JP2754330B2 - Curable polymer mortar or concrete composition and cured product obtained by curing these - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable polymer mortar or concrete composition (hereinafter referred to as "polymer mortar / concrete composition") and a cured product obtained by curing these. A polymer mortar / concrete composition using a polymerizable liquid resin containing a radical polymerizable monomer or 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 covering materials, paving materials, and precast products. The present invention relates to a polymer mortar / concrete composition using, as a binder, a polymerizable liquid resin comprising an unsaturated urethane having a specific structure and a vinyl monomer copolymerizable with the unsaturated urethane, and a cured material obtained by curing these. It is about things.

[0002]

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

However, the above-mentioned conventional polymer mortar / concrete composition has the following disadvantages. 1) In the case of using an unsaturated polyester resin as the binder, when an inorganic powdery filler or an aggregate is mixed with the binder, the viscosity becomes high and a material 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 above-mentioned unsaturated polyester resin is used for a long time in contact with water, , Strength is reduced, and a cured product having excellent water resistance cannot be obtained. 3) Those using a polymerizable liquid resin containing an unsaturated urethane obtained from a polyisocyanate and a hydroxyalkyl (meth) acrylate as a binder may solidify at room temperature or lower or generate a precipitate. Therefore, there are restrictions on workability and workability.

[0004]

The problem to be solved by the present invention is the disadvantages 1) to 3) in the conventional polymer mortar / concrete composition.

[0005]

Means for Solving the Problems Thus, the present inventors have
In order to solve the above problems, a polymer mortar using a polymerizable liquid resin containing unsaturated urethane as a binder is used.
As a result of studying the relationship between the chemical structure of the unsaturated urethane and the obtained cured product for the concrete composition and the cured product obtained by curing the same, a polyisocyanate having 2 to 4 isocyanate groups as the unsaturated urethane was obtained. It has been found that it is correct and preferred to use those obtained from specific (meth) acrylic ester monols.

That is, the present invention is a polymer mortar / concrete composition comprising a binder, an inorganic powdery filler and an aggregate, wherein the binder is an unsaturated urethane represented by the following formula (1): A polymerizable liquid resin comprising a vinyl monomer copolymerizable with unsaturated urethane and 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 about 1150 parts by weight and a cured product obtained by curing these compositions.

[0007]

(Equation 1)

In the formula 1, X: diphenyl ether-4,4'-diisocyanate
G, diphenylmethane diisocyanate, tolylene diisocyanate
Socyanate, xylene diisocyanate, dimethylene
Triphenyl triisocyanate, trimethylene tetra
Phenyltetraisocyanate or isocyane in the molecule
Polymethylene polyphenyl having an average of 2 to 4 phosphate groups
Residue obtained by removing isocyanate groups from polyisocyanate Y: Residue obtained by removing hydroxyl groups from trihydric alcohol A¹: Alkylene group having 2 to 6 carbon atoms A^Two: An alkylene group R having 2 to 4 carbon atoms¹, R^Two, R^Three: H or CH_Three  p, q, r: p and r are integers of 0 to 2 that are not simultaneously 0.
Q is an integer of 1 to 3, and 2 ≦ p + q
M satisfying + r ≦ 4: integer of 2 to 5

The unsaturated urethane represented by the formula 1 is a urethane compound obtained by reacting a (meth) acrylic ester monol with a polyisocyanate as described later.

The (meth) acrylic ester monol includes alkanetriol di (meth) acrylate derived from (meth) acrylic acid and alkanetriol, and alkanediol derived from (meth) acrylic acid and alkanediol. Mono (meth) acrylate,
Polyether diol mono (meth) acrylate derived from (meth) acrylic acid and polyether diol is included.

The alkanetriol di (meth) acrylate includes glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,2,2
Such as 6-hexanetriol di (meth) acrylate;
An alkanetriol di (meth) acrylate having 3 to 6 carbon atoms in the alkane is exemplified.

Alkanediol mono (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Alkane diol mono (meth) acrylates having 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. Monoether (meth) acrylate of polyether diol to which 2 to 5 moles of alkylene oxide having 2 to 4 carbon atoms are added.

The polyisocyanates to be reacted with these (meth) acrylic ester monols include di-tetraisocyanates. Examples of the polyisocyanate include diphenyl ether-4,4'-diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, xylene diisocyanate, dimethylene triphenyl triisocyanate, trimethylene tetraphenyl tetraisocyanate, and an average of 2 to 4 isocyanate groups in the molecule. Having polymethylene polyphenyl polyisocyanate. Among these polyisocyanates, isocyanate groups average 2.
Preference is given to using polymethylene polyphenyl polyisocyanates having 5 to 3 polymethylene polyphenyl polyisocyanates.

In the unsaturated urethane used in the present invention,
Examples of selection of (meth) acrylic ester monool to be reacted with polyisocyanate include 1) an example of a combination of alkanediol mono (meth) acrylate and trioldi (meth) acrylate, and 2) an alkanediol mono (meth) acrylate and polyether. Diol mono (meta)
Examples of combined use with acrylates and 3) Examples of combined use of alkanediol (meth) acrylate, trioldi (meth) acrylate and polyetherdiol 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 at most 6, but is preferably 2 to 4, and when two or more unsaturated urethanes are used,
It is preferable that the total number of (meth) acryloxy groups is 2.5 to 3.5 on average. In order to obtain such an unsaturated urethane, the number of isocyanate groups of the polyisocyanate used in the synthesis and the type of the (meth) acrylic ester monool are appropriately selected.

In the synthesis of unsaturated urethane, the reaction ratio of polyisocyanate / (meth) acrylic ester monol is preferably set at 1/1 in terms of a functional group molar ratio (NCO / OH). /0.95-0.95/
Even if it fluctuates in 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 monol, and a catalyst such as di-n-butyltin dilaurate is added. Is gradually added. In this case, a vinyl monomer such as methyl (meth) acrylate or styrene can be used as the inert solvent.

The vinyl monomers copolymerizable with the unsaturated urethane used in the present invention include 1) methyl methacrylate, 2) ethylene glycol diacrylate, propylene glycol dimethacrylate, 1,4-butanediol diacrylate, Alkanediol di (meth) acrylates having 2 to 6 carbon atoms in the alkane, 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) acrylate having 3 to 6 carbon atoms of alkane, 4) vinyl aromatic hydrocarbons such as styrene, methyl styrene, divinyl benzene and the like, and one or more of these are used appropriately. However, it is preferable to use methyl methacrylate, styrene, or a mixture thereof in view of the physical properties of the obtained 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 ratio of the unsaturated urethane / the vinyl monomer = 90 / The ratio of 10 to 10/90 (weight ratio) is preferable, and the ratio of the unsaturated urethane / vinyl monomer = 30/70 to 70/30 (weight ratio) is preferable.

The polymer mortar / concrete composition of the present invention contains an inorganic powdery filler. Examples of such an inorganic powdery 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 powdery filler, but the average particle size is usually 0.1 μm.
m or more, preferably 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 powdery filler and the aggregate depends on the kind and particle size, the curing method of the polymer mortar / concrete composition prepared using these, the physical properties desired for the obtained cured product, and the like. ,
300 to 1150 parts by weight per 100 parts by weight of the binder.

In the present invention, the content ratio of the inorganic powdery filler to the binder is not particularly limited, but the ratio of the inorganic powdery filler / the binder is usually 1/3.
To 3/1 (weight ratio), preferably 1/2 to 2 /
More preferably, it is set to 1 (weight ratio).

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

[0024]

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

Examples of the hydrocarbon group which blocks one end of the polyether diol include 1) an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a butyl group and a hexyl group; 2) a 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. Among them, an alkyl group having 1 to 4 carbon atoms is preferable.

A known method can be applied as a method for producing a polyether diol having one end blocked with a hydrocarbon group.
For example, a polyoxyalkylene diol having one end blocked with an alkyl group or a phenyl group by successively adding a predetermined number of moles of 1,2-alkylene oxide to one 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, which includes 1) an acidic phosphoric acid monoester in which one mole of a polyether diol having one end blocked is ester-bonded to phosphoric acid; 2) acidic phosphoric acid diester in which 2 mol of polyether diol having one end blocked is ester-bonded to phosphoric acid; 3) phosphoric acid ester salt obtained by neutralizing the acidic phosphoric acid ester with a basic compound. You. Known methods can be applied as a method for producing such a phosphate ester. This includes, for example, 1) a method of reacting 2 mol of polyetherdiol, one end of which is blocked, 1 mol of water, and 1 mol of phosphorus pentoxide to obtain 2 mol of acidic phosphoric acid monoester, and 2) closing one end. Method of reacting 3 mol of polyether diol with 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 having one end blocked and oxychloride There is a method of reacting with 1 mol of phosphorus and then hydrolyzing to obtain 1 mol of acidic phosphoric diester. The phosphoric acid ester salt can be obtained by neutralizing such acidic phosphoric acid monoester or acidic phosphoric acid diester with a basic compound. Basic compounds used for neutralization include 1) inorganic basic compounds such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; 2) ammonia, monoethanolamine, diethanolamine, triethanolamine, alkylamine, and quaternary. Organic basic compounds such as ammonium hydroxide and phosphonium hydroxide are exemplified. Among these phosphate esters, acidic phosphate esters are preferred, and particularly, acidic phosphate monoesters are preferred.
It is preferable that the acidic phosphoric acid diester has a ratio of not less than 30% by mole.

In the present invention, the content 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 powdery filler and the aggregate.
It is preferred that the amount be 5 to 2 parts by weight. Such a viscosity reducing agent is a polymer mortar / concrete composition containing a binder in a low proportion of 15% by weight or less, and even 10% by weight or less, based on the total amount of the inorganic powdery filler and the aggregate. This is particularly effective when applied to

The polymer mortar / concrete composition of the present invention preferably uses a thermoplastic polymer as a curing shrinkage reducing agent for the purpose of preventing shrinkage due to curing and obtaining a cured product having high dimensional accuracy. Examples of such thermoplastic polymers include: 1) polyalkyl (meth) acrylate obtained by polymerizing methyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, and the like; 2) polyneopentyl adipate, polypropylene adipate, poly ε-caprolactone, and the like. Saturated aliphatic polyester, 3) polystyrene, styrene-butadiene copolymer, styrene-divinylbenzene copolymer, styrene-
Examples thereof include a vinyl aromatic hydrocarbon polymer such as an acrylonitrile copolymer and a vinyl copolymer containing a vinyl aromatic hydrocarbon as a monomer component.

As the thermoplastic polymer used as the curing shrinkage reducing agent, those having compatibility with the polymerizable liquid resin used as the binder and having a glass transition temperature of 80 ° C. or less are preferable. Is preferably a polyalkyl (meth) acrylate having 1 to 8 carbon atoms, and more preferably a polyalkyl methacrylate 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, preferably It should be 3 to 15 parts by weight.

In the present invention, aluminum hydroxide is used as the inorganic powdery filler in an amount of 100 parts by weight per 100 parts by weight of the binder.
-300 parts by weight, preferably when used in a proportion of 200-300 parts by weight, it is possible to impart excellent flame retardancy to the obtained cured product, further using inorganic fibers and metal fibers and other reinforcing fibers, The resulting cured product can be provided with heat-resistant shape retention for preventing the occurrence of cracks and deformation due to flame. As such reinforcing fibers, 1) glass fibers,
Inorganic fiber such as alumina fiber, carbon fiber, titanate fiber,
2) Metal fibers such as steel, aluminum, copper and the like. Such reinforcing fibers are used in a proportion of 1 to 20% by volume in the polymer mortar / concrete composition.

In addition, when a flame retardant is used, a particularly excellent flame retardancy can be imparted to the obtained cured product. As such a flame retardant, it is preferable to use a phosphorus compound,
Specific examples include red phosphorus. The phosphorus compound used as a flame retardant is used in an amount of 1 to 50 parts by weight per 100 parts by weight of a binder as a phosphorus atom.
It is preferable to use it so that the ratio is 0 parts by weight.

A preferred embodiment for imparting flame retardancy to the obtained cured product is, for example, 200 to 300 parts by weight of aluminum hydroxide as an inorganic powdery filler or a phosphorus compound per 100 parts by weight of a binder. As a phosphorus atom
In this case, the content is 50 parts by weight, and inorganic fibers and metal fibers are contained as reinforcing fibers in the polymer mortar / concrete composition at a ratio of 5 to 20% by volume. Since the polymer mortar / concrete composition for obtaining such a cured product has a high viscosity and deteriorates workability, it is preferable to include an anionic polymer surfactant as described above as a viscosity reducing agent to improve the viscosity. 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 above-described polymer mortar / concrete composition in the presence of a curing agent. In preparing 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. In addition, a known formulation provided for the polymer mortar / concrete composition can be applied to the curing method.
For example, radical polymerization can be performed using various curing agents and curing accelerators.

Examples of the curing agent include benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, 1,1-di-
Examples include t-butylperoxy-3,3,5-trimethylcyclohexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, and these can be used alone or in a mixture of two or more. Examples of the curing accelerator include tertiary amines such as cobalt naphthenate, N, N-dimethyl-p-toluidine, and N, N-dimethylaniline. The proportion of the curing agent used depends on the curing temperature, but is usually 0.1 to 5% by weight based on the binder. When the polymer mortar / concrete composition is cured at room temperature, the type and amount of the curing agent and curing accelerator are determined so that the pot life of the binder at room temperature is usually 20 to 60 minutes. Is preferred.

The polymer mortar / concrete composition of the present invention can be applied to the production of precast products, floor coating, pavement and the like. Hereinafter, examples and the like will be described in order to make the configuration and effects of the present invention more specific. However, the present invention is not limited to the 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 (2.0 mol) of 2-hydroxyethyl methacrylate, Take 174 parts (1.0 mol) of diethylene glycol monomethacrylate and 2 parts of di-n-butyltin dilaurate, stir while maintaining at 50 ° C., and further add polymethylene polyphenyl polyisocyanate (an average of three isocyanates per molecule). 382 parts (containing a group) (1.0 mol) were added dropwise over 40 minutes. At this time, the reaction heat was generated, but the reaction temperature was kept at 60 ° C. or lower. Thereafter, 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 obtained polymerizable liquid resin A was allowed to stand at 20 ° C. for 24 hours, but no precipitation of unsaturated urethane a was observed.

In the same manner 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 the unsaturated urethane b or c, respectively, and the unsaturated urethane d or e of 55% respectively. % 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 urethanes b to e was observed.

Synthesis of Unsaturated Urethane r-1 and Preparation of Polymerizable Liquid Resin R-1 390 parts of 2-hydroxyethyl methacrylate (3.0 parts)
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 three isocyanate groups in one molecule). Similarly 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
I got The obtained polymerizable liquid resin R-1 was treated at 20 ° C. for 24 hours.
When left for a long time, a large amount of the precipitate of unsaturated urethane r-1 was generated.

In the same manner as in the case of the unsaturated urethane r-1 and the polymerizable liquid resin R-1, 6
A polymerizable liquid resin R-2 containing 0% was obtained. When the obtained polymerizable liquid resin R-2 was left at 20 ° C. for 1 hour, a large amount of unsaturated urethane r-2 precipitate was generated.

Table 1 summarizes the types of polyisocyanate, (meth) acrylic ester monol, and vinyl monomer used in preparing the polymerizable liquid resins A to R-2, and the amounts used thereof.

[0043]

[Table 1]

In Table 1, the numerical values of the amounts used in the table: the upper part is the part, the lower part () is the mole * 1: alkanediol mono (meth) acrylate * 2: polyetherdiol mono (meth) acrylate * 3: trioldi ( (Meth) acrylate PMI-3: polymethylene polyphenyl polyisocyanate (3 NCO groups) PMI-2.5: polymethylene polyphenyl polyisocyanate (average 2.5 NCO groups) MPI: methylene bisphenyl isocyanate HEMA: 2- Hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate DEMA: diethyl glycol monomethacrylate DPMA: dipropylene glycol monomethacrylate GDM: glycerin dimethacrylate MMA: methyl methacrylate ST: styrene Down TPMA: trimethylol propane trimethacrylate

Test Category 2 (Preparation and Evaluation of Polymer Mortar Composition) Preparation of Polymer Mortar Composition Binder / filler / aggregate was prepared according to JIS A1181 (how to prepare a specimen for strength test of polymer resin concrete). 100/200/500 (each part by weight) of the polymer mortar composition having the contents shown in Table 2 and binder / filler / aggregate having the contents shown in Table 3 having 100/200/800 (each part by weight). And a polymer mortar composition of
The materials used here are as follows. In addition, what did not contain a hardening agent and a hardening accelerator was prepared for slump and slump flow measurement.

Materials used Binder: used one shown in Tables 2 and 3 Filler: used heavy calcium carbonate (particle size: 2.5 μm or less, specific gravity: 2.70, water content: 0.1% or less) Aggregate: No. 4 silica sand (fine particle size 0.70-1.
Equivalent mixture (weight: 17 mm, specific gravity 2.51, water content 0.1% or less) and No. 7 silica sand (particle size 0.05 to 0.21 mm, specific gravity 2.51, water content 0.1% or less) Ratio) was used. Viscosity reducing agent: using those shown in Tables 2 and 3 Curing shrinkage reducing agent: using those shown in Table 3 Curing agent: using those shown in Tables 2 and 3 Hardening accelerator: The one shown in Table 2 and Table 3 was used. The amount of the hardening agent and the hardening accelerator used is based 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 performed according to JIS A1173 (Slump test method for polymer cement mortar). still,
As the flat plate, a glass plate having a tape with a scale attached to the back surface {specified in JIS R3202 (float, polish plate)} was used. During the slump test, the slump was measured when the flow stopped after the slump cone was pulled up. The spread of the bottom at the same point was read on a glass plate and defined 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, numerical values of the amounts used: parts A to E, R-1, R-2: those prepared in test category 1. R-1 and R-2 have precipitates R-3: Orthophthalic unsaturated polyester / styrene = 50/50 (weight ratio) unsaturated polyester resin R-4: Trimethylolpropane dimethacrylate 60
Part is mixed and dissolved in 40 parts of methyl methacrylate. Polymerizable liquid resin P-1: butoxypolyoxypropylene (16 mol) /
Polyoxyethylene (9 mol) glycol acid phosphate ester {monoester / diester = 90/10 (molar ratio)} P-2: methoxypolyoxypropylene (30 mol) glycol acid phosphate ester monoester / diester = 75 / 25 (molar ratio)} P-3: phenoxypolyoxypropylene (50 mol)
Glycol phosphate diethanolamine salt {monoester / diester = 55/45 (molar ratio)} S-1: polyisobutyl methacrylate (number average molecular weight 50,000) 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: Bindering occurred due to separation of binder * 6: High viscosity, The sample for evaluation could not be prepared because uniform kneading was not possible

Test Category 3 (Preparation of Hardened Mortar and Evaluation of Strength) Preparation of Specimens The polymer mortar compositions of Tables 2 and 3 prepared in Test Section 2 were measured to have a size of 40 × according to JIS A1181.
Specimens 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 heated and cured at 70 ° C. × 15 hours were used as test specimens.

Test Method Compressive strength JIS A
Table 4 shows the results of the tests performed according to the bisection loading method of JIS A1184 (Testing method for bending strength of polyester resin concrete). And Table 5.

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

[0054]

[Table 4]

[0055]

[Table 5]

In Table 5, * 7: A cured product was not prepared because the polymer mortar composition was heterogeneous. A minus sign in the length change rate indicates shrinkage.

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

[0058]

[Table 6]

Test Category 5 (Preparation of polymer mortar composition, preparation of cured product thereof 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. The filler: The one shown in Table 7 was used. Aggregate: No. 4 silica sand and 7 used in Test Category 2
Flame retardant using the same mixture (weight ratio) of No. silica sand Reinforcement fiber using red phosphorus: 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使用

Evaluation of kneading property and filling property of polymer mortar composition The kneading property of the prepared polymer mortar composition and the difficulty of filling into a mold were qualitatively evaluated. The results are shown in Table 8.

Preparation of Cured Product Each polymer mortar composition was molded to a size of 220 × 220 × 15 mm according to JIS A1181, and then molded at 20 ° C. ×
Curing was performed at 50% RH for 24 hours, followed by heating at 70 ° C. for 15 hours. Three cured products were prepared for each formulation, and these were used as test specimens and subjected to the following flame retardancy test.

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

[0064]

[Table 7]

In Table 7, used amount: parts, but in the case of reinforcing fibers, volume% A, E, R-3: 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 lessＦ F-2: heavy calcium carbonate ｛average particle size 2.5 μm or less, specific gravity (20 ° C.) 2.70, water content 0.1% The following: 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 the cracks in Comparative Example 10 was shown as a minimum value to a maximum value because of the large variation in the test results.

[0069]

As is clear from the above, the present invention described above has a workability and workability in which a solidified polymerizable liquid resin which does not generate a solidified substance or a precipitate at room temperature and which has excellent stability is used as a binder. Is obtained, and by curing the polymer mortar / concrete composition, a cured product having excellent water resistance can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 33/14 C08L 33/14 // (C04B 26/06 24:02 24:32 24:24 14:36 14:38 22: 02) (72) Inventor Junji Kodama 67-Janba, Hanemachi, Okazaki City, Aichi Prefecture (56) References JP-A-6-25362 (JP, A) JP-A-54-36390 (JP, A) (58) Survey (Int.Cl. ⁶ , DB name) C04B 26/06 C04B 26/16 C08L 33/14 C08L 75/14 C08F 220/36

Claims (9)

(57) [Claims] 1. Contains a binder, an inorganic powdery filler and an aggregate
Curable polymer mortar or concrete composition comprising
Wherein the binder is an unsaturated wax represented by the following formula 1.
Urethane and vinyl monomer copolymerizable with the unsaturated urethane
And the unsaturated urethane / the vinyl monomer = 9
Polymerizable with a ratio of 0/10 to 10/90 (weight ratio)
A liquid resin, wherein the inorganic powdery filler and the aggregate are
300 to 115 parts by weight per 100 parts by weight of the binder
Characterized in that it is contained in a proportion of 0 parts by weight.
Curable polymer mortar or concrete composition
Stuff. (Equation 1)[In the formula 1, X:Diphenyl ether-4,4'-diisocyanate
G, diphenylmethane diisocyanate, tolylene diisocyanate
Socyanate, xylene diisocyanate, dimethylene
Triphenyl triisocyanate, trimethylene tetra
Phenyltetraisocyanate or isocyane in the molecule
Polymethylene polyphenyl having an average of 2 to 4 phosphate groups
PolyisocyanateY is a residue obtained by removing a hydroxyl group from a trihydric alcohol A¹: Alkylene group having 2 to 6 carbon atoms A^Two: An alkylene group R having 2 to 4 carbon atoms¹, R^Two, R^Three: H or CH_Three  p, q, r: p and r are integers of 0 to 2 that are not simultaneously 0.
Q is an integer of 1 to 3, and 2 ≦ p + q
+ R ≦ 4 m: integer of 2 to 5] 2. A vinyl monomer copolymerizable with unsaturated urethane is methyl methacrylate or alkane having 2 carbon atoms.
And at least one vinyl monomer selected from alkanediol di (meth) acrylates having from 6 to 6, alkanetriol tri (meth) acrylates having 3 to 6 carbon atoms and 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 powdery filler is binder / inorganic powdery filler = 3/1 to 1/3 (weight ratio). Or a concrete composition. 4. An anionic polymer surfactant represented by the following formula 2 as a viscosity reducing agent: 0.001 to 5 parts by weight per 100 parts by weight of the total amount of the inorganic powdery filler and the aggregate. The curable polymer mortar or concrete composition according to claim 1, 2 or 3, which is contained in a proportion. (Equation 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: number of repeating oxyalkylene units Is a residue obtained by removing a hydroxyl group from a polyether diol of 5 to 100, and the oxyalkylene unit is composed of only an oxypropylene unit or both an oxypropylene unit of 50 mol% or more and an oxyethylene unit of 50 mol% or less. Residue M: H or a monovalent base m, n: 1 or 2 and satisfying m + n = 3] 5. A curing shrinkage reducing agent selected from a polyalkyl (meth) acrylate, a saturated aliphatic polyester, a vinyl aromatic hydrocarbon polymer and a vinyl copolymer containing a vinyl aromatic hydrocarbon as a monomer component. 5. The curable polymer mortar or concrete composition according to claim 1, wherein the one or more thermoplastic polymers are contained in a proportion of 1 to 50 parts by weight per 100 parts by weight of the binder. 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 powdery filler is aluminum hydroxide, which contains 100 to 300 parts by weight of aluminum hydroxide per 100 parts by weight of a binder, and is further selected from inorganic fibers and metal fibers. The curable polymer mortar or concrete composition according to claim 1, 2, 3, 4, 5, or 6, comprising one or more reinforcing fibers in a proportion of 1 to 20% by volume based on the whole. 8. The curable polymer mortar or concrete composition according to claim 7, further comprising a phosphorus compound as a flame retardant in an amount 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.