JP2536100B2 - Resin composition and concrete composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition excellent in air-drying property and toughness, and a concrete composition containing the resin composition.

[Conventional technology]

Compositions based on so-called epoxy acrylates obtained by reacting epoxy resins with unsaturated monobasic acids, in particular acrylic acid or methacrylic acid, and mixtures of monomers copolymerizable with said esters are already known. . This composition has hitherto been used, for example, as a fiber reinforced plastic, an adhesive or the like. However, known compositions
Various problems have arisen when used as a base coat, top coat, impregnant, casting material, binder for polymer concrete or coating. For example, styrene is generally used as a monomer copolymerizable with the ester. However, when a mixture of the ester and styrene is cured at room temperature with an organic peroxide, oxygen in air is used. However, there was a drawback that the hardening of the surface was hindered and stickiness remained forever.

In order to solve this drawback, there is a method of adding a wax such as paraffin wax to form a wax film on the surface and blocking oxygen, but it causes a problem in secondary adhesion and cannot be used as a primer. Wax floating unevenness occurs due to the outside air temperature, wind, and the like, and when used as an overcoating agent, impregnating agent, casting agent, coating material, or binding material, stickiness and drying unevenness occur on the surface. Further, when this mixture is cured, it does not exhibit sufficient flexibility, so that there is a defect that cracks occur in the film even with a slight strain.

[Problems to be Solved by the Invention]

The present invention eliminates the above-mentioned drawbacks and has air drying property,
Moreover, the present invention provides a resin composition having excellent toughness and a polymer concrete composition using the same.

[Means for solving the problem]

The present invention comprises (a) 5 to 60% by weight of an unsaturated ester obtained by reacting an epoxy resin with an unsaturated monobasic acid and optionally a polybasic acid, and (b) a general formula [Wherein R is H or CH ₃ and R ¹ is an alkylene group having 2 to 12 carbon atoms or two or more alkylene groups having at least 2 carbon atoms bonded by an oxygen atom, Which is an oxyalkylene group having 4 to 12 carbon atoms]. 95 to 40% by weight of dicyclopentenyloxyalkyl acrylate or dicyclopentenyloxyalkyl methacrylate.

The resin composition of the present invention comprises the above-mentioned components (a) and (b), but the epoxy resin used as the raw material of the unsaturated ester of the component (a) is not particularly limited, and for example, is generally formula [In the formula, x is an integer in the range of 0 to 15].

Examples of commercially available products include Epicoat 828, Epicoat 1001, Epicoat 1004 manufactured by Ciel Chemical Co., Ltd., AER-664H, AER-331, AER-337 manufactured by Asahi Kasei Kogyo DER330, DER660, and DER664 manufactured by Dow Chemical.

Further, a type in which a part of hydrogen atoms of the epoxy resin is replaced with halogen (for example, bromine) can also be used. An example of this type of commercially available product is Toto Kasei Epotote YDB.
−400, YDB-340, Sumitomo Chemical's Sumiepoxy ESB-340, E
SB-400, ESB-500, ESB-700, DER- made by Dow Chemical Company
542, DER-511, DER-580, Yuka Shell Co., Ltd. 1045, 105
0, 1046, DX-248, etc.

Also, the general formula [Wherein, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group, and x is an integer in the range of 0 to 15].

As a commercially available product, DE manufactured by Dow Chemical Company
Examples include N.431, DEN438, Epicoat 152, Epicoat 154 manufactured by Ciel Chemical Co., and EPN1138 manufactured by Ciba.

Further, ERL4211 manufactured by Union Carbide Co., CY208, CY221, CY350, XB2615, CY192, CY184 manufactured by Ciba Geigy, etc. are also used.

These epoxy resins can be used alone or in combination of two or more kinds. Further, in order to improve workability, an epi-bis type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin or the like and a low viscosity epoxy resin may be used in combination.

As the unsaturated monobasic acid to be reacted with the epoxy resin,
Partially esterified carboxylic acid containing acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, tricyclo [5.2.1.0 ^2,6 ] -4-decene-8 or 9 residue and unsaturated dibasic acid residue as constituent elements Etc. can be used. Examples of the partially esterified carboxylic acid include 8- or 9-hydroxytricyclodecene-4- [5.2.1.0 ^2,6 ] 1.00 to 1.20 mol and unsaturated dibasic acids such as maleic anhydride, itaconic acid and citraconic acid. There is an unsaturated dibasic acid monoester obtained by heating 1 mol at 70 to 150 ° C. under an inert gas stream.

Obtained by adding unsaturated dibasic acid such as maleic acid, fumaric acid or itaconic acid to tricyclodecadiene-4,8- [5.2.1.0 ^2,6 ] in the presence of a catalyst such as sulfuric acid or Lewis acid. Unsaturated dibasic acid monoesters can also be used.

Taking maleic acid as an example, it is as follows.

Examples of the polybasic acid used as necessary include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, adibic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, and terephthalic acid. ,
Examples include trimellitic anhydride.

As a polybasic acid that is further used if necessary,
It is preferable to use 12 or more dibasic acids. Specific examples thereof include todecanedioic acid, and Okamura Oil Co., Ltd. as a commercially available product.
SLB-12 manufactured by ULB-20, which is a mixture of isomers of unsaturated dibasic acid having 16 carbon atoms (also manufactured by Okamura Oil Co., Ltd.),
SL-20 (also manufactured by Okamura Oil Co., Ltd.), which is a mixture of saturated dibasic acid having 20 carbon atoms, and dimerized fatty acid derived from tall oil fatty acid, which is commonly called dimer acid having 36 carbon atoms, etc. There is. Commercially available products of this dimer acid include ENPOL 1022, ENPOL 1024 (manufactured by Emery), Versadim 216, Versadim 288 (manufactured by Daiichi General Co.),
There is Haridimer # 200 (manufactured by Harima Chemical Co., Ltd.).

Epoxy resin and unsaturated monobasic acid and polybasic acid optionally used, 60 ~ 150 ℃, preferably 70 ~ 130 ℃
The reaction is carried out at the temperature of to give an unsaturated ester.

The ratio of the unsaturated monobasic acid and the polybasic acid used as necessary is preferably such that the carboxyl groups of these acid components and the epoxy groups of the epoxy resin are almost equivalent.

The formation of the unsaturated ester can be examined by quantifying the carboxyl groups of the unsaturated monobasic acid and the polybasic acid used as necessary, and examining the acid value. This acid value is preferably 50 or less, more preferably 15 or less.

In order to prevent gelation due to polymerization during the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, parabenzoquinone, p-tertiary butyl catechol and hydroquinone monomethyl ether.

In addition, in the esterification reaction, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, ferric chloride, lithium hydroxide, lithium chloride, and secondary chloride. The reaction time can be shortened by using an esterification catalyst such as tin.

The resin composition of the present invention further comprises, as the component (b), a compound represented by the general formula At least one dicyclopentenyloxyalkyl acrylate or dicyclopentenyloxyalkyl methacrylate represented by the formula [wherein R and R ¹ are the same as those defined above].

These compounds are known compounds and include, for example, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxypropyl acrylate, dicyclopentenyloxypropyl methacrylate and the like. As described in JP-B No. 61-43337, these compounds are obtained by subjecting dicyclopentadiene to an addition reaction with alkylene glycol or oxaalkylene glycol to produce alkylene glycol monodicyclopentenyl ether or oxaalkylene glycol monodiene. It can be produced by subjecting cyclopentenyl ether to condensation reaction with methacrylic acid or transesterification reaction with methyl methacrylate. It is also possible to replace the methacrylic acid or methyl methacrylate with acrylic acid or methyl acrylate. Also, as described in JP-A-57-200331, it can be produced by addition reaction of alkylene glycol monoacrylate or alkylene glycol monomethacrylate with dicyclopentadiene.

The resin composition of the present invention comprises the unsaturated ester (a) 5 to
60% by weight and 95-40% by weight of the compound represented by the general formula (b). When the amount of the compound represented by the general formula is less than 40% by weight, the viscosity of the resin composition becomes high, and the work becomes difficult to perform, and when the resin composition is cured,
The surface becomes sticky, which is not preferable.

On the other hand, when the proportion of the compound represented by the general formula exceeds 95% by weight, the resin cured product obtained by curing the resin composition becomes brittle, and as a result, the obtained concrete becomes brittle and has low strength. I will end up.

The resin composition of the present invention is excellent in air drying property and toughness,
Suitable for producing polymer concrete.

That is, the present invention further comprises (A) an inert fine particulate and / or granular inorganic aggregate material, and (B) 5 to 40% by weight of the above resin composition with respect to the above aggregate material. It relates to a concrete composition.

The present invention further relates to a concrete composition in which 0.1 to 10% by weight of an organic peroxide is added to the resin composition of component (B).

The present invention further comprises 0.01 to 10% by weight of an aromatic amine-based accelerator and / or the resin composition of component (B).
Or 0.01% by weight to the resin composition of component (B)
It relates to a concrete composition containing 5% by weight of a polyvalent metal salt and / or complex.

The concrete composition of the present invention contains the above resin composition (B) and the above inorganic aggregate material, and further contains an organic peroxide, or an aromatic amine accelerator and / or a polyvalent metal salt and / or By combining the complexes, radical curing occurs at each working temperature. Particularly, when it is necessary to eliminate stickiness on the surface at room temperature or a temperature close thereto, a polyvalent metal salt and / or complex should be an essential component, and an organic peroxide or further an aromatic amine accelerator should be combined. Is.

Next, as the inert fine particulate and / or granular inorganic aggregate material (A) used in the present invention, sand, silica powder, crushed rock, for example, crushed quartz, calcite,
It is possible to use feldspar, basalt, stone, and pebble, as well as calcined bauxide, aluminum silicate, magnesium silicate, mica, and the like.

The amount of the aggregate material used is determined depending on the workability such as desired fluidity and the strength of the desired polymer concrete, and the resin composition (B) of the present invention is
The range is 5 to 40% by weight based on the aggregate material (A).

When the aggregate material is used so that the resin composition (B) is less than 5% by weight, the resin composition (B) serves as the binder even if coarsely crushed rock is used as the aggregate material. The polymer concrete obtained cannot be worked sufficiently and has low strength.

On the other hand, if it is used in an amount of more than 40% by weight, the reinforcing effect of the aggregate material will not be sufficiently exerted, and the polymer concrete will have low rigidity.

Next, as the organic peroxide, benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, acetylacetone peroxide or the like can be used.

The amount used is preferably based on the resin composition (B).
It is 0.1 to 10% by weight, more preferably 0.5 to 3% by weight.
If it is less than 0.1% by weight, the amount of radicals generated from the organic peroxide becomes insufficient, and the resin composition may not be sufficiently cured. If it exceeds 10% by weight, the organic peroxide acts as a plasticizer and the cured resin tends to be soft.

As an aromatic amine accelerator, one of aniline, N, N-dimethylaniline, N, N-diethylaniline, toluidine, N, N-dimethyl-p-toluidine, N, N-di (hydroxyethyl) toluidine, etc. The above combination can be used.

The amount thereof used is preferably in the range of 0.01 to 10% by weight, more preferably 0.1 to 1% by weight, based on the resin composition (B). If the amount used is less than 0.01% by weight, the promoting effect is not sufficient, and if it exceeds 10% by weight, the plasticizing effect is exerted,
This is not preferable because it causes a decrease in the strength of the resin cured product.

Next, the polyvalent metal salt and / or complex is generally called a desiccant (dryer), and metal salts of higher fatty acids are well known. For example, naphthenic acid, is a polyvalent metal salt of octenoic acid, the polyvalent metal is calcium,
Copper, zirconium, manganese, cobalt, lead, iron, vanadium, etc. are shown. Particularly preferred examples are cobalt octenoate and cobalt naphthenate.

As an example of the complex, an acetylacetone complex is well known, and examples thereof include cobalt acetylacetonate and manganese acetylacetonate.

These are preferably used in the range of 0.01 to 5% by weight with respect to the resin composition, but they have a function of promoting the action of the organic peroxide, and if the amount is less than 0.01% by weight, the effect is not sufficient. Even if it exceeds the weight%, no further effect is exhibited.

In addition, pigments, dyes, antioxidants, ultraviolet absorbers, flow control agents, thixotropic agents, plasticizers, waxes and the like can be added to these resin compositions and / or concrete compositions as required. is there.

〔Example〕

Next, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the examples, “parts” means “parts by weight” unless otherwise specified.

Examples 1 and 2 (1) Synthesis of dicyclopentenyloxyethyl methacrylate 660 parts dicyclopentadiene, 160 ethylene glycol
And 4 parts of paratoluenesulfonic acid were reacted at 120 ° C for 4 hours, then the temperature was lowered to 80 ° C, and methacrylic acid 43
0 parts and 4 parts of paratoluenesulfonic acid were added, and the reaction was carried out at 100 ° C. for 5 hours while distilling water, and the obtained reaction product was neutralized with magnesium oxide. The reaction product was washed with water and then purified by vacuum distillation.

(2) Synthesis of unsaturated ester (I) 411 parts of methacrylic acid, epi-bis type epoxy resin Ep-8
28,453 parts, Ep-1001, 1136 parts (all manufactured by Ciel), 0.4 parts of hydroquinone and 4 parts of trimethylbenzylammonium chloride were heated at 100 ° C. for 10 hours to obtain an unsaturated ester (I) having an acid value of 15 .

This unsaturated ester (I) was mixed with the above dicyclopentenyloxyethyl methacrylate in the proportions shown in Table 1 to obtain resin compositions (I) and (II).

To 100 parts of this resin composition, 1 part of 6% cobalt naphthenate, 0.1 part of dimethylaniline and 2 parts of 50% benzoyl peroxide paste were added, mixed well, poured into a mold, and cured at 25 ° C. for 24 hours. Then, a resin cured product having a thickness of 3 mm was obtained.

This resin cured product has a test speed of 1000 according to JIS K6901.
Bending tests were performed at mm / min. The results are shown in Table 1.

Next, to 300 parts of the above resin composition, 3 parts of 6% cobalt naphthenate, 0.3 parts of dimethylaniline and 12 parts of 50% benzoyl peroxide paste were added and mixed well, and then silica sand 5 was added.
No. 200 part was added and kneaded well to obtain a concrete composition. Then, it was poured into a triple mortar formwork specified in JIS R5201 and filled. Cured at 25 ℃ for 24 hours, 4cm
A concrete molded body of 4 cm x 12 cm was obtained. The surface of this concrete molded body that was exposed to air was completely free of stickiness. JIS about this concrete compact
A bending test was performed by the method of R5201. The results are shown in Table 1.

Comparative Example 1 As a comparative example, the same 6% cobalt naphthenate, dimethylaniline, 50 as in Example 1 was prepared using only dicyclopentenyloxyethyl methacrylate synthesized in Example 1.
% Benzoyl peroxide paste and silica sand No. 5 were used to obtain a dicyclopentenyloxyethyl methacrylate cured product and a concrete molded body with the same addition amount.

Further, a bending test was conducted by the same test method as in Example 1. The results are shown in Table 1.

Examples 3 and 4 (1) Synthesis of unsaturated ester (II) Epi-bis type epoxy resin Ep-828, 1017 parts, Halidimer # 200 (dimer acid: manufactured by Harima Kasei Co., Ltd.) 752 parts and trimethylbenzylammonium chloride. 4 copies of 110
Since the acid value became 4 after heating at ℃ for 2 hours, 230 parts of methacrylic acid and 0.4 part of hydroquinone were further added, and the heating was continued at 110 ℃. After heating for 6 hours, an unsaturated ester (II) having an acid value of 10 was obtained.

This unsaturated ester (II) and dicyclopentenyloxyethyl methacrylate synthesized in (1) of Example 1 were mixed in the proportions shown in Table 1 to obtain resin compositions (III) and (IV).
I got

Using this resin composition, a resin cured product and a concrete molded body were obtained in the same manner as in Example 1. A bending test was conducted for each, and the results are shown in Table 1.

The surface of the obtained concrete molded body which was exposed to air was completely free of stickiness.

[Effect of the invention] The resin composition of the present invention is excellent in air-drying property and toughness, and particularly when the unsaturated ester using a dibasic acid having 12 or more carbon atoms is contained, its effect is further increased. Is improved.

In addition, the concrete composition of the present invention has good air drying property and strength.

Claims (5)

(57) [Claims] 1. An unsaturated ester obtained by reacting (a) an epoxy resin with an unsaturated monobasic acid and optionally a polybasic acid, and (b) a general formula. [Wherein R is H or CH ₃ and R ¹ is an alkylene group having 2 to 12 carbon atoms or two or more alkylene groups having at least 2 carbon atoms bonded by an oxygen atom, Which is an oxyalkylene group having 4 to 12 carbon atoms]. A resin composition comprising at least one dicyclopentenyloxyalkyl acrylate or dicyclopentenyloxyalkyl methacrylate in an amount of 95 to 40% by weight. 2. The resin composition according to claim 1, wherein the polybasic acid further used as required is a dibasic acid having 12 or more carbon atoms. 3. An inorganic fine particle and / or granular inorganic aggregate material (A) which is inert, and (B) 5 to 40% by weight based on the above aggregate material.
A concrete composition comprising the resin composition described. 4. A concrete composition comprising the concrete composition according to claim 3 and 0.1 to 10% by weight of an organic peroxide added to the resin composition of the component (B). 5. The concrete composition according to claim 4, which is 0.01% by weight to 10% by weight based on the resin composition of component (B).
0.01 wt% to 5 wt% of a polyvalent metal salt based on the aromatic amine accelerator and / or the resin composition of the component (B), and / or
Alternatively, a concrete composition containing a complex.