JPH03158211A - Production of fiber-reinforced polyvinyle chloride series resin composite material - Google Patents

Abstract

PURPOSE:To uniformly impregnate a highly viscous polyvinyl chloride series resin into reinforced fiber filaments and improve the wet properties of the resin on the surface of the reinforced fiber filaments by applying a plasticizer for the polyvinyl chloride series resin to the surface of the reinforced fiber filaments and heating and pressurizing the reinforced fiber filaments for unification after immersing the same in a fluidized bed containing a polyvinyl chloride series resin composition in the form of powder. CONSTITUTION:Roving glass fiber 1 is allowed to pass continuously through a coating tank 4 containing a plasticizer, and the amount of the plasticizer is regulated so as to be 5wt.% or more to the amount of the glass fiber. Subsequently, the roving glass fiber is allowed to pass continuously through a fluidized bed 7 containing a polyvinyl chloride resin and, after the polyvinyl chloride resin in the form of powder is attached to the portion between monofilaments, the excessive polyvinyl chloride resin is removed and adjusted by slitters 12, and the glass fiber is then fed onto a lower side endless belt 23 while being cut by a cutter 21. The minimum gap between an upper side endless belt 22 and the lower side endless belt 23 is adjusted by guide rolls 27, and the polyvinyl chloride resin in the form of powder is melted while accumulated members are being pressurized in the direction of their thickness.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing a fiber-reinforced polyvinyl chloride resin composite material in which the filaments of reinforcing fibers are impregnated with a polyvinyl chloride resin.

(Prior art) Conventionally, roving-shaped continuous reinforcing fibers are passed through a fluidized bed of powdered thermoplastic resin to adhere the powdered resin to the reinforcing fibers, and then continuously passed through a heating zone. There are known methods for producing fiber-reinforced resin composites in which thermoplastic resin powder is melted and reinforcing fibers and thermoplastic resin are integrated (for example, Japanese Patent Publication No. 52-3985, Japanese Unexamined Patent Application Publication No. 1983-1989).
No. 85653, Japanese Unexamined Patent Publication No. 131027, Publication Patent No. 1983
-501943, Japanese Unexamined Patent Publication No. 63-27208, etc.).

(Problem to be Solved by the Invention) However, the conventional manufacturing method described above attempts to uniformly disperse the thermoplastic resin in the reinforcing fibers, but after impregnating the fibers with the thermoplastic resin, the resin is melted. When integrated after heating to a high temperature, high viscosity resins such as polyvinyl chloride resin have poor wetting properties on the fiber surface and deteriorate physical properties even if they appear integrated. Furthermore, when these composite materials are reheated to the melting temperature of the resin and shaped, there are problems such as the reinforcing fibers becoming fluffy.

The present invention aims to solve the above problems,
The objective is to produce a fiber-reinforced polyvinyl chloride resin composite material in which reinforcing fiber filaments are uniformly impregnated with high-viscosity polyvinyl chloride resin, and the wetting properties of the resin on the surface of the reinforcing fibers are improved. This is what we are trying to provide.

(Means for Solving the Problems) The present invention provides a method for applying a liquid polyvinyl chloride resin plasticizer at room temperature to the surface of a reinforcing fiber filament in an amount of 5% by weight or less, and then converting the reinforcing fiber filament into a powdery polychloride. The reinforcing fiber filament is immersed in a fluidized bed of a vinyl resin composition to adhere the powdered polyvinyl chloride resin composition to the reinforcing fiber filament, and then heated and pressurized to integrate the reinforcing fiber filament.

The reinforcing fibers used in the present invention include fibers that are thermally stable at the melting temperature of the powdered polyvinyl chloride resin used, and inorganic fibers such as glass fibers, carbon fibers, boron fibers, and metal fibers. fibers, or organic fibers such as aramid fibers, econol fibers, polyester fibers, and polyamide fibers, etc., and these fibers have a diameter of 1 to 50 μm.
It is used in the form of a continuous reinforcing fiber bundle in the form of a roving or strand consisting of several hundred to several thousand monofilaments. When using a continuous reinforcing fiber bundle in which monofilaments are bound together by a binding agent, the amount of the binding agent attached is preferably 1% by weight or less, more preferably 0.51% by weight or less. If it exceeds 1% by weight, it becomes difficult to open and separate the continuous reinforcing fiber bundle into monofilament units.

As for polyvinyl chloride resin, which is a high viscosity resin in the present invention, the polymerization degree is generally (
For example, with an average degree of polymerization of 200 to 1200), lumps, suspensions,
Alternatively, an emulsion can be used, such as polyvinyl chloride resin, polyvinylidene chloride resin, highly chlorinated polyvinyl chloride resin, chlorinated monomer, and monomer copolymerizable with this monomer. (e.g., vinyl chloride vinyl acetate copolymer, vinyl chloride vinylidene chloride copolymer, ethylene vinyl chloride copolymer, propylene vinyl chloride copolymer, vinyl chloride acrylic ester copolymer, vinyl chloride methacrylate copolymer, etc.).

In the present invention, additives used when molding polyvinyl chloride resins include, for example, heat stabilizers (alkyltin mercapto compounds, alkyltin carboxylates, metal soaps, epoxidized oils or esters, aryl or Alkyl or aryl/alkyl mixed phosphites (individually or in combination), internal lubricants (mono-, di-, tri-esters of glycerin, higher alcohols, neutral or basic metal soaps, etc.), external lubricants (higher fatty acids, fatty acid esters, polyethylene wax, fatty acid amides, silicone oils, etc.), antioxidants (sterically hindered phenols or bisphenols, etc.), ultraviolet absorbers (salicylic acid esters, benzophenones, benzotriazoles, cyanoacrylates, etc.), Pigments (metal oxides, carbon black, etc.), plasticizers (dioctyl phthalate, dicyclohexyl phthalate, etc.), etc. may be added.

In addition, impact modifiers such as ethylene-vinyl acetate copolymer, acrylate resin, chlorinated polyethylene resin, acrylic-butadiene-styrene copolymer, and methacrylic-butadiene-styrene copolymer may be added.

Inorganic fillers such as calcium carbonate, talc, and mica may also be added.

As the plasticizer for polyvinyl chloride resin used in the present invention, any plasticizer that is liquid at room temperature can be used. Examples of plasticizers include phthalate esters (DOP (di-2-ethylhexyl phthalate), DBP (dibutyl phthalate), etc.), adipate esters (DOA (di-2-ethylhexyl), adipate, etc.), and sebacic acid. Esters (DBS (dibutyl sebacate)), azelaic acid ester <DOZ (di-2-ethylhexyl azelate)), phosphoric acid ester (TOP (tri-2-ethylhexyl phosphate)), TCP (tricresyl phosphate) ), epoxidized vegetable oils (such as epoxidized soybean oil) are used.

When applying the plasticizer to the reinforcing fibers, any solvent can be used as long as it can uniformly dissolve the plasticizer at room temperature and has a boiling point lower than the plasticizer used. Good too.

In the present invention, the ratio of polyvinyl chloride resin and reinforcing fibers is appropriately determined depending on the physical properties required of the composite material.
It is preferable that the amount of reinforcing fibers in the reinforcing sheet is 70% or less. If it exceeds 70% by weight, it becomes difficult to obtain a uniform sheet.

The amount of plasticizer for polyvinyl chloride resin applied to the reinforcing fiber filament is 5% or less based on the reinforcing fiber,
Preferably it is 0.05 to 2% by weight or less. If the amount is more than 5% by weight, the plasticizer will cause the fibers to converge and the powdered polyvinyl chloride resin will not adhere uniformly to the reinforcing fiber filaments.

Next, a method for manufacturing a fiber-reinforced polyvinyl chloride resin composite material of the present invention will be explained with reference to the drawings.

FIG. 1 is an explanatory diagram showing one embodiment of the manufacturing method of the present invention.

The roving-shaped reinforcing fibers 1 are usually supplied in the form of a roll, set on an unwinding roll 2, and unwound from the outside so as not to be twisted. The plasticizer solution 5 is taken up by the pinch rolls 15 and then introduced into the coating tank 4 by the guide rolls 3a. The plasticizer solution 5 is impregnated into the fibers 1, and guided by guide rolls 3b to a hot air blower 6, where excess plasticizer solution 5 is blown away. The roving-shaped reinforcing fibers 1 impregnated with the plasticizer solution 5 are guided by guide rolls 8a and introduced into the fluidized bed 7, and are guided by the guide rolls 7a, 7a to pass through the fluidized bed 7. At this time, it comes into contact with the polyvinyl chloride resin powder 9 fluidized by the gas 10 and is opened, and the polyvinyl chloride resin powder 9 is impregnated and adhered between the filaments of the roving reinforcing fibers 1.

The roving-shaped reinforcing fibers 1 that have passed through the fluidized bed 7 and have the polyvinyl chloride resin attached thereto are guided by guide rolls 8b, and the rolls 11 are pressed against the roving-shaped reinforcing fibers 1 to form one band of a certain length. Subsequently, the slitter 12 is reached. When the roving reinforcing fibers l pass through the gap between the slitter 12, excess polyvinyl chloride resin is removed by the upper and lower surfaces of the slitter 12, and the amount of adhesion is kept constant.

Subsequently, the roving-shaped reinforcing fiber 1 is heated in a far-infrared heating furnace 13.
The powdered polyvinyl chloride resin is melted. Then, the roving reinforcing fiber 1 is heated on a heating roll 1.
4 to be integrated with the molten polyvinyl chloride resin, and then passed through pinch rolls 15 and cooled, thereby obtaining a polyvinyl chloride resin composite material in the form of a ribbon-like prepreg.

Further, a manufacturing method will be described with reference to FIG. 2 showing another embodiment B of the present invention.

Portions corresponding to the embodiment shown in FIG. 1 above are designated by the same reference numerals, and description thereof will be omitted.

This embodiment differs from the above embodiment B in that the process after removing the excess polyvinyl chloride resin from the roving reinforcing fibers l to which the polyvinyl chloride resin has adhered is a long continuous process, unlike the embodiment B described above. The roving-shaped reinforcing fibers 1 are cut, and slightly shorter reinforcing fibers are laminated to form a sheet to obtain a vinyl chloride resin composite material.

After removing excess polyvinyl chloride resin from the roving reinforcing fibers 1 using a slinter 12, the cutter 21 cuts the fibers into desired lengths and places them on the lower endless belt 23 protruding forward from the lower side of the canter 21. Random supply and accumulation.

Upper endless belt 22. And the lower endless belt 23 is driven by a drive roll 29 . by a drive source (motor) not shown.
30, it moves continuously at the same speed in the direction of the arrow in the figure.

The melting temperature of the powdered vinyl chloride resin is adjusted in the heating furnace 25 while the aggregate 24 fed onto the lower endless belt 23 is held between the upper endless belt 22 and the lower endless belt 23 and continuously moved in the traveling direction. Heating is performed above to melt the powdered vinyl chloride resin.

At this time, the guide roll pair 26 adjusts the gap between the upper endless belt 22 and the lower endless belt 23, pressurizes the stack 24 in the thickness direction, and flows the molten vinyl chloride resin powder between the monofilaments. The voids are filled with vinyl chloride resin to integrate the resin and reinforcing fibers. As the heating means 25, a method is adopted in which the upper endless belt 22 and the lower endless belt 23 are passed through an electric heating type or hot air circulation type heating furnace, and heating rolls are provided so as to sandwich the upper endless belt 22 and the lower endless belt 23. methods etc. are used. Next, the gap between the upper endless belt 22 and the lower endless belt 23 is removed using the guide roll 27! A fiber-reinforced resin sheet can also be obtained by cooling with the cooling means 28 while applying pressure to the P1 joint.

(Function) In the method for producing a fiber-reinforced polyvinyl chloride resin composite material of the present invention, a plasticizer for polyvinyl chloride resin that is liquid at room temperature is applied to the reinforcing fibers in advance on the surface of the reinforcing fibers. A plasticizer exists in each monofilament of the fiber, which improves the affinity between the reinforcing fiber surface and the polyvinyl chloride resin particles, improves wetting properties, lowers the viscosity when melted, and improves the compatibility of the reinforcing fiber surface with the polyvinyl chloride resin particles. When the polyvinyl chloride resin powder is impregnated, the polyvinyl chloride resin on the surface of the reinforcing fibers is uniformly dispersed between the monofilaments of the reinforcing fibers.

Furthermore, even if a polyvinyl chloride resin is used for the resin matrix, since the polyvinyl chloride resin has a low viscosity when melted, it adheres sufficiently uniformly to each monofilament.

(Example) Embodiments of the present invention will be described based on the drawings.

Example 1 - (See Figures 1 and 2) Dopio% acetone solution was used as the plasticizer solution for polyvinyl chloride resin, and polyvinyl chloride resin (average polymerization -400) 100 parts by weight Butyltin malephate stabilizer Triple foot polyethylene wax
0.5 parts by weight stearyl alcohol
A powder mixture prepared by pre-mixing 1 iOB with a super mixer was used.

As the reinforcing fiber bundle 1, a roving-shaped glass fiber (2200
After continuously passing the plasticizer (g/km) through the coating tank 4 containing the plasticizer, excess solvent was removed by a hot air blower 6, and the amount of plasticizer was 0.5% by weight based on the glass fiber. I adjusted it so that

Next, the glass tam bundle coated with the plasticizer is continuously passed through the fluidized bed 7 of polyvinyl chloride resin, and after adhering the powdered polyvinyl chloride resin between the monofilaments, the slitter 12 removes the excess polyvinyl chloride resin. After removing the vinyl chloride resin and adjusting the weight ratio of the powdered polyvinyl chloride resin and the reinforcing fibers to 7:3, the cutter 21 cuts it into 2 lengths of 11 m while cutting it onto the lower endless belt 23. supplied. The supply amount is approximately 45 (1+ m) at the center of an endless belt with a width of -600 mm, and 3320 g/m
! It was randomly supplied and accumulated so that At this time, the apparent thickness of the polyvinyl chloride resin and glass fiber mixture is approximately 2
It was 3 mm.

The upper endless belt 22 and the lower endless belt 23 are glass fiber reinforced Teflon belts (width -600-5 thickness -1
m duck) was used.

The reinforcing fiber polyvinyl chloride resin mixture supplied onto the lower endless belt 23 as described above is sandwiched between the upper endless belt 22 and the lower endless belt 230 moving at a speed of 580 mm/min and fed. The length is approximately 1500m.
Heating furnace 25 in which hot air of about 200'C is circulated at m.
The powdered polyvinyl chloride resin was melted. At this time, the upper endless belt 22 and the lower endless belt 23
The minimum gap is approximately 2,11I+m by the guide roll 27.
So that it becomes! The powdered polyvinyl chloride resin was melted while pressing the aggregate in the thickness direction.

Next, the reinforcing fiber aggregate in which the polyvinyl chloride resin is in a molten state is transferred to the upper endless belt 2 by a guide roll 27.
2 and the lower endless belt 23 was kept at 21111, and while applying pressure, the mixture was cooled by a cooling blower 28 to obtain a fiber-reinforced polyvinyl chloride resin composite material.

The obtained composite material was a sheet having a width of approximately 500 mm and a thickness of 211 mm, and the resin was well impregnated between the filaments.

(1) Cut out bending test pieces with a width of -20 mm and a length of -150 mm from three random locations in the area of 500 mm x 2000 + m of the obtained composite material, and conduct a 3-point bending test with a distance between fulcrums of -120 nu + to measure the bending strength. did.

(2) A No. 7110.1 A test piece was cut out from JIS-1 and subjected to an Izot impact test.

The test results of (1) and (2) are shown in Table-1.

Table-1 Also, from this composite material 300+mmX 30 (1++
When a sheet of 1.5 m was cut out and heated for 10 minutes in a far-infrared heating furnace with a surface temperature of 320°C, the glass fibers did not fluff even though the polyvinyl chloride resin was completely melted.

Back Twisting A ribbon-shaped prepreg was manufactured by the process shown in FIG.

As a strand-like reinforcing fiber bundle 1, PAN-based carbon fiber strand filament diameter 8 μm 1 filament number 600
0 pieces) were used.

DBP10% as plasticizer solution for polyvinyl chloride resin
Using an acetone solution, as powdered polyvinyl chloride resin, 100 parts by weight of polyvinyl chloride resin (average degree of polymerization 600), 3 parts by weight of butyltin malephate stabilizer, and 1 part by weight of calcium stearate were mixed in advance in a super mixer. The prepared powder mixture was used.

The carbon fiber bundle 1 was continuously passed through the coating tank 4 containing the plasticizer solution, and the excess solvent was removed by a hot air blower 6, so that the amount of plasticizer was 0.5% by weight based on the carbon fibers. May it be! Section II.

Next, the carbon fiber bundle coated with the plasticizer is continuously passed through the fluidized bed 7 of the polyvinyl chloride resin, and after adhering the powdered polyvinyl chloride resin between the monofilaments, the excess is removed by the slitter 12. The polyvinyl chloride resin is removed, and the weight ratio of the powdered polyvinyl chloride resin and carbon fiber is adjusted to 7=3.

Subsequently, the powdered polyvinyl chloride resin is passed through a heating furnace 13 having a far-infrared heater set at a surface temperature of about 38°C to melt the powdered polyvinyl chloride resin, and then passed through a heating roll 14 set at 220°C. Then, the filaments of the reinforcing fiber bundle 1 and the powdered polyvinyl chloride resin were taken off while being integrated to obtain a ribbon-like prepreg having a width of about 20fil11 and a thickness of about 0.3IllIl.

The obtained prepreg had a carbon fiber content of 20% by weight, and the resin was well impregnated between the filaments.

In addition, several sheets of the obtained prepreg were laminated to form a unidirectional reinforcement material with a thickness of 2.0 mm by press molding, and a bending test was conducted. The bending strength obtained was 71 kg/-2.

1 m = Soil -'' For Mr. B of Example 2, Priv I/G was created in the same manner as in Example 2, except that the plasticizer solution for polyvinyl chloride resin was changed as shown in Table 2 below. .

Several sheets of the obtained prepreg were laminated in the same manner as in Example 2,
A unidirectional reinforced material having a thickness of 2.0 mm was formed by press molding, and a bending test was conducted.

The results are shown in Table-3.

Table 2 Table 3 A composite material was produced in the same manner as in Example 1 except that no plasticizer was applied to the glass roving.

Test pieces were cut out from three random locations of the resulting composite material in the same manner as in Example 1, and the bending strength was measured and the Izot impact test was conducted.

The results are shown in Table 4.

Further, when this sheet was heated in a far-infrared heating furnace in the same manner as in Example 1, numerous fluffs were observed.

A prepreg was produced in the same manner as in Example 2 except that no plasticizer was applied to the glass fibers.

In the obtained prepreg, there were several places where the resin was not impregnated.

Further, several sheets of the obtained prepreg were laminated to form a unidirectional reinforced plate having a thickness of 2.0 mm by press molding, and a bending test was conducted. The bending strength obtained was 52kg/ff1m"
Met.

(Effects of the Invention) According to the method for producing a fiber-reinforced polyvinyl chloride resin composite material of the present invention, the polyvinyl chloride resin is uniformly present in each monofilament of the reinforcing fibers, and has good wetting properties. Therefore, the reinforcing fiber has excellent reinforcing effect and high mechanical strength.
A fiber-reinforced polyvinyl chloride resin composite material in which the reinforcing fibers do not fluff even when the matrix polyvinyl chloride resin is heated and melted is obtained.

Therefore, the composite sheet according to the present invention is not only useful as a plate material with excellent strength and impact resistance, but also can be used as a stampable sheet that is a material for press molding.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing one implementation S of the method for manufacturing a fiber-reinforced polyvinyl chloride resin composite material of the present invention, and FIG. 2 is another embodiment of the method for manufacturing a fiber-reinforced polyvinyl chloride resin composite material. It is an explanatory view with a part omitted. l: Reinforced fiber 7:'dL moving bed 4: f! ! Cloth tank 14: heating roll

Claims (1)

[Claims] (1) After coating the surface of the reinforcing fiber filament with a liquid plasticizer for polyvinyl chloride resin at room temperature of 5% by weight or less, the reinforcing fiber filament is placed in a fluidized bed of a powdered polyvinyl chloride resin composition. Production of a fiber-reinforced polyvinyl chloride resin composite material, characterized in that the powdered polyvinyl chloride resin composition is adhered to the reinforcing fiber filament by dipping, and then integrated by heating and pressurizing. Method.