JP2003105203A - Fibrous molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fibrous molding for reinforcing a synthetic resin with good shape retainability at the transportation, or the like, and good disintegradability at the dispersing in the resin. SOLUTION: This fibrous molding is an aggregate of a water insoluble fiber to be blended with a synthetic resin and comprises 80 to 99.9 mass% of the water insoluble fiber and 0.01 to 20 mass% of a water-soluble thermoplastic polymer having a softening temperature of 40 to 350 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber molded product to be mixed with a synthetic resin, a method for producing the fiber molded product, a resin composition and a fiber reinforced resin molded product.

[0002]

2. Description of the Related Art In order to enhance mechanical strength such as rigidity of a synthetic resin molded body, glass fiber, carbon fiber, metal fiber, etc. are mixed with synthetic resin and provided for various purposes. Has been done.

However, when glass fibers or metal fibers are blended, there are problems that the weight of the molded body increases and that combustion residues remain when the molded body is incinerated, and carbon fiber is expensive and the product There is a problem of raising prices.

Further, various synthetic fibers can be used in place of glass fiber or the like, but when they are kneaded with a synthetic resin, they are fluffy and cotton-like when they are put into the extruder from the hopper, so that it is difficult to feed them into the extruder. There's a problem. For this reason, a method of introducing a fiber molded product bundled with a water-soluble polymer such as starch or carboxymethyl cellulose is adopted, but such a fiber molded product is poor in disintegration and thus difficult to disperse in a synthetic resin, There is a problem that the mechanical strength of the obtained resin molding is reduced. Further, if the binding force between the fibers in the fiber molding is weakened, the dispersibility in the synthetic resin is improved to some extent, but it may be destroyed by the impact applied during transportation or the like.

The present invention provides shape retention in transportation and the like,
A fiber molded body which has excellent disintegration properties during melt-kneading and is suitable as a reinforcing material for synthetic resin, a method for producing the fiber molded body, a resin composition using the fiber molded body, and the resin composition molded An object is to provide a resin molded body.

[0006]

Means for Solving the Problems As a means for solving the above problems, the present invention is a fiber molding containing water-insoluble fibers to be mixed with a synthetic resin, wherein the water-insoluble fibers are 80-99.9 mass%.
And a water-soluble thermoplastic resin having a softening temperature of 40 to 350 ° C. of 0.01 to 20% by mass, the fiber molded body being an assembly of the water-insoluble fibers, a method for producing the fiber molded body, Provided is a resin composition obtained by melting and kneading the fiber molding, and a resin molding obtained by molding the resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The water-insoluble fiber used in the present invention is
Fibers made of natural or synthetic resin, cellulosic fibers, flax fibers, kudzu fibers, coconut fibers, jute fibers, hemp fibers, aspen fibers, nez fibers, protein fibers, polyamide fibers, polyester fibers, polyurethane fibers, Examples thereof include polyolefin fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyfluoroethylene fibers, polyacrylic fibers and the like.

The water-insoluble fiber is preferably highly flexible,
Among the above-mentioned materials, ceruce fibers, flax fibers, kudzu fibers, coconut fibers, jute fibers, hemp fibers, aspen fibers and nez fibers are preferable, and cellulosic fibers are more preferable.

As the cellulosic fiber, beaten vegetation, one obtained from cotton, hemp, cotton, viscose rayon, copper ammonia rayon, etc. can be used.
Cellulose content of 80% by mass or more is preferable, and 9
It is more preferably 0% by mass or more, further preferably 98% by mass or more.

The average diameter of the cellulosic fibers is preferably 0.1 to 1000 μm, more preferably 5 to 100 μm.
μm, more preferably 10 to 50 μm, particularly preferably 20 to 30 μm, and the average length is preferably 0.1.
~ 1000 mm, more preferably 0.2-500 mm,
It is more preferably 0.3 to 50 mm, and particularly preferably 0.
It is 5 to 5 mm.

The water-soluble and softening temperature used in the present invention is 4
The thermoplastic polymer having a temperature of 0 to 350 ° C. acts as a binder so that the water-insoluble fibers are bound together with an appropriate binding force having both shape retention and disintegration.

When the softening temperature of the thermoplastic polymer is 40 ° C. or higher, the fiber moldings may be fused with each other when fed to the extruder, or the fiber moldings may be blocked during storage and transportation. To be prevented. When the temperature is 350 ° C or lower,
The disintegration property of the fiber molding is good, and therefore the dispersibility in the synthetic resin is good.

The thermoplastic polymer may be selected from polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyvinylpyrrolidone, water-soluble nylon and the like.

The content ratio of the water-insoluble fiber and the thermoplastic polymer is such that the water-insoluble fiber is 80 to 99.9% by mass, preferably 85 to 99% by mass, more preferably 90 to 95% by mass. The combined amount is 0.01 to 20% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass.
It is% by mass. When the content ratio of the thermoplastic polymer is 0.01% by mass or more, the shape retention is good, so that the fiber molded body is prevented from collapsing during transportation and the like, and fluffing and the like are also prevented. When the content is 20% by mass or less, disintegration is good, and dispersibility in synthetic resin is good.

If desired, the fiber molded product may contain other components. Other components include thermosetting resins, thermoplastic resins to be compounded, antioxidants, UV inhibitors, lubricants, copper damage inhibitors, pigments, dyes, antistatic agents, foaming agents, radiation shielding agents, etc. Can be mentioned.

The fiber molding of the present invention has an outer circumference of preferably 5 to 35 mm, more preferably 7 to 30 mm, further preferably 10 to 15 mm, and a length of preferably 3 to 2 mm.
0 mm, more preferably 3 to 10 mm, further preferably 3
A columnar molded body having a size of ˜5 mm is preferable. The cross-sectional shape of the columnar molded body in the width direction may be any of a circle, a square, a pentagonal or more polygonal shape, and an indeterminate shape.

The shape retention of the fiber molded article of the present invention is preferably 50% or more, more preferably 60% or more, still more preferably 80% or more, particularly preferably 99%.
The disintegration rate is preferably 50% or less, more preferably 40% or less, further preferably 30% or less, and particularly preferably 10% or less.

(Shape retention rate) At room temperature, the fiber molded body was placed in a polyethylene bag and allowed to fall naturally from a height of 1 m 10 times in total, and the weight (W ₂ ) of the fiber molded body and the initial state of the fiber molded body. Using the weight (W ₁ ), the following formula: (W ₂ / W ₁ ) × 1
Request from 00.

(Disintegration rate) In a temperature atmosphere of 40 to 350 ° C., with a plastic plate of 2 × 2 × 0.2 cm,
From the vertical direction, the initial weight (W _A ) of the fiber molding is 1000.
Using the weight (W _B ) of the maximum molded body remaining when collapsed by applying a double amount of pressure (load) and the initial weight, the following formula: (W _B
/ W _A ) × 100.

The fiber molded article of the present invention can be obtained by adding and mixing the water-insoluble fiber, the thermoplastic polymer and water in a suitable mixing means and then molding.

The temperature at the time of mixing and molding is not lower than the softening temperature of the thermoplastic polymer, but is preferably in the range of the softening point temperature of the thermoplastic polymer to 20 ° C. higher than the temperature.

The mixing ratio of the water-insoluble fiber and the thermoplastic polymer is as described above, and the amount of water added is preferably 5 to 200 with respect to 100 parts by weight of the total weight of the water-insoluble fiber and the thermoplastic polymer. Parts by mass, more preferably 10 to 10
The amount is 0 parts by mass, more preferably 20 to 80 parts by mass, and particularly preferably 30 to 50 parts by mass.

A turbo mill, a reaction vessel with stirring blades, a V-type mixer, a tumbler, a high speed mixer, a ribbon type mixer, a jet crusher, etc. can be used as the mixing means, and a roller pressure type disk die is used as the forming means. An attached granulator, a screw extrusion granulator, a spray cooler granulator, a multi-stage cylindrical granulator, or the like can be used.

The resin composition of the present invention comprises 100 parts by weight of a synthetic resin and 5 to 500 parts by weight of a fiber molding, preferably 10 parts by weight.
To 100 parts by mass, more preferably 20 to 50 parts by mass, are obtained by melt-kneading.

The synthetic resin may be a thermoplastic resin or a thermosetting resin, and examples of the thermoplastic resin include polyamide, styrene polymer, polyester, polyurethane, polyether, polyester ether, polyamide ether, polyphenylene oxide, polycarbonate, polyolefin, Acrylic resins, methacrylic resins, polyvinyl chloride, polyvinylidene chloride, etc. can be mentioned, and as thermosetting resins, phenol resins, melamine resins, unsaturated polyester resins, epoxy resins, urea resins, polyurethane resins, silicone resins, etc. Can be mentioned.

The fiber-reinforced resin molded product of the present invention is obtained by molding the above resin composition into a desired shape according to the intended use by a known molding means such as extrusion molding or injection molding. This resin molded product is particularly suitable for applications that require mechanical strength such as rigidity, and examples thereof include various parts used in the following automobiles.

Instrument panel, meter case,
Interior parts such as air conditioner, audio, glove box, air duct, air bag grid, register, pillar garnish, roof liner, sunroof slider, rear parcel shelf, rear tray, door trim, steering wheel, switches, slip joint, ventilator fin, wiper lever, etc. Bumper, bumper beam, bumper fascia, roof, bumper guard, front fender, rear fender, canopy, hood, radiator grille, tailgate outer panel, spoiler, side mall, side protector, side sill garnish, cowl top garnish, wheel cover, wheel Cap, outside handle, outer door handle, pillar garnish, fen -Mirrors, rear lamps, headlamps, lamp housings, cowl top ventilation, emblems, ornaments, rear panels, air spoilers, rear wiper arms, exterior parts such as door mirror stays, engine covers, cylinder head covers, engine mounts for chassis systems and oils. Blow-by type cylinder head cover, oil filler duct, oil filler cap, oil reserve tank,
Plug seal, oil level gauge, hose connector, oil separator, blow-by pipe, oil strainer, fuel injector, fuel strainer, fuel delivery pipe, vacuum tank, canister and air cleaner case for intake system,
Element holder, air inlet pipe, air intake duct, supercharging joint duct, supercharging bypass hose, intercooler tank, intercooler hose, intake chamber, surge tank, resonator, pump manifold for intake manifold and cooling system, thermostat cover, LLC Reserve tank, LLC outlet duct, LLC hose connector, water inlet, radiator tank, cooling fan and cam drive system cam sprocket, tensioner bush, belt idler, timing belt cover, chain guide, canister and fuel system delivery pipe,
Fuel piping, filter housing and electrical system connectors, junction box, fuse block, sensor housing, switch case, angle sensor holder, ABS actuator, exhaust gas control valve, ECU housing, relay block, unit case, harness connector, air flow meter housing, Distributor cover, distributor rotor, ignition coil cover and transmission inhibitor inhibitors, oil strainer,
Engine components such as vacuum pump case, seal ring, speedometer gear, speedometer holder, accumulator piston, governor gear, air blizzer hose, torque converter stator, shift lever base, mechanical parts and relays, power window gear case
Body parts such as sensors, door lock actuators, spiral cables, combination levers, switches, meter bobbins, counters, power seat bases, brake booster pistons around brakes, piston ring parts, and other clips and fasteners.

The fiber-reinforced resin molded product of the present invention is also used in addition to various mechanical parts, electric / electronic parts, sliding parts, sound absorbing materials, medical instrument container materials to be incinerated after use, wood substitutes for construction ( It can be used as a wood grain material, a housing for communication equipment, a radiation shielding material, and the like.

[0029]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

Example 1 As a water-insoluble fiber, the average diameter was 20 μm and the average length was 0.1 μm.
Using a cellulose-based fiber agglomerate of 85 mm and an α-cellulose content of 99% by mass, polyvinyl alcohol (PVA) as a thermoplastic polymer (melting point 161 ° C., glass transition temperature 26 ° C.) (CP-1210, manufactured by Kuraray Co., Ltd.) A 1% by mass aqueous solution of 1) was used to obtain a fiber molding by the following method.

First, the cellulosic fiber agglomerate is applied to a turbo mill (a pulverizer manufactured by Turbo Kogyo Co., Ltd.) to disintegrate it into a single fiber state, and then the cellulosic fibers discharged from the turbo mill are dissolved in an aqueous thermoplastic polymer solution. Was sprayed. The spraying amount at this time is 5 kg of the aqueous solution of the thermoplastic polymer for 100 kg / hr of the discharge amount of the cellulosic fibers of the turbo mill.
It was set to 0 kg / hr.

Next, the mixture of the cellulosic fibers and the thermoplastic polymer was directly applied to a granulator equipped with a roller pressure type disk die (manufactured by Dalton Co., Ltd.) to form a columnar fiber molding having a circumference of 10 mm and a length of 4 mm. Got The shape retention rate and the collapse rate of these fiber moldings were measured. The rate of disintegration was measured at a temperature of 50 ° C. and a weight of the fiber molded body of 20.
g, load of 20 kg with plastic (nylon 6) plate
I went there. The results are shown in Table 1.

Example 2 As a thermoplastic polymer, polyethylene glycol (PE
G) (Molecular weight 1000) (Hodogaya Chemical Co., Ltd.,
A fiber molding was obtained in the same manner as in Example 1 except that PTG-1000) was used. Table 1 shows the measurement results of the shape retention rate and the collapse rate.

Comparative Example 1 As a water-insoluble fiber, a silane coupling agent [vinyl.
Tris (β-methoxyethoxy) silane] treated glass fiber having a diameter of 10 μm and a length of 3 mm (Asahi Glass Co., Ltd.)
A fiber molding was obtained in the same manner as in Example 1, except that Table 1 shows the measurement results of the shape retention rate and the collapse rate.

Comparative Example 2 Sodium carboxymethyl cellulose (CMCNa) (manufactured by Daicel Chemical Industries, Ltd., in place of the thermoplastic polymer,
A fiber molded body was obtained in the same manner as in Example 1 except that CMC Daicel was used. Table 1 shows the measurement results of the shape retention rate and the collapse rate.

[0036]

[Table 1]

As is clear from Table 1, the fiber molded product composed of the cellulose fiber and the thermoplastic polymer had good shape retention and disintegration property. On the other hand, Comparative Example 1 has poor shape-retaining property and disintegrating property and is difficult to practically use, and Comparative Example 2 has poor disintegrating property and is not suitable as a compounding agent for resins.

Examples 3 and 4 and Comparative Examples 3 and 4 Examples 1 and 2 and Comparative Example 1 and 100 were used for 100 parts by mass of homopolypropylene (230 ° C., melt rate flow of 2.16 kg was 10 g / min), respectively. 30 parts by mass of the fiber molded body obtained in 2 was mixed and melt-kneaded using a same-direction twin-screw extruder having a screw diameter of 30 mm (cylinder temperature was set to 190 ° C.) to obtain pellets.

These pellets were clamped at a pressure of 100 tons,
An ISO standard test piece was prepared by an injection molding machine having a screw diameter of 32 mm (cylinder temperature was set to 190 ° C.), and each test item shown in Table 2 was measured. The details of the measuring method are as follows. The results are shown in Table 2.

Tensile strength (MPa): An ISO tensile test piece (thickness 4 mm, total length 150 mm dumbbell piece) was set to 23.
After standing for 90 hours at a temperature of 50 ° C. and a humidity of 50% RH, measurement was performed using UTM-5T manufactured by Orientec Co., Ltd. Set the gap between the grips to 115 mm and the distance between the marked lines to 50 mm,
The tensile speed was measured at 50 mm / min.

Flexural modulus (MPa): ISO bending test pieces (length 80 mm, width 10 mm, thickness 4 mm) were
After standing for 90 hours at a temperature of 50 ° C. and a humidity of 50% RH, measurement was performed using UTM-5T manufactured by Orientec Co., Ltd. Support table R = 5 mm, indenter R = 5 mm, support point distance 64 m
It was set to m and measured at a test speed of 2 mm / min.

Combustion residue (mass%): 800 in oven
The ratio of the weight of the combustion residue to the initial weight when burned at 0 ° C for 5 minutes was determined.

Dispersibility: Hot pressing was performed using the pellets to prepare a sheet having a thickness of 0.5 mm, and it was confirmed whether or not there were fiber aggregates having a diameter of 1 mm or more.

[0044]

[Table 2]

The molded products of Examples 3 and 4 were excellent in tensile strength and flexural modulus because the fiber molded products of Examples 1 and 2 were uniformly dispersed in polypropylene. Furthermore, since the specific gravity is small, it is lighter than the molded products of Comparative Examples 3 and 4, and there is no combustion residue.

Since the molded article of Comparative Example 3 has good dispersibility,
The tensile strength and the flexural modulus were excellent, but it was heavier than the molded products of Examples 1 and 2 and had a large amount of combustion residues. Furthermore, since the silane coupling agent treatment is performed, the manufacturing cost is higher than in Examples 1 and 2.

The molded product of Comparative Example 4 had poor dispersibility, aggregates of fibers were observed, the specific gravity was not uniform, and there was a width. Therefore, the tensile strength and flexural modulus were poor.

[0048]

EFFECTS OF THE INVENTION Since the fiber molding of the present invention has excellent shape retention and disintegration, it has good dispersibility in synthetic resin and is suitable as a reinforcing material for synthetic resin. Furthermore, since the resin molded product containing the fiber molded product of the present invention is lightweight and has high mechanical strength, it is suitable as a material for fields requiring rigidity and the like, and since there is no combustion residue, it can be easily disposed of. Is.

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Claims (11)

[Claims] 1. A fiber molded product containing water-insoluble fibers to be mixed with a synthetic resin, the water-insoluble fibers being 80 to 99.9% by mass.
And a water-soluble thermoplastic polymer having a softening temperature of 40 to 350 ° C. in an amount of 0.01 to 20% by mass, which is an aggregate of the water-insoluble fibers. 2. The outer circumference is 5 to 35 mm and the length is 3 to 20.
The fiber molded body according to claim 1, which is a columnar molded body of mm. 3. The water-insoluble fiber is a cellulosic fiber, flax fiber, waste fiber, coconut fiber, jute fiber, hemp fiber,
The fiber molding according to claim 1 or 2, which is selected from aspen fibers and Nez fibers. 4. The fiber molded article according to claim 1, 2 or 3, wherein the water-insoluble fiber is a cellulosic fiber. 5. The fiber molding according to claim 4, wherein the cellulosic fiber has an α-cellulose content of 80% or more. 6. The cellulose-based fiber has an average diameter of 0.1.
The fiber molded body according to claim 4 or 5, wherein the fiber molded body has a diameter of ˜1000 μm and an average length of 0.1 to 1000 mm. 7. Water-soluble and having a softening temperature of 40 to 350 ° C.
2. The thermoplastic polymer of is selected from polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyvinylpyrrolidone, and water-soluble nylon.
The fiber molded body according to any one of 1 to 6. 8. The fiber molding according to claim 1, which has a shape retention of 50% or more and a disintegration rate of 50% or less. (Shape retention rate) At room temperature, the fiber molded body was placed in a polyethylene bag and allowed to fall naturally from a height of 1 m 10 times in total (W ₂ ), and the initial weight of the fiber molded body (W ₂ ). ₁ ) and the following formula: (W ₂ / W ₁ ) × 100. (Disintegration rate) 2 × in an atmosphere of a temperature of 40 to 350 ° C.
A plastic plate of 2 × 0.2 cm, the initial weight of the fiber molded article (W _A) of the 1000-fold amount of pressure (load) applied from the vertical direction, the weight of the maximum compacts remaining when disrupted (W _B ) And the initial weight, the following formula: (W _B / W _A ) ×
Calculate from 100. 9. The method for producing a fiber molded body according to claim 1, wherein the water-insoluble fiber is 80 to 99.9% by mass, the water-soluble fiber has a softening temperature of 40 to 350 ° C. 0.01 to 20% by mass of the thermoplastic polymer, and 5 to 5 parts by mass of the total weight of the water-insoluble fiber and the thermoplastic polymer.
A method for producing a fiber molding, which comprises mixing 200 parts by mass of water at a softening temperature of the thermoplastic polymer or higher, and then molding and drying. 10. A synthetic resin, 100 parts by mass, and
A resin composition obtained by melt-kneading 5 to 500 parts by mass of the fiber molding obtained in any one of 9 above. 11. A fiber-reinforced resin molded product obtained by molding the resin composition according to claim 10.