JPH07102995B2 - Fiber-reinforced curable material and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a lightweight fiber-reinforced cured material having excellent mechanical properties and used for construction, civil engineering, etc., and a method for producing the same.

<Prior Art> In the fields of construction and civil engineering, inorganic materials such as cement and gypsum and organic materials such as synthetic resins and asphalt are widely used today. Since ancient bricks, these materials have been improved in various mechanical properties by incorporating fibers.

For example, asbestos fibers, polyolefin fibers, carbon fibers, glass fibers, polyamide fibers, etc. are used as reinforcing fibers. However, asbestos fiber has a composition similar to that of an inorganic material, and thus has an excellent adhesive force at the interface, but has problems such as pneumoconiosis, and it has recently been revealed that it is not preferable in terms of environment and health. Polyolefin and polyamide fibers are used to prevent cracking due to earthquakes and shocks, but they have problems such as insufficient elastic modulus and insufficient thermal properties. Glass fibers are insufficient in terms of high density and weight reduction, and when cement is used as an inorganic material, there is also a problem of alkali resistance. Although carbon fiber has a high elastic modulus, its elongation is smaller than that of the base material, and it cannot be said to be sufficient for impact.

<Object of the present invention> An object of the present invention is to provide a fiber-reinforced cured material which has no environmental problems, is excellent in heat resistance and impact resistance, is lightweight and has high strength, and a method for producing the same.

<Means for Solving Problems> That is, according to the present invention, a strength of 20 g / d or more and an elastic modulus of 700 g / d obtained from an aromatic polyester exhibiting anisotropy when melted.
Fibers above, obtained from a fiber-reinforced curable material consisting of an inorganic material and an aromatic polyester exhibiting anisotropy when melted, a fiber having a strength of 20 g / d or more and an elastic modulus of 700 g / d or more to a paste-like inorganic material The present invention relates to a method for producing a fiber-reinforced curable material, which is characterized in that it is mixed, cast, and then cured.

In the present invention, the polyester exhibiting anisotropy when melted means that when the polyester sample powder is placed on a heating sample stand between two polarizing plates which are orthogonal to each other at 90 ° and the temperature is raised, It means that it has the property of transmitting light. Such aromatic polyesters are those composed of aromatic dicarboxylic acids, aromatic diols and / or aromatic hydroxycarboxylic acids and their derivatives shown in JP-B Nos. 56-18016 and 55-20008. In some cases, these and an alicyclic dicarboxylic acid,
Also included are copolymers with alicyclic diols, aliphatic diols and their derivatives. As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, 4,4'-dicarboxydiphenyl, 2,6-dicarboxynaphthalene, 1,2-bis (4-carboxyphenoxy) ethane, etc., and their alkyls and aryls are used. , And alkoxy and halogen group nuclear substitution products. Aromatic diols include hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylethane, 2,2-bis (4- Hydroxyphenyl) propane,
4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 2,6-dihydroxynaphthalene,
1,5-dihydroxynaphthalene, etc. and alkyls thereof,
Examples thereof include nuclear substitution products of aryl, alkoxy and halogen groups. Examples of the aromatic hydroxycarboxylic acid include p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxynaphthalene-6-carboxylic acid, 1-hydroxynaphthalene-5-carboxylic acid, and their alkyl, aryl, alkoxy and halogen groups. The nuclear substitution product of is mentioned.
Examples of the alicyclic dicarboxylic acid include trans-1,4-dicarboxycyclohexane, cis-1,4-dicarboxycyclohexane and the like, and their substituted alkyl, aryl and halogen groups. Tr for alicyclic and aliphatic diols
ans-1,4-dihydroxycyclohexane, cis-1,4-dihydroxycyclohexane, ethylene glycol, 1,4
Examples include butanediol and xylylenediol.

Among these combinations, preferred aromatic polyesters as the object of the present invention include, for example, (1) p-hydroxybenzoic acid residue 40 to 70 mol%, the above aromatic dicarboxylic acid residue 15 to 30 mol% and aromatic Copolyester consisting of 15 to 30 mol% of diol residue, (2) Copolyester consisting of terephthalic acid and / or isophthalic acid and chlorohydroquinone, phenylhydroquinone, and / or hydroquinone, (3) p-hydroxybenzoic acid residue 20 ~ 80 mol% and 2-
Examples thereof include copolyesters containing 20 to 80 mol% of hydroxynaphthalene-6-carboxylic acid residues.

Above all, the polyester in which the p-hydroxybenzoic acid residue accounts for 40 to 70 mol% of the polyester has high crystallinity, excellent alkali resistance, heat resistance, and molecular orientation, and fibrillates when mixed by applying shearing force. It has the advantage of increasing the contact area with the material and improving the dispersibility.

Using these starting materials, polyesters can be used as they are or by esterification with aliphatic or aromatic monocarboxylic acids or their derivatives, aliphatic alcohols or phenols or their dielectrics, etc.
Carry out polycondensation reaction.

As the polycondensation reaction, known bulk polymerization, solution polymerization, suspension polymerization method or the like can be adopted, and at 150 to 360 ° C. at atmospheric pressure or 10
Polymerization catalyst such as Sb, Ti, Ge compounds under reduced pressure of ~ 0.1 torr,
Stabilizers such as phosphorus compounds and fillers such as TiO ₂ , CaCO ₃ , and talc may be added as the case may be.

The polymer thus obtained is used as it is, or is heat-treated on powder in an inert gas or under reduced pressure to prepare a sample for spinning.
Alternatively, it can be used by once granulating with an extruder.

When these samples are made into fibers by melt spinning, a known screw type extruder can be used as an apparatus used for melt spinning.

As for the cylinder temperature of the extruder, the tip (maximum temperature) is
280 to 420 ° C, particularly 300 to 400 ° C is preferable.

The spun fiber may be left as it is, or it may be taken down by winding an oil agent on it. Winding or withdrawing speed is 10 to 10,000
m / min, but from the viewpoint of productivity and stable spinning, 50-2,000 m /
min is preferred.

Fibers having 1 to 20 denier, more preferably 2 to 16 denier in terms of strength and elastic modulus can be used in the present invention.

The obtained fiber can be used as it is, but by subjecting it to heat treatment, drawing or a combination thereof, it is possible to further increase the strength and elasticity.

The fiber used in the present invention has a strength of 20 g / d or more and an elastic modulus of 700 g / d or more.

The form of the fiber can be selected according to the forming method, the formed body, and the use, such as continuous fiber, short fiber, non-woven fabric, woven fabric and knitted fabric.
However, when short fibers are used, the length of the fibers is preferably 1 to 100 mm, and more preferably 3 to 30 mm from the viewpoints of dispersibility of the fibers in the paste-like inorganic material and physical properties. . Further, since this fiber easily fibrillates, it may be fibrillated by applying a shearing force in advance, or may be fibrillated by mixing.

The inorganic material and the organic material used in the present invention are kneaded with water, or are heated and melted to form a paste and then mixed with the above fibers.

Examples of the inorganic material include cement, concrete, lime, mortar, fly ash, diatomaceous earth and gypsum.

After mixing, the product is cast into a desired shape such as a flat plate, a corrugated plate, a cylinder or a block by casting according to a known method, and then cured to give a final product.

As a curing method, when it is kneaded with water into a paste form, it is dried and the water is removed, and when it is melted into a paste form, it is cooled below the solidification point of the material. Can be used.

<Operation and Effect> The thus obtained fiber-reinforced cured material has no environmental problems, is excellent in heat resistance and impact resistance, and is lightweight and has high strength.

Such a fiber-reinforced curable material can be used as a building civil engineering material such as a straight material, a floor material, a wall material, a straw, a pavement material, a pipe, a board, an aquarium, a manhole, a pile or a road.

<Examples> Reference examples, examples, and comparative examples are shown below for illustrating the present invention in detail, but these are merely examples and are not intended to be limiting.

The optical anisotropy was measured by placing the sample on a heating stage and observing it under polarized light with a temperature rise of 25 ° C./min.

Reference Example 1 p-acetoxybenzoic acid 7.20 Kg (40 mol), terephthalic acid 2.49 Kg (15 mol), isophthalic acid 0.83 Kg (5 mol),
4,4'-Diacetoxydiphenyl (5.45 Kg, 20.2 mol) was charged into a polymerization tank having a comb-type stirring blade, heated in a nitrogen gas atmosphere while stirring, and polymerized at 330 ° C for 3 hours.

During this period, the acetic acid formed was removed, polymerization was carried out with vigorous stirring, and then gradually cooled, and the polymer was taken out of the system at 200 ° C.

The yield of polymer was 11.00 kg, which was 98.2% of the theoretical yield.
This is crushed with a hammer mill from Hosokawa Micron Co., Ltd.
The following particles were used.

5 in a rotary kiln under a nitrogen atmosphere at 280 ° C
After the time treatment, optical anisotropy was observed at 850 ° C or higher.

This polyester was melt-spun using a 30 mm diameter screw type extruder. The nozzle used has a hole diameter of 0.07 mm and a hole length
It has 0.14 mm and 308 holes.

When melt-spun at 370 ° C., spinning was performed extremely stably, and a pale yellow transparent fiber was obtained.

When this fiber was treated in nitrogen at 320 ° C for 3 hours, 3.2
1 denier, strength 29.1 g / d, elongation 2.9%, elastic modulus 1,010 g / d
Met.

Example 1 The fiber of Reference Example 1 was cut into a length of 12 mm by a cutter, and 7 parts by weight of the fiber was mixed with 100 parts by weight of Portland cement and 75 parts by weight of water in a kneading paste.

After being sufficiently dispersed in the paste, it was placed in a mold, air-dried for 10 days, and then taken out to obtain a plate-like fiber-reinforced curable material having a length of 400 mm, a width of 400 mm, and a thickness of 5 mm.

Using this as a test piece, 800 g of a steel ball was dropped as an impact test and the distance at which a crack was formed was measured. It cracked at a fall distance of 41 cm.

Comparative Example 1 A flat plate was produced in the same manner as in Example 1 except that fibers obtained by spinning polyethylene terephthalate RT-580 manufactured by Toyobo were used. A crack occurred at a drop distance of 24 cm.

Comparative Example 2 A flat plate was prepared in the same manner as in Example 1 except that standard asbestos was used instead of the fiber. This flat plate cracked at a fall distance of 18 cm.

Example 2 Using the fiber of Reference Example 1, a plain weave fabric was prepared at a yarn density of 4 yarns / cm, put into a mold, and 100 parts by weight of Portland cement and 75 parts by weight of water were poured and the mixture was air-dried for 12 days and then taken out. A fiber reinforced cured material with a fiber volume fraction of 3% was made.

When a bending test of a 60 mm × 60 mm × 140 mm test piece was conducted at 120 mm between fulcrums, the bending strength was 270 kg / cm ² .

Comparative Examples 3 and 4 Test pieces were obtained in the same manner as in Example 2 except that a polyethylene terephthalate woven fabric and standard asbestos were respectively used instead of the fiber woven fabric of Example 2. The bending strengths were 57 and 48 Kg / cm ² , respectively.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location D01F 6/62 308 6/84 303 B (72) Inventor Toshiyuki Kobashi 3-3-1, Kanaokahigashi-cho, Okayama-shi, Okayama No. Nihon Honran Co., Ltd. (56) Reference JP-A-47-39170 (JP, A) JP-A-55-21491 (JP, A) JP-A-60-204649 (JP, A) JP-A-61 -160421 (JP, A)

Claims (2)

[Claims] 1. A fiber-reinforced curable material comprising an inorganic material and fibers having a strength of 20 g / d or more and an elastic modulus of 700 g / d or more obtained from an aromatic polyester which exhibits anisotropy when melted. 2. Fibers obtained from an aromatic polyester exhibiting anisotropy when melted and having a strength of 20 g / d or more and an elastic modulus of 700 g / d or more are mixed in a paste-like inorganic material and cast-molded. A method for producing a fiber-reinforced curable material characterized by post-curing.