JP2512036B2 - Acrylic resin concrete composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to an acrylic resin concrete composition, and more specifically, it has low toxicity, low volatility, high flammability, low odor, low shrinkage, and fast setting. Further, it relates to an acrylic resin concrete composition excellent in bending strength, compressive strength and workability.

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION Resin concrete used for applications such as floors and walls of buildings or pavement for roads has a shorter hardening time and a shorter working time than the cement mortar type that is generally used conventionally. Since it can be shortened, it has become popular rapidly in recent years.
By the way, resin concrete is classified into various types according to the difference in the resin as the main component, and for example, epoxy type, unsaturated polyester type, polyurethane type, acrylic type and the like are well known. These various resin concretes have various advantages and disadvantages depending on the properties of the resin as the main component. For example, epoxy resin concrete has excellent adhesiveness to a base material and water resistance, but has the drawback of poor solvent resistance and weather resistance.
At the following low temperatures, the curing time becomes extremely long, so that it also has a drawback that the on-site workability deteriorates. Although unsaturated polyester resin concrete has excellent solvent resistance, it has the drawbacks of poor weather resistance and workability at constant temperature, and large shrinkage during curing. As described above, although many resin concretes have some drawbacks, acrylic resin concretes have recently been particularly noted because they have relatively good weather resistance and workability at constant temperature.

Acrylic resin concrete composition
According to No. 57-74316, dicyclopentenyl oxyacrylate and dicyclopentenyl oxymethacrylate used as one component of the “acrylic polymerized concrete composition” have low volatility, high flash point and little odor. However, it has recently been revealed that dicyclopentenyloxy acrylate and dicyclopentenyloxy methacrylate have high toxicity, and it is preferable to refrain from using dicyclopentenyloxy acrylate and dicyclopentenyloxy methacrylate.

Therefore, despite the low toxicity, it is strongly desired to develop an acrylic resin concrete composition which has low volatility, high flash point, low odor, low shrinkage, fast curing property, and is excellent in bending strength and compression strength. It was rare.

OBJECT OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and despite low toxicity, low volatility, high flash point, low odor, low shrinkage, fast curing property. And
Moreover, it is an object of the present invention to provide an acrylic resin concrete composition having excellent bending strength and compressive strength.

SUMMARY OF THE INVENTION The acrylic resin concrete composition according to the present invention is an acrylic resin concrete composition containing a liquid acrylic monomer (A) and a powder component (B), wherein the liquid acrylic monomer (A) is The following general formula [I] or general formula [II] [Wherein R ¹ is hydrogen or a methyl group, A is alkylene, hydroxyalkylene, polyalkylene or poly (hydroxyalkylene), and B is And R ² is a lower alkyl group].

The acrylic resin concrete composition according to the present invention has the above [I] as a liquid acrylic monomer (A).
Since it uses the substituted acrylates represented by the formula or [II] formula, it has low toxicity, low volatility, high flash point, low odor, and excellent in fast hardening, bending strength and compressive strength. There is.

Detailed Description of the Invention Hereinafter, the acrylic resin concrete composition according to the present invention will be specifically described.

Liquid Acrylic Monomer (A) The following general formulas [I] and [II] are used as the liquid acrylic monomer (A) in the acrylic resin concrete composition according to the present invention. [Wherein R ¹ is hydrogen or a methyl group, A is alkylene, hydroxyalkylene, polyalkylene or poly (hydroxyalkylene), and B is And R ² is a lower alkyl group], specifically, 4-methylcyclohexyl acrylate, 4-isopropylcyclohexyl methacrylate, 4-t-butylcyclohexyl acrylate, 4- Alkylcyclohexyl acrylates such as t-butylcyclohexyl methacrylate, 4-isobutylcyclohexyl methacrylate, 4-t-butylcyclohexyloxyethyl acrylate, alkylcyclohexyloxyalkyl acrylates such as 4-t-butylcyclohexyloxyethyl methacrylate, 2-hydroxy 3-cyclohexylpropyl acrylate, 2-hydroxy-3
- cyclohexyl propyl methacrylate, A is -CH ₂ CH (OH) CH ₂ in the general formula [II] - a, and B
Acrylates such as alkylcyclohexyl (hydroxyalkyl) acrylates such as alkylcyclohexyl (hydroxyalkyl) acrylate represented by the general formula [2] in which is a cyclohexyl group, t-butylcyclohexyl group, or methylcyclohexyl group are used. . Of these, 4-t-butylcyclohexyl acrylate is preferably used. Compounds preferably used as the alkylcyclohexyloxyalkyl acrylates and compounds preferably used as the alkylcyclohexyl (hydroxyalkyl) acrylates are represented by the following formulas [III] and [IV], respectively.

In the formula [III], R ¹ is hydrogen or a methyl group, R ² is a lower alkyl group having 1 to 4 carbon atoms, and n is 1
~ 6) (In the formula [IV], R ¹ is hydrogen or a methyl group, and R ² is a lower alkyl group having 1 to 4 carbon atoms.) In the present invention, the total amount of the liquid acrylic monomer (A) is Acrylates, alkylcyclohexyloxyalkyl acrylates, or alkylcyclohexyl (hydroxyalkyl))
Acrylates such as acrylates can be used alone. Further, in the present invention, a compound selected from the group of acrylates such as the above-mentioned alkylcyclohexyl acrylates, alkylcyclohexyloxyalkyl acrylates and alkylcyclohexyl (hydroxyalkyl) acrylates may be used alone or confused. Can be used.

It can also be used in combination with the alkylcyclohexyl acrylates, alkylcyclohexyloxyalkyl acrylates, and alkylcyclohexyl (hydroxyalkyl) acrylates. In the present invention,
A compound selected from the group of the above-mentioned vinyls of bicyclo [2,2,1] heptane-2-carboxylate can be mixed and used.

In the present invention, as the liquid acrylic monomer (A),
Liquid acrylic monomers other than acrylates such as the alkylcyclohexyl acrylates, alkylcyclohexyloxyalkyl acrylates, and alkylcyclohexyl (hydroxyalkyl) acrylates may be used in combination. Specifically, alkyl (meth) acrylates such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth)
Acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexylene glycol di (meth) acrylate, 2,
2-bis [4- (meth) acryloyloxyl] propane, 2,2-bis [4- (meth) acryloyloxycyclohexyl] propane, 2,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxyphenyl ]
Propane, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are used.

In the present invention, compounds selected from the group of such liquid acrylic monomers can be used alone or in combination.

In the acrylic resin concrete composition according to the present invention, the total amount of the liquid acrylic monomer (A) is 100% by weight.
In this case, the acrylates such as the alkylcyclohexyl acrylates, the alkylcyclohexyloxyalkyl acrylates, the alkylcyclohexyl (hydroxyalkyl) acrylates are
The liquid acrylic monomer other than acrylates such as the above-mentioned alkylcyclohexyl acrylates, alkylcyclohexyloxyalkyl acrylates, alkylcyclohexyl (hydroxyalkyl) acrylates is used in an amount of preferably 30 to 80% by weight. 100% by weight of the total amount of liquid acrylic monomer (A)
In this case, it is desirable to use it in an amount of 0 to 50% by weight, preferably 20 to 40% by weight.

In the present invention, the liquid acrylic monomer (A)
Is usually used in an amount of about 8 to 25 parts by weight with respect to 100 parts by weight of the powder component described below.

Plasticizer In the present invention, in the liquid acrylic monomer (A),
A plasticizer can be added if necessary. As the plasticizer used in the present invention, specifically, dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dipentyl phthalate, dioctyl phthalate,
Phthalates such as di-2-ethylhexyl phthalate, diisodecyl phthalate and butylbenzyl phthalate, paraffin oils and the like are used. Further, in the present invention, an internal plasticizer such as α, β-unsaturated carboxylic acid ester copolymerizable with a liquid acrylic monomer, for example, diethyl maleate, dibutyl maleate, dioctyl maleate, dibutyl fumarate, dioctyl fumarate. Can also be used.

In the present invention, the plasticizer added to the liquid acrylic monomer (A), including the internal plasticizer, is usually used in an amount of less than 20 parts by weight with respect to 100 parts by weight of the liquid acrylic monomer.

Powder Component As the powder component used in the present invention, specifically,
Aggregates such as natural gravel, silica or crushed aggregate, fine aggregate and coarse aggregate such as artificial aggregate, and fillers such as calcium carbonate, barium sulfate, kaolin, and silica sand powder are used.

The aggregate used in the present invention is usually used in an amount of 70% by weight or more when the total amount of powder components is 100% by weight. Further, the filler is usually used in an amount of 30% by weight or less when the total amount of the powder component is 100% by weight.

Further, in the present invention, if necessary, in the powder component,
Inorganic pigments such as titanium white and red iron oxide, and organic pigments such as benzidine yellow, Hansa yellow and resole red can be added as colorants.

Further, a fine spherical or pulverized methacrylate polymer such as polymethyl methacrylate and / or a methacrylate copolymer such as a copolymer of methyl methacrylate and ethyl acrylate may be added to the powder component. Methacrylate polymers and methacrylate copolymers include the aforementioned alkylcyclohexyl acrylates, alkylcyclohexyloxyalkyl acrylates, alkylcyclohexyl (hydroxyalkyl)
Since it has a function of preventing volatilization of volatile components contained in the liquid acrylic monomer (A) such as acrylates,
Suppressing the odor of liquid acrylic monomers (A) such as alkylcyclohexyl acrylates, alkylcyclohexyloxyalkyl acrylates, and alkylcyclohexyl (hydroxyalkyl) acrylates by adding a methacrylate polymer and / or a methacrylate copolymer Because it is possible to
It is desirable to add a methacrylate polymer and / or a methacrylate copolymer. The methacrylate polymer and / or methacrylate copolymer optionally used in the present invention is generally used in an amount of 8 parts by weight or less based on 100 parts by weight of the aggregate and the filler.

Curing of acrylic resin concrete composition Curing of the acrylic resin concrete composition according to the present invention is performed by using a polymerization initiator and a room temperature polymerization accelerator.

Specific examples of the polymerization initiator used in the present invention include peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide, and azo compounds. The polymerization initiator used in the present invention is usually 0.1 to 100 parts by weight with respect to 100 parts by weight of the liquid acrylic monomer (A).
Used in an amount of 20 parts by weight.

As the room temperature polymerization accelerator used in the present invention, specifically, a cobalt salt such as cobalt naphthenate and cobalt octenoate is used alone, or a combination of these cobalt salts and amines is used.

As the amines used in the present invention, any of a primary amine, a secondary amine, and a tertiary amine may be used,
Specifically, aniline, toluidine, xylidine, phenylenediamine, N, N-dimethylaniline, N, N-diethylaniline, N, N-di (β-hydroxyethyl) aniline, N, N-dimethyltoluidine, N, N-diethyltoluidine, N, N-diethanol-p-toluidine, N, N-dimethylanisidine, N, N-diethylanisidine, N, N-dimethyl-pt-butylaniline, N, N-diethyl- pt
-Butylaniline, N, N-dimethyl-p-chloroaniline, diphenylamine, N, N- (β-hydroxyethyl) -p-toluidine, N, N-dimethylaminobenzaldehyde, N, N-dimethylbenzyl acid, etc. are used. To be

Among them, N, N-dimethyl-p-toluidine, N, N-diethanol-p-toluidine, N, N-dimethyl-p-butylaniline, N, N-dimethylanisidine, N, N-dimethyl-p- Chloraniline, N, N-bis (β-hydroxyethyl) -p-toluidine, N, N-dimethylaminobenzaldehyde and the like, preferably a tertiary amine having an electron donor substituent at the p-position of at least benzenes, N, N
-Dimethyl-p-toluidine, N, N-diethanol-p
-Toluidine, N, N-dimethyl-pt-butylaniline, N, N-dimethylaminobenzaldehyde are particularly preferred.

The room temperature polymerization accelerator used in the present invention is usually 0.1 to 100 parts by weight with respect to 100 parts by weight of the liquid acrylic monomer (A).
Used in an amount of 20 parts by weight.

EFFECTS OF THE INVENTION The acrylic resin concrete composition according to the present invention contains, as a liquid acrylic monomer (A), an alkylate such as alkylcyclohexyl acrylates, alkylcyclohexyloxyalkyl acrylates, and alkylcyclohexyl (hydroxyalkyl) acrylates. Since it is used, it has low toxicity, low volatility, high flash point and low odor, and is also excellent in quick-hardening property, flexural strength and compressive strength.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 As a powder component of an acrylic resin concrete composition, 50 parts by weight of natural round-shaped No. 3 silica sand, 30 parts by weight of natural round-shaped No. 50 silica sand, and a stearic acid-treated heavy surface 20 parts by weight of high-quality calcium carbonate, 0.07 parts by weight of iron black, 0.45 parts by weight of titanium white, and 3 parts by weight of a methacrylate copolymer of fine spherical methyl methacrylate and butyl acrylate were mixed with a mortar mixer to obtain 2 parts.
After mixing with stirring for a minute, a powder component colored in a uniform cement color was obtained.

On the other hand, 65 parts by weight of 4-t-butylcyclohexyl methacrylate (BCH), 12.5 parts by weight of 2-hydroxyethyl methacrylate, 12.5 parts by weight of methyl tetraethylene glycol methacrylate, and 0.5 parts by weight of 1,4-butanediol dimethacrylate. And were measured and mixed to obtain an acrylic monomer mixed solution.

To this acrylic monomer mixed solution, 4.5 parts by weight of paraffinic oil as a plasticizer and 5 parts by weight of ground N, N-dimethylminobenzaldehyde as a polymerization accelerator were added, and then the mixture was stirred for 1 hour to obtain paraffinic oil and N. , N-
Dimethylminobenzaldehyde was dissolved in the acrylic monomer mixed solution.

Acrylic monomer mixed solution thus obtained
To 14 parts by weight, 0.14 parts by weight of a 6% cobalt xylene octenoate solution as a polymerization accelerator was added, and as a polymerization initiator, a benzoyl peroxide powder having a purity of 50% (trade name "silical BPO" Mitsui Kasei Co., Ltd.) was added. 4) were mixed and mixed, then 100 parts by weight of the powder component was added and mixed with stirring with a spatula for 1 minute to obtain a uniform resin concrete composition.

The resin concrete composition thus obtained was smelled and subjected to a flow test, a bending test, a compression test, and a test of the curing property according to the following methods.

[Flow test] Sample resin concrete composition, inner diameter 49mm, height
After putting in a 55.5 mm SUS simple flow cone, pull out and measure the flow value of the sample.

[Bending strength test and compression test] The resin concrete composition as a sample was tested according to JIS R 5201.
40 mm x 40 mm x 160 m using the triple formwork specified in
A test piece of m is prepared, and a bending test and a compression test are performed on the test piece of 7 days old.

[Curing property test] Automatic curing shrinkage tester for resin concrete with internal dimensions of 40 mm x 40 mm x 160 mm [Annual Report of Architectural Institute of Japan Kanto Branch Research Report (Structure) 7,1976, pp.373-376, Presenter] [Mura Katsunori et al., Reference] is installed in a thermo-hygrostat at 20 ° C, and the curing shrinkage amount of a sample resin concrete composition kept at 20 ° C is measured.

Simultaneously with the measurement of the curing shrinkage amount, a thermocouple is embedded in the center of the sample, and the maximum exothermic temperature at the time of curing and the time until the maximum exothermic temperature is reached are measured as a measure of the curing time. The above temperature and time are read from the record of the XY recorder.

 Table 1 shows the results.

Comparative Example 1 A resin concrete composition was obtained and tested in the same manner as in Example 1 except that tetrahydrofurfuryl methacrylate (THF) was used in place of 4-t-butylcyclohexyl methacrylate (BCH) in Example 1. Was done.

 Table 1 shows the results.

Comparative Example 2 A resin concrete composition was obtained in the same manner as in Example 1 except that cyclohexyl methacrylate (CH) was used instead of 4-t-butylcyclohexyl methacrylate (BCH) in Example 1.

When the obtained resin concrete composition was smelled, it had a strong odor.

 Table 1 shows the results.

Claims (1)

(57) [Claims] 1. An acrylic resin concrete composition containing a liquid acrylic monomer (A) and a powder component (B), wherein the liquid acrylic monomer (A) is
The following general formula [I] or general formula [II] [Wherein R ¹ is hydrogen or a methyl group, A is alkylene, hydroxyalkylene, polyalkylene or poly (hydroxyalkylene), and B is Wherein R ² is a lower alkyl group], and an acrylic resin concrete composition comprising a substituted acrylate represented by the formula: