JP2003073529A - Composite composition and resin concrete molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite composition having high fluidity, rich moldability and excellent chemical and impact resistances and rigidity and capable of affording a molded product usable as a structural member and a resin concrete molded body using the composite composition. SOLUTION: This composite composition is composed by including at lease one kind of inorganic aggregate such as silica sand in a curable resin composition consisting essentially of a norbornene monomer such as cyclopentadiene and a metathesis polymerization catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite composition which can be suitably used for obtaining a composite material having excellent chemical resistance, abrasion resistance and impact resistance, and a resin using this composite composition. Concerning concrete compacts.

[0002]

2. Description of the Related Art Conventionally, sewer pipes and the like are made of concrete or resin concrete (see Japanese Unexamined Patent Publication No. Hei 10 (1999) -58242).
182205), but concrete ones have the drawback of poor chemical resistance and abrasion resistance, and resin concrete ones are made of concrete. Although the chemical resistance is improved as compared with, the performance is insufficient. Further, in the case of resin concrete, since the original epoxy resin composition for resin concrete and the phenol resin composition have high viscosity, the resin composition for resin concrete has poor fluidity. Therefore, it is not possible to obtain a pipe material or the like in which the fitting convex portion, the concave portion, the flange portion and the like are integrally formed by a molding method such as cast molding.

Therefore, the inventors of the present invention, on the other hand, have a high viscosity represented by polydicyclopentadiene, and a norbornene-based resin excellent in chemical resistance and abrasion resistance has low viscosity and excellent fluidity. We also noticed that it is suitable for the molding of precision molded products because it is obtained by polymerizing norbornene-based monomers in a molding die in the presence of a catalyst. However, since the norbornene-based resin has a low elastic modulus, it has a drawback that it cannot be used for applications requiring rigidity, for example, structural members.

[0004]

In view of such circumstances, the present invention has a high fluidity and a high moldability, and is excellent in chemical resistance, impact resistance and rigidity, and is used as a structural member. It is an object of the present invention to provide a composite composition capable of obtaining a possible molded product and a resin concrete molded product using the composite composition.

[0005]

In order to achieve such an object, the composite composition of the present invention comprises at least one curable resin composition containing a norbornene-based monomer and a metathesis polymerization catalyst as main components. It is configured to include the inorganic aggregate.

In the composite composition of the present invention, the viscosity of the curable resin composition is not particularly limited as long as it can be molded, but if a molded product having irregularities on its surface is to be molded accurately, The viscosity at 25 ℃ is 600cps
It is preferably not more than 400 cps, more preferably not more than 400 cps. That is, if the viscosity is too high, the sedimentation and defoaming of the inorganic aggregate during molding will not be carried out smoothly, and the density of the inorganic aggregate will vary, and sufficient rigidity will not be obtained, and voids may occur, leading to molding defects. There is.

In order to adjust the viscosity, for example, 1% by weight to 20% of a filler or a rubber component is added to the curable resin composition.
A method of adding in the range of 0% by weight can be mentioned. As the filler, calcium carbonate, aluminum hydroxide, magnesium carbonate, sodium hydrogen carbonate, clay, talc, mica, kaolin, fly ash, montmorillonite,
Examples thereof include glass balloons, silica balloons, and heat-expandable vinylidene chloride particles.

As the rubber component, natural rubber, polybutadiene, polyisoprene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block co-assembly, EPDM, ethylene-vinyl acetate co-assembly and hydrides thereof Is mentioned.

Examples of the norbornene-based monomer include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene, dihydrodicyclopentadiene and hydrodicyclopentadiene, tetracyclic compounds such as tetracyclododecene, and tricyclopentadiene. Pentacycles, such as
Heptacycles such as tetracyclopentadiene, and their alkyl-substituted products (eg, methyl, ethyl, propyl,
Butyl substitution), alkylidene substitution (eg ethylidene substitution), aryl substitution (eg phenyl, tolyl substitution), epoxy group, methacrylic group, hydroxyl group, amino group, carboxyl group, cyano group , A halogen group, an ether group, a derivative having a polar group such as an ester bond-containing group, and the like. They are,
They may be used alone or in combination of two or more.

However, it is preferable to use dicyclopentadiene as the norbornene-based monomer in view of availability, reactivity, balance of physical properties of polymer, cost and the like.

Although the curable resin composition contains a reaction catalyst, the reaction catalyst is not particularly limited, but the reaction is not hindered in the presence of oxygen or water, so that the ruthenium metathesis polymerization is carried out. Examples include catalysts. The ruthenium-based metathesis polymerization catalyst is a ruthenium-carbene complex represented by the following general formula (1).

[0012]

[Chemical 1] (In the formula (1), R1 and R2 are independently of each other hydrogen,
A C2-C20 alkenyl group, a C1-C20 alkyl group,
Aryl groups, C1 to C20 carboxylates, C1 to C2
0 alkoxy group, C2 to C20 alkenyloxy group,
An aryloxy group, a C2 to C20 alkoxycarbonyl group, or a C1 to C20 alkylthio group (these are C1 to C20).
To C5 alkyl group, halogen, C1 to C5 alkoxy group, or C1 to C5
Optionally substituted by an alkyl group, a halogen, a phenyl group substituted by a C1 to C5 alkoxy group), X1 and X2 each independently represent an arbitrary anionic ligand, L1 and L2, independently of each other, represents any neutral electron donor, and two or three of X1, X2, L1 and L2 may together form a polydentate chelating ligand) And a ruthenium-vinylidene complex represented by the following general formula (2):

[0013]

[Chemical 2] (In the formula (2), R3 and R4 are independently of each other hydrogen, C
2 to C20 alkenyl group, C1 to C20 alkyl group, aryl group, C1 to C20 carboxylate, C1 to C20 alkoxy group, C2 to C20 alkenyloxy group, aryloxy group, C2 to C20 alkoxycarbonyl group , C1
To C20 alkylthio groups (which may be substituted by C1 to C5 alkyl groups, halogens, C1 to C5 alkoxy groups, or C1 to C5 alkyl groups,
Halogen, optionally substituted by a phenyl group substituted by a C1 to C5 alkoxy group) or a ferrocene derivative, X3 and X4 each independently represent any anionic ligand, L3 and L4 represents, independently of each other, any neutral electron donor, and two or three of X3, X4, L3 and L4 may together form a polydentate chelating ligand) Is mentioned.

More preferred ruthenium-carbene complexes represented by the general formula (1) are represented by the formulas R1 and R2
Are independently of each other hydrogen, a methyl group, an ethyl group, a phenyl group, or a vinyl optionally substituted by a methyl group, an ethyl group or a phenyl group, and X
1 and X2 are each independently C1 or Br, and L1 and L2 are independently trimethylphosphine group, triethylphosphine group, triphenylphosphine group or tricyclohexylphosphine group,
Examples include ruthenium-carbene complexes.

Ruthenium-represented by the above general formula (1)
Carbene complex or ruthenium represented by the general formula (2)
Since the vinylidene complex is poured into the mold while being mixed, it is preferable to add a solvent to make it a liquid form. As an example, it is preferable to use it after diluting it with a solvent. Examples of the solvent include toluene, benzene, tetrahydrofuran (THF), dichloromethane and the like. In addition, it is not preferable to dissolve the ruthenium-carbene complex in a solvent or an acid in which active hydrogen is present, because the stability of the complex is impaired.

The ruthenium-vinylidene complex of the general formula (2) has higher stability in air than the ruthenium-carbene complex of the general formula (1), but the same can be said.

In the method for producing a norbornene-based polymer molded article of the present invention, the mixing ratio of the ruthenium-carbene complex or the ruthenium vinylidene complex to the norbornene-based monomer is preferably in the range of 1/5 to 1/500000 mol. More preferably, 1/30 to 1/2000
It is in the range of 00 mol. The mixing ratio of the catalyst may be set based on the curing time required within this range.

In the curable resin composition of the present invention, if necessary, an antifoaming agent, an antioxidant, a coloring agent, a polymer modifier, a flame retardant, a foaming agent, a thixotropic agent, an antistatic agent. Various additives such as a molecular weight modifier, a pigment, a dye, and an elastomer as an impact resistance improver may be blended.

The inorganic aggregate is not particularly limited as long as it is used as an aggregate of conventional concrete, but silica sand is preferable. When silica sand is used, in order to achieve the closest packing of silica sand in the molded body obtained by the composite composition of the present invention, No. 6 silica sand (average particle size 300 μm) alone or No. 3 silica sand (average particle size) is used. It is preferable to use a mixture of diameter 1 mm) and No. 7 silica sand (average particle diameter 200 μm).

On the other hand, the resin concrete molded product according to the present invention is obtained by curing the composite composition according to any one of claims 1 to 3. Further, the concrete resin concrete molded body is not particularly limited, but for example, is provided in the middle of the sewer pipe line provided along the manhole member, the energy-reducing work (a steep slope, etc., and flows down the sewer pipe line. Decrease the momentum of drainage), face plate.

[0021]

EXAMPLES Examples of the present invention will be described in detail below.
A curable resin composition containing dicyclopentadiene as a norbornene-based monomer as a main component and a ruthenium-based metathesis polymerization catalyst dissolved in a solvent (25 ° C. viscosity 100 c
ps) and No. 3 silica sand as an inorganic aggregate and No. 7 silica sand were mixed at a ratio of 1: 0.5 to prepare a mixture I.

Example 1 Dicyclopentadiene (25
Viscosity 100 cps) and the above mixture I as the inorganic aggregate were mixed by stirring with a mixer to obtain a ratio of 13:87 to obtain a molding material. This molding material was placed on a steel plate, flattened, and heat-cured in an oven to obtain a plate-shaped cured product.

Example 2 Calcium carbonate powder was added to the curable resin composition of Example 1 at a ratio of 10% by weight to prepare 25
A cured product was obtained in the same manner as in Example 1 except that the curable resin composition having a viscosity at 300 ° C. adjusted to 300 cps was used.

Example 3 Calcium carbonate powder was added to the curable resin composition of Example 1 at a ratio of 40% by weight to prepare 25
A cured product was obtained in the same manner as in Example 1 except that the curable resin composition whose viscosity at 1000C was adjusted to 1000 cps was used.

Comparative Example 1 A cured product was obtained in the same manner as in Example 1 except that an unsaturated polyester resin (25 ° C. viscosity 1500 cps) was used as the curable resin composition.

Comparative Example 2 A cured product was obtained in the same manner as in Example 1 except that ordinary Portland cement was used instead of the curable resin composition.

Comparative Example 3 Only the curable resin composition of Example 1 was placed on a steel plate, flattened and heat-cured in an oven to obtain a plate-shaped cured product.

The voids, nitric acid resistance, elastic modulus, and shapeability of the cured products obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were examined respectively, and the results are shown in Table 1.
The void rate was measured by a method according to JIS K7053. The nitric acid resistance was obtained by immersing the cured product in a 40 wt% nitric acid solution at 60 ± 2 ° C for 5 hours, measuring the weight change, and dividing by the cross-sectional area (the smaller the better the nitric acid resistance). It was The elastic modulus was measured by the method according to JIS K7171. The shapeability was judged by visually observing the appearance.

[0029]

[Table 1]

From Table 1 above, it can be seen from Examples 1 to 3 that the composite composition of the present invention can provide a molded article useful as a structural member having excellent corrosion resistance and rigidity. Further, by lowering the viscosity of the curable resin composition from Examples 1 and 2, the shapeability is improved, and a molded article having convex portions or concave portions such as flanges on the wall surface can be easily obtained. I understand well.

[0031]

Since the composite composition according to the present invention is constituted as described above, it has high fluidity and rich moldability, and also has excellent chemical resistance, impact resistance, rigidity and structure. It is possible to obtain a resin concrete molded body that can be used as a member. Further, the resin concrete molded body of the present invention molded by using this composite composition is excellent in chemical resistance, impact resistance and rigidity.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobuhiro Goto             2-2 Kamitobagamichocho, Minami-ku, Kyoto             Gaku Kogyo Co., Ltd. F term (reference) 4J002 CE001 DJ006 FD010 FD016                       FD206 GL02

Claims (4)

[Claims] 1. A composite composition containing at least one inorganic aggregate in a curable resin composition containing a norbornene-based monomer and a metathesis polymerization catalyst as main components. 2. The viscosity (25 ° C.) of the curable resin composition is 60.
The composite composition according to claim 1, which is 0 cp or less. 3. The composite composition according to claim 1, wherein the norbornene-based monomer contains dicyclopentadiene as a main component. 4. A resin concrete molded body obtained by curing the composite composition according to any one of claims 1 to 3.