JPS62100487A - Fiber reinforced hardening material and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fiber-reinforced cured material with excellent mechanical properties and a method for producing the same.

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

For example, asbestos fiber, polyolefin fiber, carbon fiber, glassllI#It! , polyamide fibers, etc. are used as liA fibers for reinforcement.

However, asbestos fibers have a composition similar to that of inorganic materials, and although they have excellent adhesion at the interface, it has recently become clear that they pose problems such as pneumoconiosis and are not environmentally friendly. Polyolefin and polyamide fibers are primarily used to prevent cracks caused by earthquakes and impacts, but they have problems such as insufficient elastic modulus and insufficient thermal properties η. Glass fiber has a large density and is insufficient in terms of forming a single irises, and when cement is used as the inorganic material, there is also a problem of alkali resistance. Although carbon fiber has a high modulus of elasticity, its elongation is lower than that of the base material, and it cannot be said to be sufficient for equilibrium impact.

<Object of the present invention> An object of the present invention is to provide an Im-supplied reinforced cured material that is free from environmental problems, has excellent heat resistance and anti-glare properties, is lightweight and has high strength, and a method for producing the same.

<Means for Solving the Problems> The present invention provides a fiber-reinforced hardened abrasive material made of a delicate, inorganic material and/or organic material obtained from an aromatic polyester that exhibits anisotropy when melted; A fiber-reinforced hardening material characterized in that a fine material obtained from an aromatic polyester exhibiting anisotropy when melted is applied to a paste-like inorganic material and/or organic material, which is cast and then cured. It converts to M-adic system.

In the present invention, a polyester that exhibits anisotropy when melted means that when a polyester sample powder is placed on a heating sample stage L between two polarizing plates crossed at 90° and the temperature is raised, the polyester flows -QJ In terms of turbidity, it means something that has the property of being able to transmit light. As such aromatic polyester, Japanese Patent Publication No. 56-18016 and No. 55
Composed of aromatic dicarboxylic acids, aromatic diols and/or aromatic hydroxycarboxylic acids and derivatives thereof, as shown in fathom No. 20008. Comonomers with group diols and derivatives thereof are also included. Here, aromatic dicarboxylic acids include terephthalic acid, isophthalic acid,
Examples include 4°4'-dicarboxydiphenyl, 2,6-dicarboxynaphthalene, 1,2-bis(4-carboxyphenoxy)ethane, and their alkyl, aryl, alkoxy, and halogen-substituted products. Aromatic diols include hydroquinone, resorcinol, 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
Examples include '-dihydroxydiphenyl sulfide, 2.6-dihydroxynaphthalene, 1.5-dihydroxynaphthalene, and their alkyl, aryl, alkoxy, and halogen-substituted products. Aromatic hydroxycarboxylic acids such as teha-P-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxynaphthalene-6-carboxylic acid, l-hydroxynaphthalene-5-carboxylic acid, and their alkyl, aryl, alkoxy, and halogen groups Examples include nuclear substitution products. As an alicyclic dicarboxylic acid, tr
ans -1,4-dicarboxycyclohexane, ei
Examples include s-1,4-dicarboxycyclohexane, and substituted products of these with alkyl, aryl, and halogen groups. As alicyclic and aliphatic diols, crans-1
s 4-dihydroxycyclohexane, ois-1,4
-dihydroxycyclohexane, ethylene glycol b
Examples include i4-butanediol and xylylene diol.

Among these combinations, preferred aromatic polyesters for the present invention include (1) 40 to 70 mol% of P-hydroxybenzoic acid residues, 15 to 80 mol% of the above aromatic dicarboxylic acid residues, and aromatic polyesters. Diol residues 15-8
(2) a copolyester consisting of 0 mol% of terephthalic acid and/or isophthalic acid and chlorohydroquinone, phenylhydroquinone, and/or hydroquinone; (3) 20 to 80 mol% of P-hydroxybenzoic acid residues; 2-hydroxynaphthalene-6-carboxylic acid residue 20~
Copolycil, which consists of 80 mol%, has high crystallinity, alkali resistance, heat resistance, and molecular orientation, and when mixed under gentle shearing force, it fibrillates, increasing the contact area with the base material and dispersing. It has the advantage of improving sex.

Using these starting materials, polygostyl can be obtained as is or by esterification with aliphatic or aromatic monocarboxylic acids or derivatives thereof, aliphatic alcohols or phenol M or derivatives thereof, Polycondensation also performs a reaction.

As the polycondensation reaction, known bulk polymerization, solution polymerization, or suspension polymerization can be adopted, and the polycondensation reaction can be carried out at 150 to 86 °C under normal pressure or under reduced pressure of 1 to 8 torr.
b, Ti, a catalyst such as an Os compound, a stabilizer such as a phosphorus compound, and TiO2.

Oa COs% A filler such as talc may be added as necessary.

The obtained polymer is used as it is or as a powder by heat treatment in an inert gas or under reduced pressure to prepare a sample for spinning.

Alternatively, it can also be used after being granulated once using an extruder.

Each sample is made into fibers by melt spinning.
A known screw type extruder can be used as a device for melt spinning.

The cylinder temperature of the extruder is preferably 280 to 420°C, particularly SOO to 400°C at the tip (maximum temperature).

The first fiber is spun until its final stage, or after it has been coated with an oil and wound up, it is drawn off. Winding or drawing speed is 10-1
0.000 m7m, but from the viewpoint of productivity and stable spinning, 50 to 2,000P+1/l1m is preferable.

In terms of strength and elongation, fibers of 1 to 20 deniers, more preferably 2 to 16 deniers, can be used in the present invention.

The obtained fibers can be used as they are, but they can be made even higher in strength and elasticity by being subjected to heat treatment, stretching, or a combination of these.

The strength of the fiber used in the present invention is 15 P/d or more, preferably 20 P/d or more, and the elastic modulus is 500 Vd or more, preferably 700 P/d or more.

The form of the fibers can be selected from continuous fibers, short fibers, unmarried woven fabrics, knitted fabrics, etc., depending on the molding method, molded product, and purpose. However, when short fibers are used, the length of the m-pongee is 8 to 80 m11 for paste-like inorganic fibers. or,
Since these fibers are easily fibrillated, they may be fibrillated by applying shearing force in advance or may be fibrillated by mixing.

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

Inorganic materials include cement, concrete, lime, mortar, fly ash, diatomaceous earth, gypsum, etc.; organic materials include coal tar, asphalt, polyvinyl chloride, polyethylene, and other synthetic resins. .

After mixing, the mixture is cast according to a known method to form a molded product in the desired shape, such as a flat plate, a corrugated cylinder, or a block, and then hardened to form a final molded product.

As a hardening method, a method can be used in which the material is kneaded with water and then cooled to below the solidification point of the material.

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

Such fiber-reinforced hardened materials can be used as construction and civil engineering materials such as slate, floor materials, wall materials, straw, paving materials, pipes, boards, water tanks, manholes, piles, roads, etc.

(lO) <Example> In order to explain the present invention in detail, reference examples, examples, and comparative examples are shown below, but these are illustrative values and are not limited thereto.

light? To measure anisotropy, place the IC sample on a heating stage.
The temperature was raised at 25° C./i under polarized light and was visually observed.

Reference example! P-acetoxybenzoic acid M 7.20 Kg (40 mol), Terephthal M 2.49 Kr (15 mol), Isophthalic acid 0.88 Kr (6 mol), 4.4'-Sifset J
F shi') -) z knee ik 5.45% (2
0.2 mol) into a tank with an L-shaped stirring blade,
IN stitched with 111 strokes under nitrogen gas atmosphere, 880
The mixture was incubated at ℃ for 8 hours.

During this time, the acetic acid formed was removed, the mixture was stirred vigorously, and then the mixture was gradually cooled, and the mixture was taken out of the system at 200C.

The yield of 1 coalescence is 11.0 (IN, the theoretical yield of 98.2
%Met. This was pulverized with a hammer mill manufactured by Wire Micron Co., Ltd. to give a powder of 2.5 waf-L.

This was treated in a rotary kiln under a nitrogen atmosphere at 280°C for 5 hours, and optical anisotropy was observed at 850°C at 11°.

This polyester was melt-spun using a screw extruder with a diameter of 80111. The nozzle used has a hole diameter Q, (
The hole length is 17 m, the hole length is 0.14111°, and the number of holes is 808.

When melt-spun at 870°C, the spinning was extremely stable, and pale yellow transparent fibers were obtained.

When this m-liner was treated in nitrogen at 820°C for 8 hours,
8.21 denier, strength 29.1y/il, elongation 2.9
%, and the elongation rate was 1,010 y/d.

Example 1 The fiber of Reference Example 1 was cut to 12w% with a cutter,
A portion of 7NIIJ was mixed with 100% of Portland cement.

After being sufficiently dispersed in the paste, it was put into a mold and air-dried for 10 days, then taken out and 4QQm long.

A flat fiber-reinforced hardened material with a width of 400111% and a thickness of 5 sm was prepared.

This was used as a test piece for an impact test of 800? A steel ball was dropped and the distance at which a crack appeared was measured. A crack appeared at a fall distance of 41ffi.

Comparative Example 1 Cracks were generated in Toyobo's η polyethylene terephthalate 1.

Comparative Example 2 A flat plate was produced in the same manner as in Example 1 except that standard asbestos was used instead of fiber. This flat plate cracked at a falling distance of 13 seconds+.

Example 2 Using the fibers of Reference Example 1, a plain weave fabric was prepared with a density of 4/- system density/ION, placed in a mold, poured with a kneaded paste of 1 part of Portland cement and 1 part of 75 ml of water, air-dried for 12 days, and then taken out. W2 with m ring volume fraction 8%
N. Created a reinforced and hardened material.

6 0111X 6 0111X 1 40mI (2)
When the bending test of the test piece was conducted with 120 words between the supports 2
The bending strength was 70 V4/''.

Comparative Examples 8 and 4 Test specimens were obtained in the same manner as in Example 2, except that polyethylene terephthalate fabric and standard asbestos were used instead of the M4 pongee fabric in Example 2, respectively.The bending strengths were 57 and 48, respectively. (It was a country.

\、 ＼゛－＼、 ””””’21, k゛1. , 1. ,,,・1, 1゛゛＼、1・ 4 Shipa Go to ゛-3 (14 completed)

Claims (1)

[Scope of Claims] 1) A fiber-reinforced cured material consisting of fibers obtained from an aromatic polyester that exhibits anisotropy when melted and an inorganic material and/or organic material 2) An aromatic polyester that exhibits anisotropy when melted 1. A method for producing a fiber-reinforced hardening material, which comprises mixing fibers obtained from the above into a paste-like inorganic material and/or organic material, casting the mixture, and then curing the mixture.