.
The addition amount of the tertiary amine is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of syrup (X) from the viewpoint of balance between curability and pot life (workability), and 0.2. -8 mass parts is more preferable, and 0.3-5 mass parts is especially preferable. When the addition amount of the tertiary amine is 0.05 parts by mass or more, good surface curability is easily obtained. When the added amount of the tertiary amine is 10 parts by mass or less, an appropriate pot life can be easily obtained.

<Other curing accelerators>
You may make the syrup composition (L) of this invention contain polyvalent metal soaps, such as cobalt naphthenate, cobalt octylate, and cobalt acetoacetyl, as hardening accelerators other than tertiary amine.
0.2-2 mass parts is preferable with respect to 100 mass parts of syrup (X), and, as for the addition amount of this other hardening accelerator, 0.3-1 mass part is more preferable.

<Plasticizer>
You may add the plasticizer for aiming at the softening of hardened | cured material and reduction of the shrinkage | contraction at the time of hardening to the syrup composition (L) in this invention.
Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, di-2-ethylhexyl phthalate, and diisodecyl phthalate; adipic acid esters such as di-2-ethylhexyl adipate and octyl adipate; dibutyl sebacate, di-2-ethylhexyl seba Examples include sebacic acid esters such as Kate; dibasic fatty acid esters such as azelain esters such as di-2-ethylhexyl azelate and octyl azelate; tributyl acetyl citrate; paraffins such as chlorinated paraffin.
A plasticizer may be used individually by 1 type and may be used in combination of 2 or more type.
The addition amount of the plasticizer is preferably 20 parts by mass or less with respect to 100 parts by mass of syrup (X). When the added amount of the plasticizer is 20 parts by mass or less, the curability tends to be good, and the plasticizer does not exude on the surface of the cured product.

<Silane coupling agent>
In the syrup composition (L) in the present invention, a silane coupling agent is added for the purpose of stabilizing the adhesion to the substrate, durability of the adhesive strength, and stabilization of the adhesion to the aggregate. Also good.
Examples of silane coupling agents include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glucidoxypropyl. Examples include trimethoxysilane and γ-mercaptopropyltrimethoxysilane.
The addition amount of the silane coupling agent is preferably 10 parts by mass or less with respect to 100 parts by mass of syrup (X), and more preferably 5 parts by mass or less from the viewpoint of curability and cost. Surface hardening while maintaining the adhesion between the syrup composition (L) and the aggregate and the adhesion of the compound to the substrate by keeping the addition amount of the silane coupling agent to 10 parts by mass or less Property is improved.

<Polymerization inhibitor>
A polymerization inhibitor may be added to the syrup composition (L) in the present invention for the purpose of improving storage stability and adjusting the polymerization reaction.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2-6-di-t-butyl 4-methylphenol, and the like.
The addition amount of the polymerization inhibitor is preferably 0.01 to 0.1 parts by mass, and more preferably 0.02 to 0.08 parts by mass with respect to 100 parts by mass of syrup (X).

<Oligomer>
In order to improve the surface curability, an oligomer having a (meth) acryloyl group may be added to the syrup composition (L) of the present invention.
Examples of the oligomer include urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate.
Urethane (meth) acrylate reacts with hydroxyl group-containing (meth) acrylate, polyisocyanate having two or more isocyanate groups in one molecule, and polyol having two or more hydroxyl groups in one molecule by a known method. Can be obtained.
The epoxy (meth) acrylate is obtained by reacting a polybasic acid anhydride, a partially esterified product of a hydroxyl group-containing (meth) acrylate, a bifunctional bisphenol A type epoxy resin, and an unsaturated monobasic acid by a known method. It is The bifunctional bisphenol A type epoxy resin is a general-purpose epoxy resin obtained by reacting bisphenol A and epichlorohydrin.
Polyester (meth) acrylates are polybasic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, succinic acid, maleic acid, fumaric acid and adipic acid or their anhydrides, and polyhydric alcohol compounds such as ethylene glycol and propylene glycol. And a (meth) acrylic acid adduct or glycidyl (meth) acrylate and a polybasic acid anhydride.

<Other polymer components>
The syrup composition (L) in the present invention can also contain styrene / butadiene copolymer, vinyl chloride / vinyl acetate copolymer, cellulose acetate butyrate resin, epoxy resin, and the like as other polymer components. is there.

<Other additives>
In the syrup composition (L) in the present invention, an ultraviolet absorber, a light stabilizer, and an antifoaming agent can be added at an arbitrary ratio as necessary. Moreover, you may add thixotropic agents, such as antioxidant, a leveling agent, and an aerosil.
Furthermore, pigments such as titanium oxide, iron oxide, bengara and ultramarine may be added, and a quality pigment such as calcium carbonate may be added.

  Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4. Derivatives of 2-hydroxybenzophenone such as 4,4'-dibutoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butyl) Phenyl) benzotriazole or a halide thereof, phenyl salicylate, p-tertiarybutylphenyl salicylate, and the like. These may be used alone or in combination of two or more.

  Examples of the light-resistant stabilizer include bis (2,2,6,6, -tetramethyl-4piperidyl) sebacate, bis (1,2,2,6,6, -pentamethyl-4-piperidyl) sebacate, 1- [2 -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Examples include -2,2,6,6, -tetramethylpiperidine and 4-benzoyloxy-2,2,6,6, -tetramethylpiperidine. These may be used alone or in combination of two or more.

  Examples of the antifoaming agent include known antifoaming agents. Specific examples include an acrylic antifoaming agent in which a special acrylic polymer is dissolved in a solvent, a vinyl antifoaming agent in which a special vinyl polymer is dissolved in a solvent, and the like, which are commercially available from Enomoto Kasei Co., Ltd. Dispalon series (Product names: OX-880EF, OX-881, OX-883, OX-77EF, OX-710, OX-8040, 1922, 1927, 1950, P-410EF, P-420, P-425, PD-7, 1970, 230, 230HF, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, etc.) are more preferred, and among the Disparon series, 230, 230HF, LF-1980 LF-1985 is more preferable, and 230 and LF-1985 are particularly preferable. Moreover, BYK-052 and BYK-1752 marketed by Big Chemie Japan are preferable.

As the thixotropic agent, an organic thixotropic agent such as urethane urea, fatty acid amide, organic bentonite, and oxidized polyethylene wax is preferable. If necessary, fine silica is used in combination. Examples of combinations of thixotropic agents include a combination of fatty acid amide and fine silica, a combination of organic bentonite and fine silica, a combination of fatty acid amide, organic bentonite and fine silica, and a combination of oxidized polyethylene wax and fine silica. The average primary particle diameter of the fine silica is preferably 7 to 40 μm.
By containing the thixotropic agent, structural viscosity is imparted to the syrup composition (L), thixotropy is increased, and the hollow particles can be uniformly distributed, and the storage stability of the syrup composition (L) is improved. . Moreover, workability | operativity, such as when constructing the compound of this invention, for example to an inclined surface, can be improved.
The content of the thixotropic agent is 0.5 to 5% by mass in total of urethane urea, fatty acid amide and / or organic bentonite, and 1 to 10% by mass of fine silica in 100% by mass of the syrup composition (L). Preferably there is. If the content of the thixotropic agent is too small, the effect of addition becomes insufficient. On the other hand, when there is too much content of a thixotropic agent, the fluidity | liquidity of a syrup composition (L) will worsen and it will become impractical. The thixotropic agent may be added to the syrup composition (L) or may be used in the aggregate.

<Aggregate>
The formulation of the present invention contains a syrup composition (L) and aggregate. The composition of the present invention is, for example, a road pavement as a resin mortar containing a syrup composition (L) and fine aggregate, or a resin concrete containing a syrup composition (L) and coarse aggregate and / or fine aggregate. It can be used for civil engineering applications such as road bridge decks, slab tracks, and piers, and architectural applications such as factory floors and kitchen floors. In particular, it can be suitably used for applications that require high strength and require little variation in strength with respect to temperature changes.

Specific examples of the aggregate include silica sand No. 3, silica sand No. 4, silica sand No. 5, silica sand No. 6, quartz sand No. 7, quartz sand No. 8, river sand, ceramic aggregate, calcium carbonate, silica sand powder, which pass through a 5 mm sieve. Fine aggregates such as silica fume, aluminum hydroxide, microsilica, alumina and slag; coarse aggregates such as crushed stone having a particle diameter of 5 mm or more, gravel, and gravel.
As an aggregate, a mixture of silica sand 3, silica sand 5 and calcium carbonate; a mixture of silica sand 3, silica sand 4, silica sand 6 and calcium carbonate; silica sand 3, silica sand 4, silica sand 5, silica sand 7 , And a mixture of calcium carbonate; and the like can be suitably used.
In addition, when it is desired to apply the composition of the present invention to a thickness of 3 cm or more, it is preferable to combine a fine aggregate made of the above mixture and a coarse aggregate having a particle size of 5 mm or more in combination.
The compounding quantity of an aggregate is 400-1500 mass parts with respect to 100 mass parts of syrup compositions (L).
If the aggregate is less than 400 parts by mass, the resin of the syrup composition (L) and the aggregate are likely to be separated, and it is difficult to obtain a uniform cured product. On the other hand, if it exceeds 1500 parts by mass, it becomes difficult to mix the resin and the aggregate sufficiently uniformly, and the workability deteriorates. A preferable range of the amount of the aggregate is 550 to 1400 parts by mass with respect to 100 parts by mass of the syrup composition (L), and a more preferable range is 700 to 1350 parts by mass.
In the present invention, 100 parts by mass of the reference syrup composition (L) is the total mass of the remaining components excluding the curing agent and aggregate among the components contained in the composition to be cured.

<Organic peroxide>
In order to cure the blend of the present invention, it is preferable to add an organic peroxide as a curing agent, and it is more preferable to use a redox catalyst in which a curing accelerator and an organic peroxide are combined.
As the organic peroxide, a known organic peroxide can be used as a polymerization initiator capable of initiating radical polymerization. Specific examples include diacyl peroxide, alkyl peroxide, and ketone peroxide. Of these, diacyl peroxide is preferable, and benzoyl peroxide (benzoyl peroxide) is particularly preferable. The benzoyl peroxide is preferably in the form of liquid, paste or powder diluted with an inert liquid or solid to a concentration of about 30 to 55% by mass from the viewpoint of handleability.
An organic peroxide may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the organic peroxide added is preferably adjusted as appropriate so that the pot life of the blend is 5 to 60 minutes. If the organic peroxide is added within this range, the polymerization reaction starts immediately after the addition, and the curing of the syrup composition (L) proceeds.
0.5-10 mass parts is preferable with respect to 100 mass parts of syrup (X), and, as for the addition amount of an organic peroxide, 1-5 mass parts is more preferable. When the addition amount of the organic peroxide is 1 part by mass or more, curability tends to be good. When the amount of the organic peroxide added is 10 parts by mass or less, the coating workability of the blend and the various physical properties of the resulting cured product are improved satisfactorily.

<Coating method>
The compound of the present invention can be used as a covering material / reinforcing material or a filler for a floor surface, a wall surface, a road pavement surface, a road bridge deck surface, a slab track surface and the like.
As a method for coating floors, walls, road paving surfaces, road bridge decks, slab track surfaces, etc., after applying a primer on the construction surface to ensure good adhesion to the ground, Examples include a method in which the compound of the invention is applied and laminated, and in some cases, a topcoat layer is further laminated. When the blend is cured, a laminate made of a cured product is formed on the construction surface. In addition, syrup composition (L) can also be used for a primer and a top coat.
Examples of the coating method of the composition of the present invention include a known coating method using a gold trowel, a spraying machine (such as a mortar spraying coating machine), and the like.
The temperature during coating is preferably -20 to 50 ° C, particularly preferably -10 to 40 ° C. From the viewpoint of workability, the pot life is preferably 5 to 60 minutes, and the curing time is preferably within 10 to 90 minutes. The pot life and the curing time can be adjusted by adjusting the amounts of the curing agent and the curing accelerator according to the temperature at the time of coating.
As a use environment after hardening of the blend, a use temperature range of −30 to 90 ° C. is preferable, and a range of −10 to 80 ° C. is particularly preferable. The blend of the present invention is a low-temperature-sensitive blend with little variation in physical properties with respect to temperature changes, and since it is difficult for strength changes to occur when the use environment is 80 ° C. or lower, sufficient performance can be exhibited even at high temperatures. .
Cured product obtained by curing the formulations of the present invention, when a reference 20 ° C., the flexural strength: 10 N / mm ² or more, the compressive strength: 15N / mm ² or more can be achieved. Further, the fluctuation range of the strength due to the temperature change for both the bending strength and the compressive strength can be obtained as follows: (strength at 20 ° C.−strength at 80 ° C.) / Strength at 20 ° C. = 0.5 or less. Can achieve 0.35 or less.
Further, if it is in a temporary state, it is not particularly limited to the above-mentioned operating temperature range, and for example, it can be used sufficiently without being deformed even when it is temporarily in contact with hot water or the like.

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples.
In the examples, all “parts” indicate “parts by mass”, and all “%” other than humidity indicates “% by mass”.

[Synthesis Example 1: Preparation of Composition S-1 Containing Polymer (B)]
First, the first stage reaction was performed. That is, 135 parts of deionized water and 0.4 part of polyvinyl alcohol (degree of saponification 80%, degree of polymerization 1,700) as a dispersing agent were added to a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer and stirred. After the polyvinyl alcohol is completely dissolved, the stirring is once stopped, 4 parts of methacrylic acid (hereinafter abbreviated as MAA), 60 parts of methyl methacrylate (hereinafter abbreviated as MMA), n-butyl methacrylate (hereinafter referred to as n-BMA). 36 parts, 2,2'-azobis-2-methylbutyronitrile (hereinafter abbreviated as AMBN) 0.2 parts as a polymerization initiator, n-dodecyl mercaptan (hereinafter abbreviated as n-DM) as a chain transfer agent .) 0.8 part, 0.1 part of sodium carbonate as an electrolyte was added and stirred again, heated to 75 ° C. and reacted for 2.5 hours, heated to 98 ° C. and held for 1.5 hours. Reaction was terminated. After cooling to 40 ° C., the obtained aqueous suspension is filtered through a nylon filter cloth having a mesh opening of 45 μm, the filtrate is washed with deionized water, dehydrated, dried at 40 ° C. for 16 hours, and granular vinyl. A system polymer (first copolymer) was obtained. The obtained granular vinyl polymer had a Tg of 72 ° C. and a weight average molecular weight of 41,500. The Tg of the granular vinyl polymer was calculated from the homopolymer Tg described in the polymer handbook using the Fox equation.

  The second stage reaction was then performed. That is, in a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 6.6 parts of glycidyl methacrylate (hereinafter abbreviated as GMA), 1.5 parts of tetrabutylammonium bromide as an esterification catalyst, and 2, 0.1 parts of 6-di-t-butyl-4-methylphenol (hereinafter abbreviated as BHT) and 108.2 parts of methyl methacrylate were added, and the granular vinyl polymer obtained above (the first 1 Copolymer) 100 parts are gradually added, and after the entire amount is added, the temperature is raised to 90 ° C. and held for 2 hours, and composition S-1 containing polymer (B) having an acid value of 0.3 mg KOH / g and MMA is added. Obtained. The molar ratio of GMA used in the second stage reaction (hereinafter referred to as the MAA / GMA molar ratio) was 1.0 / 1.0 with respect to 1 mole of MAA used in the first stage reaction. It was.

[Synthesis Example 2: Preparation of Composition S-2 Containing Polymer (B)]
In the first stage reaction of Synthesis Example 1, the amount of MMA used was changed from 60 parts to 78 parts, the amount of MAA used was changed from 4 parts to 2 parts, and the amount of n-BMA used was changed from 36 parts to 20 parts. . Otherwise in the same manner as in Synthesis Example 1, a granular vinyl polymer (first copolymer) having a Tg of 86 ° C. and a weight average molecular weight of 43,000 was obtained.
A second stage reaction was carried out using the obtained granular vinyl polymer. In the second stage reaction of Synthesis Example 1, the amount of GMA used was changed from 6.6 parts to 3.3 parts, and the amount of MMA used was changed from 108.2 parts to 104.9 parts. Otherwise, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain a composition S-2 containing a polymer (B) having an acid value of 0.4 mgKOH / g and MMA. The molar ratio of MAA / GMA was 1.0 / 1.0.

[Synthesis Example 3: Preparation of Composition S-3 Containing Polymer (B)]
In the first stage reaction of Synthesis Example 1, the amount of MAA used was changed from 4 parts to 2 parts, the amount of MMA used was changed from 60 parts to 68 parts, and instead of 36 parts of n-BMA, isobornyl methacrylate was used. 30 parts (hereinafter abbreviated as IBXMA) were used, and 0.4 parts of lauroyl peroxide (hereinafter abbreviated as LPO) were used instead of 0.2 parts of AMBN. Other than that was carried out similarly to the synthesis example 1, and obtained the granular vinyl polymer (1st copolymer) of Tg119 degreeC and the weight average molecular weight 40,000.
A second stage reaction was carried out using the obtained granular vinyl polymer. Same as Synthesis Example 1, except that the amount of GMA used was changed from 6.6 parts to 3.3 parts and the amount of MMA used was changed from 108.2 parts to 104.9 parts in the second stage reaction of Synthesis Example 1. The composition S-4 containing the polymer (B) having an acid value of 0.3 mgKOH / g and MMA was obtained. The molar ratio of MAA / GMA was 1.0 / 1.0.

[Synthesis Example 4: Preparation of Composition S-4 Containing Polymer (B)]
In the first stage reaction of Synthesis Example 1, 36 parts of n-BMA were replaced with 36 parts of ethyl methacrylate (hereinafter abbreviated as EMA), and the amount of n-DM used was changed from 0.8 parts to 0.18 parts. Was used. Otherwise in the same manner as in Synthesis Example 1, a granular vinyl polymer (first copolymer) having a Tg of 83 ° C. and a weight average molecular weight of 150,000 was obtained.
A second stage reaction was carried out using the obtained granular vinyl polymer. The reaction was conducted in the same manner as in Synthesis Example 1 to obtain a composition S-4 containing a polymer (B) having an acid value of 0.3 mgKOH / g and MMA. The molar ratio of MAA / GMA was 1.0 / 1.0.

[Preparation Example 1: Production of syrup composition L-1]
Using composition S-1 obtained in Synthesis Example 1, syrup composition L-1 was prepared with the formulation shown in Table 1. In addition, the compounding quantity (unit: mass part) of composition S-1-S-4 described in Table 1 is the total amount of the polymer (B) and MMA contained in this composition, and it writes together. The value in () is the amount (unit: part by mass) of the polymer (B) contained in the blended compositions S-1 to S-4. Therefore, for example, in the syrup composition L-1, the content of the methyl methacrylate monomer (A) in 100 parts by mass of syrup (X) is 80.1 parts by mass.

  In a 1 L flask equipped with a stirrer, thermometer, and cooling tube, 40 parts of composition S-1 containing the polymer (B) obtained in Synthesis Example 1, 60 parts of MMA, 0.03 part of BHT, paraffin wax (product name) 115, manufactured by Nippon Seiki Co., Ltd., melting point 47 ° C., hereinafter abbreviated as P-115.) 0.4 part, paraffin wax (product name 130, manufactured by Nippon Seiki Co., Ltd., melting point 55 ° C., hereinafter abbreviated as P-130) 0.3 part, paraffin wax (product name H150, manufactured by Nippon Seiki Co., Ltd., melting point 66 ° C., hereinafter abbreviated as P-150), 0.2 part, N, N-di (2-hydroxyethyl) -p-toluidine (Hereinafter abbreviated as PTEO) 0.5 parts and 0.5 part of BYK-1752 (manufactured by Big Chemie Japan Co.) as an antifoaming agent are added, heated at 70 ° C. for 2 hours, dissolved, cooled and cooled to a syrup composition. L-1 was obtained.

[Preparation Examples 2 to 4: Production of syrup compositions L-2 to L-4]
Syrup compositions L-2 to L-4 were obtained in the same manner as in Preparation Example 1, except that the formulation was changed as shown in Table 1.

[Preparation Example 5: Production of syrup composition L-5]
A syrup composition L-5 was obtained in the same manner as in Preparation Example 1, except that the formulation was changed as shown in Table 1.
In Table 1, 2-HPMA is 2-hydroxypropyl methacrylate, and PTMG is polytetramethylene glycol dimethacrylate (Blenmer PDT-650 manufactured by NOF Corporation).

[Preparation Example 6: syrup composition L-6]
A syrup composition L-6 was obtained in the same manner as in Preparation Example 1, except that the formulation was changed as shown in Table 1. In this example, the polymer (B) was not used, and instead, a copolymer-1 having an n-butyl methacrylate unit but having no polymerizable double bond was used.
Copolymer-1 is a copolymer having a weight average molecular weight of 41,000 obtained by copolymerizing 60 parts of MMA and 40 parts of n-BMA. Note that 2-EHA is 2-ethylhexyl acrylate, and the plasticizer is adipic acid (product name: Adeka Sizer P-300, manufactured by Adeka Corporation, hereinafter abbreviated as a plasticizer).

The abbreviations in the table are as follows.
S-1: First copolymer / GMA + MMA = 100 / 6.6 + 108.2 (parts).
First copolymer = MMA / n-BMA / MAA = 60/36/4 (part), Tg: 72 ° C., Mw: 41,500.
S-2: First copolymer / GMA + MMA = 100 / 3.3 + 104.9 (parts).
First copolymer = MMA / n-BMA / MAA = 78/20/2 (parts), Tg: 86 ° C., Mw: 43,000.
S-3: First copolymer / GMA + MMA = 100 / 3.3 + 104.9 (parts).
First copolymer = MMA / IBXMA / MAA = 68/30/2 (parts), Tg: 119 ° C., Mw: 40,000.
S-4: First copolymer / GMA + MMA = 100 / 6.6 + 108.2 (parts).
First copolymer = MMA / EMA / MAA = 60/36/4 (part), Tg: 83 ° C., Mw: 150,000.
Copolymer-1: MMA / n-BMA = 60/40 (part), Tg: 66 ° C., Mw: 41,000.
MMA: methyl methacrylate.
2-EHA: 2-ethylhexyl acrylate.
2-HPMA: 2-hydroxypropyl methacrylate.
PTMG: Polytetramethylene glycol dimethacrylate (Blemmer PDT-650 manufactured by NOF Corporation).
PEGDMA: Polyethylene glycol dimethacrylate (NK ester 3G manufactured by Shin-Nakamura Chemical Co., Ltd.).
Plasticizer: Adipic acid type (Adeka Sizer P-300 manufactured by ADEKA).
BHT: 2,6-di-tert-butyl-4-methylphenol.
BYK-1752: foam-breaking polymer + petroleum naphtha (manufactured by Big Chemie Japan Co., Ltd.).
P-130, P-150, HNP-9: Paraffin wax (manufactured by Nippon Seiki Co., Ltd.).
PTEO: N, N-di (2-hydroxyethyl) -P-toluidine.

[Formulation Example 1: Formulation]
To 100 parts of the syrup composition L-1 obtained in Preparation Example 1, 1.96 parts of benzoyl peroxide (manufactured by Gunpaku Akzo, pure content 50%, hereinafter abbreviated as BPO50) as a curing agent was added and mixed. Thereafter, 900 parts of aggregate KM-2 (product name: KM-2, manufactured by Ryohin Co., Ltd., hereinafter abbreviated as KM-2) was added and mixed to prepare a blend.

[Composition Examples 2-9]
A formulation was obtained in the same manner as in Formulation Example 1 except that the formulation was changed as shown in Table 2. In the blending examples 5 and 7, the aggregate KM-2 was not used, but the aggregate KM-17A (product name: KM-17A, manufactured by Ryohin Co., Ltd., hereinafter abbreviated as KM-17A) was used instead. In the blending example 6, the aggregate KM-2 was further added with gravel with a particle size of 5 mm.
[Formulation Example 10]
100 parts of syrup composition L-6 obtained in Preparation Example 6 (79.5 parts by mass as syrup (X)), 1.59 parts of BPO50 as a curing agent (2 parts with respect to syrup (X)) Then, 900 parts of KM-2, an aggregate, was added and mixed to prepare a blend.

[Evaluation]
(Viscosity, specific gravity)
The viscosity and specific gravity of each syrup composition L-1 to 6 obtained in Preparation Examples 1 to 6 were measured. The results are shown in Table 1.
The viscosity was measured at 20 ° C. using a B-type viscometer (BM type, manufactured by Tokimec).
Specific gravity measured the specific gravity in 20 degreeC using the specific gravity cup.

(Curing time)
Add 2 parts by mass of BPO50 as a curing agent to 100 parts of syrup (X) in the syrup composition (L) to the syrup compositions L-1 to 6 obtained in Preparation Examples 1-6. By mixing, a syrup composition containing BPO was obtained. The syrup composition containing BPO was introduced from the bottom of a test tube having a diameter of 10 mm and a length of 120 mm to 70 mm, and a thermocouple was placed in the center in the depth direction of the syrup composition. While the test tube was left in water at 20 ° C. to cure the syrup composition, the exothermic temperature was measured over time with the thermocouple. The time from the addition of BPO to the time when the maximum exothermic temperature was reached was determined, and this time was taken as the curing time. The results are shown in Table 1.

(Kneadability)
In preparing the blends in Formulation Examples 1 to 10, the kneadability between the syrup composition (L) and the aggregate at 20 ° C. was evaluated.
That is, 2 parts of BPO as a curing agent is added to syrup composition (L) with respect to 100 parts of syrup (X) in the syrup composition (L) and mixed. After being put into a container in a mechanical kneader, the aggregate shown in Table 2 is added, and aggregate KM-2, KM-17A, or KM-2 and boulder gravel with a particle size of 5 mm are added, and a condensation test specified in JIS R 5201 It knead | mixed for 1 minute with the mortar mixer in the kneader for the machine kneading of the item. The mixing property of the aggregate and the syrup composition (L) during kneading was visually observed and evaluated based on the following criteria. The results are shown in Table 2.
A: The syrup composition (L) and the aggregate were very familiar and uniform very quickly (within 45 seconds).
○: The syrup composition (L) and the aggregate were sufficiently familiar and uniform.
X: The syrup composition (L) and the aggregate were unfamiliar and non-uniform.

(Coating workability)
The workability when the blends obtained in Blending Examples 1 to 10 were coated on a concrete plate was evaluated.
That is, the thickness of the composition was applied to a concrete plate (30 cm × 30 cm × 6 cm) obtained by applying and curing a primer (Acrysilup DR-90, manufactured by Hishijo Co., Ltd.) at a rate of 0.3 kg / m ^2. Evaluation of the iron workability when coating was performed so that the thickness was 5 mm was evaluated based on the following criteria. The results are shown in Table 2.
In addition, about the compounding example 6, applied thickness was 10 mm and evaluated.
A: The composition could be quickly and sufficiently leveled with a trowel, and evenly applied by several trowel operations.
○: The blend could be sufficiently leveled with a trowel and applied uniformly.
X: When the blend was leveled with a trowel, the viscosity was high and difficult to level, and / or it took a very long time to obtain a uniform surface.

(Material separability)
When the blends obtained in blending examples 1 to 10 were coated on a concrete plate or were cured, the material separability was evaluated.
That is, when the composition was applied to the same concrete plate as used for the above-described evaluation of the coating workability so as to have a thickness of 5 mm, or after being cured, the material separability was visually observed, and the following criteria were used. Based on the evaluation. The results are shown in Table 2.
In addition, about the compounding example 6, applied thickness was 10 mm and evaluated.
A: The syrup composition (L) and the aggregate were uniform without separation.
X: Aggregate sank and the syrup composition (L) floated very unevenly, and the syrup composition (L) accumulated in the lower layer and was uneven.

(Bending strength)
The blends obtained in Formulation Examples 1 to 10 were poured into a 4 cm × 4 cm × 16 cm form defined by JIS R 5201 and cured at 20 ° C. to obtain a cured product. After 1 day or more after curing, the cured product was allowed to stand at each test temperature for 4 hours or more, and the cured product was set to the test temperature. Then, bending strength was measured based on JISR5201 under test temperature. The test temperature was −10, 20, 60, and 80 ° C. The results are shown in Table 2.

(Compressive strength)
The cured product of the blend was set to each test temperature in the same manner as the evaluation of the bending strength, and then the compressive strength was measured based on JIS R 5201 at the test temperature. The results are shown in Table 2.

(Intensity fluctuation due to temperature change)
For both the bending strength and the compressive strength, a value represented by “(strength at 20 ° C.−strength at 80 ° C.) / Strength at 20 ° C.” was obtained as a fluctuation range of strength due to temperature change. The results are shown in Table 2.

As shown in the results of Table 1, the syrup compositions of Preparation Examples 1 to 4 have low viscosity.
As shown in the results of Table 2, formulation examples 1 to 6 were prepared using the syrup compositions of Preparation Examples 1 to 4 and the amount of aggregate was within the scope of the present invention. And a uniform blend is obtained, and the bending strength and compressive strength are high. Moreover, about both bending strength and compressive strength, the value represented by (strength at 20 ° C.−strength at 80 ° C.) / Strength at 20 ° C. is as small as 0.33 or less. This shows that the strength fluctuation of the material due to temperature is small and good.
In contrast, Formulation Examples 7 and 8 in which the syrup composition of Preparation Example 1 was used and the blending amount of the aggregate was out of the scope of the present invention were inferior in kneadability or material separability and used in the blend. Did not come. In addition, since the uniform compound was not obtained, the compound 7-8 did not measure the physical property of hardened | cured material.
Moreover, although the compounding example 9 with little content of the MMA monomer (A) in syrup (X) and the compounding example 10 which did not use a polymer (B), kneadability and a uniform compound are obtained. High viscosity and poor coating workability. In addition, in Formulation Example 10, both the bending strength and the compressive strength were significantly reduced in strength at 60 ° C., so the physical properties of the cured product at 80 ° C. were not measured. Further, in Formulation Example 9, the value represented by (strength at 20 ° C.−strength at 80 ° C.) / Strength at 20 ° C. is greater than 0.6 for both bending strength and compressive strength, and the temperature of the cured product The intensity change due to is large.

The blend of the present invention has a low viscosity and is excellent in kneading property, coating workability, and material uniformity.
The cured product of the present invention has high strength and excellent physical property stability against strength change due to temperature. Therefore, it is suitable for resin mortar or resin concrete used for civil engineering and construction such as coverings such as floor surfaces, wall surfaces, and road pavement surfaces.

Claims (3)

  Polymer having a methyl methacrylate monomer (A) 60 to 85% by mass and an alkyl (meth) acrylate unit or cycloalkyl (meth) acrylate unit having an alkyl group having 2 or more carbon atoms and a double bond ( B) 100 parts by weight of syrup (X) containing 15 to 40% by weight and 100 parts by weight of the syrup composition (L) containing 0.1 to 5 parts by weight of wax (C). Formulation formed by blending ~ 1500 parts by mass.   The blend according to claim 1, wherein the polymer (B) has an alkyl methacrylate unit or an isobornyl (meth) acrylate unit having an alkyl group having 2 to 4 carbon atoms. A cured product obtained by adding 0.5 to 10 parts by mass of an organic peroxide to 100 parts by mass of the syrup (X) in the composition and curing the compound according to claim 1 or 2. The strength at 20 ° C. is bending strength: 10 N / mm ² or more, compressive strength: 15 N / mm ² or more, and (strength at 20 ° C.−strength at 80 ° C.) / Strength at 20 ° C. = 0. Hardened | cured material which is 5 or less.