JPH0761848A - Curable polymer mortar or concrete composition and cured product obtained by curing these - Google Patents

Abstract

PURPOSE:To obtain a hardenable composition containing a specific polymerizable liquid resin binder, an inorganic powdery filler and an aggregate at specific ratios, having excellent workability and applicability and giving a hardened product having excellent water-resistance. CONSTITUTION:This composition contains (A) a polymerizable liquid resin as a binder composed of an unsaturated urethane expressed by the formula and a vinyl monomer copolymerizable with the unsaturated urethane at an (unsaturated urethane/vinyl monomer) weight ratio of 90/10 to 10/90 and (B) 300-1,150 pts.wt. (based on 100 pts.wt. of the binder) of an inorganic powdery filler and aggregate in total. In the formula, X is residue obtained by removing isocyanate group from polyisocyanate, Y is residue obtained by removing hydroxyl group from trihydric alcohol, A<1> and A<2> are 2-6C and 2-4C alkylene groups, respectively, R<1>, R<2> and R<3> are H or CH3, p and r are integers of 0-2 and at least one of them is not 0, q is integer of 1-3, 2<=p+q+r<=4 and m is integer of 2-5.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable polymer mortar or concrete composition (hereinafter referred to as a polymer mortar / concrete composition), and a cured product obtained by curing these. A polymer mortar / concrete composition using a polymerizable liquid resin containing a radically polymerizable monomer or a macromer as a binder is widely used. For example, a polymer mortar / concrete composition using an unsaturated polyester resin, which is a typical polymerizable liquid resin, is used for construction materials such as floor coatings, paving materials, and precast products. The present invention relates to a polymer mortar-concrete composition using an unsaturated urethane having a specific structure as a binder and a polymerizable liquid resin composed of a vinyl monomer copolymerizable with the unsaturated urethane, and a curing obtained by curing these. It is about things.

[0002]

2. Description of the Related Art Conventionally, polymer mortar / concrete compositions using unsaturated polyester resins as binders (Japanese Patent Publication No. 62-12934 and Japanese Patent Publication No. 62-143916), polyisocyanates and hydroxyalkyl ( What uses a polymerizable liquid resin containing an unsaturated urethane obtained from (meth) acrylate (JP-A-54-33585, JP-A-54-36392,
JP-A-54-36390), a (meth) polyhydric alcohol
What uses a polymerizable liquid resin containing an acrylic acid partial ester and another vinyl monomer (Japanese Patent Publication No. 1-3077).
7, JP-B-3-3623) and the like have been proposed.

However, the above-mentioned conventional polymer mortar-concrete compositions have the following drawbacks. 1) When an unsaturated polyester resin is used as the binder, if an inorganic powder filler or an aggregate is mixed with the binder, the viscosity becomes high, and a resin having good fluidity cannot be obtained. In addition, it takes a long time to cure, resulting in poor workability and workability. 2) When a polymerizable liquid resin containing a (meth) acrylic acid partial ester of a polyhydric alcohol and another vinyl monomer as a binder or the unsaturated polyester resin described above is used, it may be exposed to water for a long time. However, the strength is lowered, and a cured product having excellent water resistance cannot be obtained. 3) The one using a polymerizable liquid resin containing an unsaturated urethane obtained from polyisocyanate and hydroxyalkyl (meth) acrylate as a binder has a high melting point, so that it solidifies or precipitates at a temperature below room temperature. There are restrictions on workability and workability due to the generation of objects.

[0004]

The problem to be solved by the present invention is a drawback of the above-mentioned 1) to 3) in the conventional polymer mortar-concrete composition.

[0005]

However, the present inventors have
To solve the above problems, a polymer mortar using a polymerizable liquid resin containing unsaturated urethane as a binder.
Regarding the concrete composition and the cured product obtained by curing these, the relationship between the chemical structure of the unsaturated urethane and the cured product obtained was studied, and as a result, polyisocyanate having 2 to 4 isocyanate groups was obtained as the unsaturated urethane. It has been found that it is correct and suitable to use those obtained with specific (meth) acrylic ester monools.

That is, the present invention relates to a polymer mortar-concrete composition containing a binder, an inorganic powder filler and an aggregate, wherein the binder is an unsaturated urethane represented by the following formula 1 and A polymerizable liquid resin comprising a vinyl monomer copolymerizable with an unsaturated urethane and having a ratio of the unsaturated urethane / the vinyl monomer = 90/10 to 10/90 (weight ratio). The total amount of the powdery filler and the aggregate is 300 per 100 parts by weight of the binder.
The present invention relates to a polymer mortar-concrete composition characterized by being contained in a proportion of ˜1150 parts by weight and a cured product obtained by curing these.

[0007]

[Formula 1]

[In the formula 1, X: a residue obtained by removing an isocyanate group from polyisocyanate Y: a residue obtained by removing a hydroxyl group from a trivalent alcohol A ¹ : an alkylene group having 2 to 6 carbon atoms A ² : a carbon number 2 To alkylene groups R ¹ , R ² , R ³ : H or CH ₃ p, q, r: p, r are integers of 0 to 2 which are not 0 at the same time, and q is an integer of 1 to 3. And 2 ≦ p + q
+ R ≦ 4 is satisfied m: an integer of 2 to 5]

The unsaturated urethane represented by the formula 1 is a urethane compound obtained by reacting (meth) acrylic ester monool and polyisocyanate as described below.

The above (meth) acrylic ester monool includes alkanetriol di (meth) acrylate derived from (meth) acrylic acid and alkanetriol, and alkanediol derived from (meth) acrylic acid and alkanediol. Mono (meth) acrylate,
Included are polyether diol mono (meth) acrylates derived from (meth) acrylic acid and polyether diols.

Examples of alkanetriol di (meth) acrylate include glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,2,
Such as 6-hexanetriol di (meth) acrylate,
Examples thereof include alkanetriol di (meth) acrylates having 3 to 6 carbon atoms.

As alkanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Examples include alkanediol mono (meth) acrylates having an alkane of 2 to 6 carbon atoms such as 1,6-hexanediol mono (meth) acrylate.

Examples of the polyether diol mono (meth) acrylate include diethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate and pentabutylene glycol mono (meth) acrylate. The mono (meth) acrylate of the polyether diol which added 2-5 mol of C2-C4 alkylene oxide is mentioned.

The polyisocyanates to be reacted with these (meth) acrylic ester monools include di-tetraisocyanates. Examples of the polyisocyanate include 1) aromatic diisocyanates such as various tolylene diisocyanates, diphenyl ether-4,4'-diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, xylene diisocyanate, or diisocyanates having an aromatic group, and 2) dimethylene triisocyanate. Examples thereof include tri- or tetraisocyanates such as phenyltriisocyanate and trimethylenetetraphenyltetraisocyanate, and 3) polymethylenepolyphenylpolyisocyanate having an average of 2 to 4 isocyanate groups in the molecule. Of these polyisocyanates, it is advantageous to use polymethylene polyphenyl polyisocyanates having an average of 2.5 to 3 isocyanate groups.

In the unsaturated urethane used in the present invention,
The selection examples of the (meth) acrylic ester monool to be reacted with polyisocyanate include 1) a combination example of alkanediol mono (meth) acrylate and triol di (meth) acrylate, and 2) alkanediol mono (meth) acrylate and polyether. Diol mono (meta)
Examples of combined use with acrylate, 3) Examples of combined use of alkanediol (meth) acrylate, triol di (meth) acrylate and polyether diol mono (meth) acrylate are included.

In the unsaturated urethane used in the present invention,
The total number of (meth) acryloxy groups contained in the molecule may include from 2 to a maximum of 6, but is preferably from 2 to 4, and when using two or more kinds of unsaturated urethane,
The total number of (meth) acryloxy groups is preferably 2.5 to 3.5 on average. In order to obtain such an unsaturated urethane, the number of isocyanate groups of the polyisocyanate used for its synthesis and the type of the (meth) acrylic ester monool are appropriately selected.

The reaction ratio of polyisocyanate / (meth) acrylic ester monool in the synthesis of unsaturated urethane is preferably 1/1 in terms of functional group molar ratio (NCO / OH). /0.95-0.95/
Even if it fluctuates within the range of 1, there is no particular problem. Usually, in the synthesis of unsaturated urethane, an inert solvent is added to (meth) acrylic ester monool, and a catalyst such as di-n-butyltin dilaurate is further added to the polyisocyanate while maintaining the temperature at 50 to 80 ° C. The method of gradually adding is adopted. In this case, a vinyl monomer such as methyl (meth) acrylate or styrene can be used as the inert solvent.

Vinyl monomers copolymerizable with unsaturated urethane used in the present invention include 1) methyl methacrylate, 2) ethylene glycol diacrylate, propylene glycol dimethacrylate, 1,4-butanediol diacrylate, neo. Alkanediol di (meth) acrylates having 2 to 6 carbon atoms such as pentyl glycol dimethacrylate and 1,6-hexanediol diacrylate, 3) glycerin trimethacrylate, 1,2,6-hexanetriol triacrylate, Such as trimethylolpropane trimethacrylate,
Alkane triol di (meth) acrylates having 3 to 6 carbon atoms, 4) vinyl aromatic hydrocarbons such as styrene, methylstyrene, divinylbenzene and the like, and one or more of these are appropriately used. However, it is preferable to use methyl methacrylate, styrene, or a mixture thereof in view of the physical properties of the resulting cured product.

The binder used in the present invention comprises an unsaturated urethane represented by the formula 1 and a vinyl monomer copolymerizable with the unsaturated urethane, and the unsaturated urethane / the vinyl monomer = 90 / The ratio is 10 to 10/90 (weight ratio), but the unsaturated urethane / the vinyl monomer is preferably 30/70 to 70/30 (weight ratio).

The polymer mortar-concrete composition of the present invention contains an inorganic powder filler. Examples of the inorganic powder filler include calcium carbonate, silica, clay, talc, aluminum hydroxide and the like. The present invention does not particularly limit the particle size, shape, particle size distribution, etc. of the inorganic powder filler, but the average particle size is usually 0.1 μm.
Those having a size of m or more are used, and preferably those having a size of 1 to 100 μm.

The polymer mortar-concrete composition of the present invention contains an aggregate. Examples of such aggregates include fine aggregates such as silica sand, river sand, mountain sand and glass beads, and coarse aggregates such as river gravel and crushed stone. The total content of the inorganic powder filler and the aggregate depends on the type and particle size, the curing method of the polymer mortar / concrete composition prepared using these, the desired physical properties of the cured product obtained, and the like. ,
It is 300 to 1150 parts by weight per 100 parts by weight of the binder.

Although the present invention does not particularly limit the content ratio of the inorganic powder filler to the binder, the ratio of the inorganic powder filler is usually inorganic powder filler / binder = 1/3.
~ 3/1 (weight ratio) is preferable, and 1/2 ~ 2 /
More preferably, it is 1 (weight ratio).

Also in the polymer mortar-concrete composition of the present invention, if the content ratio of the inorganic powder filler and the aggregate is increased, the viscosity is inevitably increased and the fluidity is lowered. In order to keep the fluidity of the prepared polymer mortar / concrete composition high and improve the workability and workability, an anionic polymer surfactant represented by the following formula 2 is used as a viscosity reducing agent. Is preferred.

[0024]

[Formula 2] [In Formula 2, R: a hydrocarbon group selected from an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, and a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms; A: the number of repeating oxyalkylene units Is a residue obtained by removing a hydroxyl group from a polyether diol having a molecular weight of 5 to 100, and the oxyalkylene unit is composed of only oxypropylene units or both 50 mol% or more oxypropylene units and 50 mol% or less oxyethylene units. Which is a residue M: H or a monovalent base m, n: 1 or 2, and satisfying m + n = 3]

In the formula 2, A is a residue (hereinafter referred to as diol residue) obtained by removing a hydroxyl group from polyether diol. In this case, the polyether diol has a repeating number of oxyalkylene units of 5 to 100, preferably 1
The polyether diol of 5 to 60, wherein the oxyalkylene unit comprises only oxypropylene unit or both 50 mol% or more oxypropylene unit and 50 mol% or less oxyethylene unit.

As the hydrocarbon group for blocking one end of the polyether diol, 1) an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, isopropyl group, butyl group and hexyl group, 2) cyclohexyl group, 3) phenyl group,
4) A phenyl group substituted with an alkyl group having 1 to 4 carbon atoms such as a methylphenyl group and an isobutylphenyl group. Of these, an alkyl group having 1 to 4 carbon atoms is preferable.

As a method for producing a polyether diol having one end blocked with a hydrocarbon group, a known method can be applied.
For example, a polyoxyalkylene diol having one end blocked with an alkyl group or a phenyl group is prepared by successively adding a predetermined number of moles of 1,2-alkylene oxide to 1 mole of alcohol or phenol in the presence of a basic catalyst. There is a way to get.

The anionic polymer surfactant represented by the formula 2 is a phosphoric acid ester, and 1) an acidic phosphoric acid monoester in which 1 mol of a polyether diol having one end blocked is ester-bonded with phosphoric acid, 2) An acidic phosphoric acid diester in which 2 mol of a polyether diol having one end blocked and an ester bond with phosphoric acid are included. 3) A phosphoric acid ester salt obtained by neutralizing these acidic phosphoric acid esters with a basic compound is included. It As a method for producing such a phosphoric acid ester, a known method can be applied. For this, for example, 1) a method of obtaining 2 mol of acidic phosphoric acid monoester by reacting 2 mol of polyether diol with one end blocked, 1 mol of water and 1 mol of phosphorus pentoxide, 2) blocking one end Method of reacting 3 mol of polyether diol and 1 mol of phosphorus pentoxide to obtain 1 mol of acidic phosphoric acid monoester and 1 mol of acidic phosphoric acid diester, 3) 2 mol of polyether diol with one end blocked and oxychlorination There is a method in which 1 mol of phosphorus is reacted and then hydrolyzed to obtain 1 mol of acidic phosphoric acid diester. The phosphate ester salt can be obtained by neutralizing the acidic phosphoric acid monoester or acidic phosphoric acid diester with a basic compound. The basic compounds used for neutralization include 1) inorganic basic compounds such as sodium hydroxide, potassium hydroxide and lithium hydroxide, 2) ammonia, monoethanolamine, diethanolamine, triethanolamine, alkylamines and quaternary compounds. Examples thereof include organic basic compounds such as ammonium hydroxide and phosphonium hydroxide. Among these phosphoric acid esters, acidic phosphoric acid esters are preferable, and above all, acidic phosphoric acid monoesters are 70
It is preferable that the acidic phosphoric acid diester is 30 mol% or less in the mol% or more.

In the present invention, the content ratio of the viscosity reducing agent is 0.001 to 5 parts by weight per 100 parts by weight of the total amount of the inorganic powder filler and the aggregate, but 0.00
It is preferable that the amount is 5 to 2 parts by weight. The viscosity reducing agent is a polymer mortar-concrete composition containing the binder in a low proportion of 15% by weight or less, and further 10% by weight or less, with respect to the total amount of the inorganic powder filler and the aggregate. It is especially effective when applied to.

In the polymer mortar-concrete composition of the present invention, it is preferable to use a thermoplastic polymer as a curing shrinkage reducing agent for the purpose of preventing shrinkage due to curing and obtaining a cured product with high dimensional accuracy. Examples of such thermoplastic polymers include 1) polyalkyl (meth) acrylates obtained by polymerizing methyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, etc., 2) polyneopentyl adipate, polypropylene adipate, poly ε-caprolactone, etc. Saturated aliphatic polyester, 3) polystyrene, styrene-butadiene copolymer, styrene-divinylbenzene copolymer, styrene-
Examples thereof include vinyl aromatic hydrocarbon polymers such as acrylonitrile copolymer and vinyl copolymers containing vinyl aromatic hydrocarbon as a monomer component.

The thermoplastic polymer used as the curing shrinkage reducing agent is preferably one having compatibility with the polymerizable liquid resin used as the binder and having a glass transition temperature of 80 ° C. or lower, among which an alkyl group is preferable. Is preferably a polyalkyl (meth) acrylate having 1 to 8 carbon atoms, and more preferably a polyalkylmethacrylate having an alkyl group having 2 to 6 carbon atoms. The present invention does not particularly limit the content ratio of the thermoplastic polymer used as the curing shrinkage reducing agent, but the thermoplastic polymer is usually 1 to 50 parts by weight per 100 parts by weight of the binder, and preferably It should be 3 to 15 parts by weight.

In the present invention, aluminum hydroxide is used as the inorganic powder filler in an amount of 100 parts by weight per 100 parts by weight of the binder.
~ 300 parts by weight, preferably used in a proportion of 200 to 300 parts by weight, it is possible to impart excellent flame retardancy to the obtained cured product, further using a reinforcing fiber such as an inorganic fiber or a metal fiber, The resulting cured product can be provided with heat-resistant shape-retaining properties that prevent cracking and deformation due to flames. Examples of such reinforcing fibers are 1) glass fibers,
Inorganic fibers such as alumina fibers, carbon fibers, and titanic acid fibers,
2) Metal fibers such as steel, aluminum and copper can be used. The reinforcing fibers are used in the polymer mortar-concrete composition in an amount of 1 to 20% by volume.

Further, when a flame retardant is used, it is possible to impart particularly excellent flame retardancy to the obtained cured product. As the flame retardant, it is preferable to use a phosphorus compound,
A specific example is red phosphorus. The phosphorus compound used as the flame retardant is used in a proportion of 1 to 50 parts by weight as phosphorus atoms per 100 parts by weight of the binder, but 10 to 5 parts by weight.
It is preferable to use it in a proportion of 0 parts by weight.

A preferred embodiment for imparting flame retardancy to the obtained cured product is 200 to 300 parts by weight of aluminum hydroxide as an inorganic powder filler per 100 parts by weight of the binder, or a phosphorus compound. 10 as the phosphorus atom
It is a case where it is contained at a ratio of 50 parts by weight, and inorganic fibers or metal fibers as reinforcing fibers are contained in the polymer mortar-concrete composition at a ratio of 5 to 20% by volume. The polymer mortar-concrete composition for obtaining such a cured product has a high viscosity and deteriorates workability. Therefore, in order to improve this, an anionic polymer surfactant as described above is contained as a viscosity reducing agent. Is preferred, whereby a flame-retardant polymer mortar-concrete composition having excellent workability can be obtained.

The cured product of the present invention is obtained by curing the polymer mortar-concrete composition as described above in the presence of a curing agent. For the preparation of the polymer mortar-concrete composition of the present invention, known formulations provided for the polymer mortar-concrete composition containing a polymerizable liquid resin can be applied. Further, as the curing method, the known formulation provided for the polymer mortar-concrete composition can be applied.
For example, radical polymerization can be performed using various curing agents and curing accelerators.

As such a curing agent, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, 1,1-di-
Examples thereof include t-butylperoxy-3,3,5-trimethylcyclohexane and bis (4-t-butylcyclohexyl) peroxydicarbonate, which may be used alone or in a mixture of two or more. Further, as the curing accelerator, tertiary amines such as cobalt naphthenate, N, N-dimethyl-p-toluidine, N, N-dimethylaniline and the like can be mentioned. The use ratio of the curing agent varies depending on the curing temperature, but is usually 0.1 to 5% by weight with respect to the binder. When the polymer mortar / concrete composition is cured at room temperature, the type and amount of the curing agent and the curing accelerator are determined so that the pot life of the binder is usually 20 to 60 minutes at room temperature. It is preferable.

The polymer mortar-concrete composition of the present invention can be applied to the production of precast products, floor coating, construction of pavement and the like. Examples are given below in order to make the constitution and effects of the present invention more specific, but the present invention is not limited to these examples. In the following Examples and the like, parts are parts by weight and% is% by weight, unless otherwise specified.

[0038]

【Example】

Test Category 1 (Synthesis of unsaturated urethane and preparation of polymerizable liquid resin) Synthesis of unsaturated urethane a and preparation of polymerizable liquid resin A 544 parts of methyl methacrylate, 260 parts of 2-hydroxyethyl methacrylate (2.0 mol), Take 174 parts (1.0 mol) of diethylene glycol monomethacrylate and 2 parts of di-n-butyltin dilaurate, hold at 50 ° C. and stir, and further add polymethylene polyphenyl polyisocyanate (average of 3 isocyanates in 1 molecule). 382 parts (containing a group) (1.0 mol) was added dropwise over 40 minutes. At this time, the reaction heat was generated, but the reaction temperature was kept at 60 ° C or lower. Then, the temperature was maintained at 60 ° C. for 1 hour to complete the synthesis. A polymerizable liquid resin A containing 60% of unsaturated urethane a was obtained. The polymerizable liquid resin A thus obtained was allowed to stand at 20 ° C. for 24 hours, but no precipitation of unsaturated urethane a was observed.

As in the case of the unsaturated urethane a and the polymerizable liquid resin A, the polymerizable liquid resins B and C containing 60% of each of the unsaturated urethane b or c and the unsaturated urethane d or e of 55 are respectively prepared. % Of polymerizable liquid resins D and E were obtained. The resulting polymerizable liquid resins B to E were allowed to stand at 20 ° C. for 24 hours, but no precipitation of unsaturated urethane b to e was observed.

Synthesis of unsaturated urethane r-1 and preparation of polymerizable liquid resin R-1 2-hydroxyethyl methacrylate 390 parts (3.0
Mol), 515 parts of methyl methacrylate, 3 parts of di-n-butyltin dilaurate, and 382 parts (1.0 mol) of polymethylene polyphenyl polyisocyanate (containing an average of 3 isocyanate groups in one molecule) (1.0 mol). Similar to the case of the saturated urethane a and the polymerizable liquid resin A, the polymerizable liquid resin R-1 containing 60% of the unsaturated urethane r-1.
Got The resulting polymerizable liquid resin R-1 was added at 20 ° C. for 24 hours.
When left for a long time, a large amount of a precipitate of unsaturated urethane r-1 was generated.

Unsaturated urethane r-2 was added in the same manner as in the case of unsaturated urethane r-1 and polymerizable liquid resin R-1.
A polymerizable liquid resin R-2 containing 0% was obtained. When the resulting polymerizable liquid resin R-2 was allowed to stand at 20 ° C. for 1 hour, a large amount of unsaturated urethane r-2 precipitates were generated.

Table 1 shows the types of polyisocyanates, (meth) acrylic ester monools and vinyl monomers used in the preparation of the polymerizable liquid resins A to R-2, and their amounts used.

[0043]

[Table 1]

In Table 1, numerical values of the amounts used in the table: upper part is part, lower part () is mol * 1: alkanediol mono (meth) acrylate * 2: polyether diol mono (meth) acrylate * 3: triol di ( (Meth) acrylate PMI-3: Polymethylene polyphenyl polyisocyanate (3 NCO groups) PMI-2.5: Polymethylene polyphenyl polyisocyanate (2.5 NCO groups on average) MPI: Methylene bisphenyl isocyanate HEMA: 2- Hydroxyethyl Methacrylate HPMA: 2-Hydroxypropyl Methacrylate DEMA: Diethyl Glycol Monomethacrylate DPMA: Dipropylene Glycol Monomethacrylate GDM: Glycerine Dimethacrylate MMA: Methyl Methacrylate ST: Sty Down TPMA: trimethylol propane trimethacrylate

Test Category 2 (Preparation of polymer mortar composition and its evaluation) Preparation of polymer mortar composition Binder / filler / aggregate was prepared in accordance with JIS A1181 (Method of preparing test specimen for strength test of polymer resin concrete). 100/200/500 (each part by weight) of the polymer mortar composition shown in Table 2 and 100/200/800 (each part by weight) of the binder / filler / aggregate content shown in Table 3 And a polymer mortar composition were prepared.
The materials used here are as follows. For the measurement of slump and slump flow, one containing no curing agent and no curing accelerator was prepared.

Materials used Binder: The one shown in Table 2 and Table 3 was used. Filler: Heavy calcium carbonate (particle size 2.5 μm or less, specific gravity 2.70, water content 0.1% or less) was used. Aggregate: As fine aggregate, No. 4 silica sand (particle size 0.70 to 1.
17 mm, specific gravity 2.51, water content 0.1% or less) and an equivalent mixture of No. 7 silica sand (particle size 0.05 to 0.21 mm, specific gravity 2.51, water content 0.1% or less) (weight) Ratio) used Viscosity reducing agent: used those shown in Tables 2 and 3 Curing shrinkage reduction agent: used those shown in Table 3 Curing agent: used those shown in Tables 2 and 3 Curing accelerator: The one shown in Table 2 and Table 3 was used. The amount of the curing agent and the curing accelerator used depends on the pot life of the binder at 20 ° C. (JIS K6833 (general test method for adhesives)). } Is set to 35 ± 5 minutes.

Slump and Slump Flow Test A slump test was conducted according to JIS A1173 (polymer mortar slump test method). still,
As the flat plate, a glass plate (specified in JIS R3202 (float, polishing plate)) having a scale-attached tape attached to the back surface was used. During the slump test, the slump was measured when the flow was stopped after the slump cone was pulled up. In addition, the spread of the bottom at the same point was read on the glass plate, and the result was taken as a slump flow. The test results are shown in Tables 2 and 3.

[0048]

[Table 2]

[0049]

[Table 3]

In Tables 2 and 3, the numerical values of the amounts used: Part A to E, R-1, R-2: those prepared in Test Category 1 Note that R-1 and R-2 have precipitates. R-3: unsaturated polyester resin of orthophthalic acid type unsaturated polyester / styrene = 50/50 (weight ratio) R-4: trimethylolpropane dimethacrylate 60
Parts of 40 parts of methyl methacrylate mixed and dissolved in a polymerizable liquid resin P-1: butoxypolyoxypropylene (16 mol) /
Polyoxyethylene (9 mol) glycol acidic phosphoric acid ester {monoester / diester = 90/10 (molar ratio)} P-2: methoxypolyoxypropylene (30 mol) glycol acidic phosphoric acid ester {monoester / diester = 75 / 25 (molar ratio)} P-3: phenoxypolyoxypropylene (50 mol)
Glycol phosphate ester diethanolamine salt {monoester / diester = 55/45 (molar ratio)} S-1: polyisobutyl methacrylate (number average molecular weight 50000) S-2: polyethyl acrylate (number average molecular weight 450
00) BPO: Dibenzoyl peroxide * 4: Methyl ethyl ketone peroxide DMT: N, N-dimethyl-p-toluidine NaCo: Cobalt naphthenate * 5: Binder generated due to separation of binder * 6: High viscosity, Samples for evaluation could not be prepared because uniform kneading was not possible.

Test Category 3 (Preparation of Hardened Mortar and Evaluation of Its Strength, etc.) Preparation of Specimen The polymer mortar compositions shown in Tables 2 and 3 prepared in Test Category 2 were measured according to JIS A1181 to have a size of 40 ×.
The test pieces were molded into 40 × 160 mm, dried and cured at 20 ° C. × 50% RH for 28 days, and dried and cured at 20 ° C. × 50% RH for 1 day and then heat cured at 70 ° C. for 15 hours.

Test method Compressive strength Using a folded piece of a beam subjected to a bending strength test, JIS A
Bending Strength Performed According to 1183 (Compressive Strength Testing Method for Polyester Resin Concrete by Folded Beams) The test results performed according to the bisection loading method of JIS A1184 (Testing method for bending strength of polyester resin concrete) are shown in Table 4. And shown in Table 5.

The rate of change in length of the polymer mortar composition shown in Table 3 prepared in Test Category 2 during curing was measured according to JIS A1129 (Method for testing length change of mortar and concrete). The test results are shown in Table 5.

[0054]

[Table 4]

[0055]

[Table 5]

In Table 5, * 7: Since the polymer mortar composition was inhomogeneous, a cured product was not prepared. In the rate of change in length, a minus sign indicates shrinkage.

Test Category 4 (Evaluation of Water Resistance of Cured Polymer Mortar) Water resistance was evaluated by the following test method using the cured polymer mortar of Table 4 obtained in Test section 3 as a test sample. Test method Weight of the specimen immersed in water at 20 ° C. for 28 days,
The compressive strength and the bending strength were measured, and the water absorption rate and the strength ratio were calculated as follows from the respective measured values of the specimen before immersion. Water absorption rate (%) = (weight increase due to immersion / weight of specimen before immersion) x 100 Compression or bending strength ratio (%) = (compression or bending strength of specimen after immersion / of specimen before immersion) Compressive or bending strength) x 1
The results of the 00 test are shown in Table 6.

[0058]

[Table 6]

Test Category 5 (Preparation of Polymer Mortar Composition, Preparation of Cured Product and Evaluation thereof) Preparation of Polymer Mortar Composition A polymer mortar composition having the contents shown in Table 7 was prepared according to JIS A1181. The materials used here are as follows.

Materials used Binder: The one shown in Table 7 was used Filler: The one shown in Table 7 was used Aggregate: No. 4 silica sand and 7 as used in Test Category 2
Flame retardant: Red phosphorus was used, using an equal mixture of No. silica sand Reinforcing fiber: Steel fiber {0.5 × 0.5 × 30 mm, specific gravity (20 ° C) 7.8, yield point 19.0 Kg / mm ² , tensile strength 32.0 Kg / mm ² } was used

Evaluation of Kneadability and Fillability of Polymer Mortar Composition The difficulty of kneadability and filling ability of the prepared polymer mortar composition into a mold was qualitatively evaluated. The results are shown in Table 8.

Preparation of Cured Product According to JIS A1181, each polymer mortar composition was molded into a size of 220 × 220 × 15 mm and then at 20 ° C. ×
Dry curing was performed at 50% RH for 24 hours, and then heat curing was performed at 70 ° C. for 15 hours to prepare three cured products of each formulation, and these were used as test pieces and subjected to the following flame retardancy test.

Flame Retardancy Test A surface test of Class 3 flame retardancy specified in Ministry of Construction Notification No. 1231, JIS A1321 (flame retardancy test method for building interior materials and construction method) was performed. The results are shown in Table 9.
All results are the average of three tests.

[0064]

[Table 7]

In Table 7, the amount used: parts, but in the case of reinforcing fibers, the volume% A, E, R-3: those prepared in Test Category 1 F-1: Aluminum hydroxide {average particle size 2.0 μm , Specific gravity (20 ° C.) 2.45, water content 0.1% or less} F-2: heavy calcium carbonate {average particle size 2.5 μm or less, specific gravity (20 ° C.) 2.70, water content 0.1% Below} CoOc: Cobalt octenoate A, E, R-3, P-1, P-2, BPO, * 4, DM
T: Same as shown in Tables 2 and 3

[0066]

[Table 8]

[0067]

[Table 9]

In Table 9, the width of cracks in Comparative Example 10: Since the test results have a large variation, the values are shown as the minimum value to the maximum value.

[0069]

As is apparent from the above, according to the present invention described above, workability and workability that contain a polymerizable liquid resin having excellent stability, which does not cause solidification or precipitation at room temperature, as a binder. The polymer mortar / concrete composition having excellent water resistance can be obtained, and a cured product having excellent water resistance can be obtained by curing the polymer mortar / concrete composition.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ouzaki ▼ Tatsuhiko 6-74, Eiraku-cho, Nishio-shi, Aichi (72) Inventor Junji Kodama 67 Hen-cho, Hanemachi, Okazaki-shi, Aichi

Claims (9)

[Claims] 1. A curable polymer mortar or concrete composition containing a binder, an inorganic powder filler and an aggregate, wherein the binder is an unsaturated urethane represented by the following formula 1 and the unsaturated urethane: Consisting of a vinyl monomer copolymerizable with a saturated urethane and the unsaturated urethane / the vinyl monomer = 9
It is a polymerizable liquid resin having a ratio of 0/10 to 10/90 (weight ratio), and the total amount of the inorganic powder filler and the aggregate is 300 to 115 per 100 parts by weight of the binder.
A curable polymer mortar or concrete composition, characterized in that it is contained in an amount of 0 part by weight. [Formula 1] [In Formula 1, X: Residue obtained by removing isocyanate group from polyisocyanate Y: Residue obtained by removing hydroxyl group from trivalent alcohol A ¹ : Alkylene group having 2 to 6 carbon atoms A ² : C ^{2 to} 4 carbon atom The alkylene groups R ¹ , R ² , R ³ : H or CH ₃ p, q, r: p, r are integers of 0 to 2 which are not 0 at the same time, and q is an integer of 1 to 3, and 2 ≦ p + q
+ R ≦ 4 is satisfied m: an integer of 2 to 5] 2. The vinyl monomer copolymerizable with unsaturated urethane is methyl methacrylate or alkane having 2 carbon atoms.
To 6 are alkanediol di (meth) acrylates, alkane triol tri (meth) acrylates in which the alkane has 3 to 6 carbon atoms, and one or more vinyl monomers selected from vinyl aromatic hydrocarbons. Item 2. The curable polymer mortar or concrete composition according to Item 1. 3. The curable polymer mortar according to claim 1, wherein the ratio of the binder and the inorganic powder filler is binder / inorganic powder filler = 3/1 to 1/3 (weight ratio). Or a concrete composition. 4. An anionic polymer surfactant represented by the following formula 2 is added as a viscosity reducing agent in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the total amount of the inorganic powder filler and the aggregate. The curable polymer mortar or concrete composition according to claim 1, 2 or 3, which is contained in a ratio. [Formula 2] [In Formula 2, R: a hydrocarbon group selected from an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, and a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms; A: the number of repeating oxyalkylene units Is a residue obtained by removing a hydroxyl group from a polyether diol having a molecular weight of 5 to 100, and the oxyalkylene unit is composed of only oxypropylene units or both 50 mol% or more oxypropylene units and 50 mol% or less oxyethylene units. Which is a residue M: H or a monovalent base m, n: 1 or 2, and satisfying m + n = 3] 5. The curing shrinkage reducing agent is further selected from polyalkyl (meth) acrylates, saturated aliphatic polyesters, vinyl aromatic hydrocarbon polymers and vinyl copolymers containing vinyl aromatic hydrocarbons as monomer components. The curable polymer mortar or concrete composition according to claim 1, 2, 3 or 4, which comprises 1 to 50 parts by weight of 100 or more parts by weight of one or more thermoplastic polymers described above. 6. The curable polymer mortar or concrete composition according to claim 5, wherein the thermoplastic polymer is a polyalkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms. 7. The inorganic powder filler is aluminum hydroxide, containing 100 to 300 parts by weight of aluminum hydroxide per 100 parts by weight of the binder, and further selected from inorganic fibers and metal fibers. The curable polymer mortar or the concrete composition according to claim 1, 2, 3, 4, 5 or 6, which contains one or two or more kinds of reinforcing fibers in a proportion of 1 to 20% by volume in the whole. 8. The curable polymer mortar or concrete composition according to claim 7, which further contains a phosphorus compound as a flame retardant in a proportion of 1 to 50 parts by weight per 100 parts by weight of the binder as a phosphorus atom. 9. A cured product obtained by curing the curable polymer mortar or concrete composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8.