JP2001200068A - Glass-fiber continuous wire rod for vinyl chloride resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass-fiber continuous wire rod which is excellent in impact strength, resistance to thermal expansion, and external appearance and is suitable especially for producing a large-size or long-size, fiber-reinforced vinyl chloride resin molding, and to provide a vinyl chloride resin molding produced by using the same. SOLUTION: This glass-fiber continuous wire rod is prepared by impregnating a continuous glass fiber strand comprising bundled monofilaments with a resin melt containing (a) a polymer miscible with a vinyl chloride resin and (b) a crystalline polymer immiscible with a vinyl chloride resin and has an average sectional diameter of 0.2-1.5 mm and a glass fiber content of 10-60 vol.%. The vinyl chloride resin molding contains the wire rods continuously arranged in the longitudinal direction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a long-sized vinyl chloride resin molded article which is excellent in impact resistance, thermal expansion resistance, surface appearance, etc., and which is obtained especially by a large-sized molded article or a draw molding. The present invention relates to a glass fiber continuous wire suitable for production and a fiber-reinforced vinyl chloride resin molded article using the same.

[0002]

2. Description of the Related Art Vinyl chloride resins have been used as molded articles in a wide range of applications such as architectural members, industrial members and electric equipment members. However, there is a problem that heat resistance, mechanical strength, dimensional stability, thermal expansion resistance and the like are not sufficient depending on the use. In order to improve these points, it is known that a vinyl chloride resin molded article is filled with glass fibers to improve the properties thereof.

[0003] However, a vinyl chloride resin molded article reinforced with glass fibers is inferior in melt flow properties as compared with other resins, so that the vinyl chloride resin has poor wettability with the glass fibers and has a uniform glass fiber property. Is not dispersed, and the melt flow characteristics of the vinyl chloride resin mixed with the glass fiber are low. As a result, the glass fiber is damaged at the time of melt-kneading and the resin is thermally degraded, resulting in poor impact strength. Furthermore,
The desired properties, such as poor surface appearance, could not be easily obtained because the glass fibers were raised on the surface of the molded article and the surface became rough.

[0004] In order to solve the above problem, the present applicants have
As disclosed in Japanese Patent Application Laid-Open No. 9-255736, a glass coated with a polymer that is miscible with a vinyl chloride polymer, a polymer that is immiscible with the vinyl chloride polymer and is crystalline, and a peroxide. A vinyl chloride resin molded article reinforced with such glass fibers using fibers has been proposed. With this, the impact resistance, elastic modulus,
The water resistance, surface appearance and formability were improved to a considerable extent.

[0005] However, the glass fiber used for reinforcing the vinyl chloride resin is coated with the resin, but the cross-sectional thickness is as large as 2.2 mm or more, and the length is 1 to 5 cm. The order was short. A vinyl chloride resin molded article reinforced by this method may still have insufficient mechanical strength, thermal expansion resistance, and dimensional stability, and this may cause a problem particularly in a molded article having a large dimension. In the case of the molded article of the above, the mechanical strength was remarkably inferior. Further, in this case, there is a problem that the surface appearance due to the protrusion of the glass fiber of the molded product is still insufficient.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and is a fiber-reinforced vinyl chloride resin excellent in mechanical strength such as impact resistance, thermal expansion resistance and surface appearance. Glass fiber continuous wire rod suitable for producing molded articles, especially large-sized molded articles, and fiber-reinforced vinyl chloride resin molded articles for long molded articles obtained by pultrusion molding, etc., and vinyl chloride-based wires using the same. A resin molded article is provided.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the present invention provides a method for producing a polymer (a) which comprises a continuous glass fiber strand in which a plurality of monofilaments are bundled, and which is miscible with a vinyl chloride resin. ) And a molten resin containing a crystalline polymer (b) that is immiscible with a vinyl chloride resin and has an average cross-sectional diameter of 0.2 to 1.
It is a glass fiber continuous wire for a vinyl chloride-based resin molded product, having a diameter of 5 mm and a glass fiber content of 10 to 60% by volume.

The glass fiber continuous wire for a vinyl chloride resin molded article according to the present invention is a glass fiber strand obtained by bundling monofilaments, wherein a specific resin is melt-impregnated in a specific amount by a specific amount. Consists of small continuous wires. Such a glass fiber continuous wire,
It consists of strands obtained by bundling monofilaments, and has a large flexibility due to its small cross-sectional diameter, so that it does not break or break, and is integrally mixed and filled with the reinforced vinyl chloride resin, A molded body reinforced because of its continuity provides a reinforcing effect that cannot be obtained conventionally.

The reinforcing effect is that the resin impregnated in the glass fiber strand is impregnated with the polymer (a) which is miscible with the vinyl chloride resin and the polymer which is immiscible with the vinyl chloride resin. Since it is made of a resin containing the coalesced (b), it is extremely excellent in combination with the large interfacial adhesion between the molded vinyl chloride polymer and the glass fiber.

Thus, the vinyl chloride resin molded article reinforced with the glass fiber continuous wire of the present invention has improved mechanical strength such as impact resistance, and is excellent in thermal expansion resistance and surface appearance. Make it possible to get In particular, in the case of a long molded body, by arranging such continuous fiber wires in one direction and including them, a molded body having excellent characteristics which cannot be obtained conventionally can be obtained.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin in the present invention means a resin substantially consisting of a vinyl chloride polymer. Therefore, not only the vinyl chloride homopolymer but also 60% by mass or more of the constituent components are chloride. It includes a copolymer composed of polymer units based on vinyl. Preferred specific examples include vinyl chloride polymer, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl acetate copolymer-vinyl chloride polymer graft copolymer, and the like. Also, chlorinated polyvinyl chloride is included, and a single resin or a blend of two or more of these resins is also included.

The polymer forming such a vinyl chloride resin can be obtained by a suspension polymerization method, an emulsion polymerization method, or a bulk polymerization method. The average degree of polymerization of these polymers is preferably in the range of 400 to 1500, and particularly preferably 450 to 1000. If the average degree of polymerization is too small, the mechanical properties such as impact resistance and elastic modulus and the thermal stability are lowered, which is not preferable. On the other hand, if the average degree of polymerization is too large, the melt fluidity is lowered and molding becomes difficult, which is not preferable.

The glass fiber strand used in the glass fiber continuous wire of the present invention is a continuous glass fiber in which a plurality of glass monofilaments are bundled. This is a glass fiber packaged in a roving shape, a cake shape, or the like, and is preferably a glass fiber made of one glass fiber strand per package. By using the glass fiber composed of such one glass fiber strand, the fiber opening is facilitated and the impregnation property is improved.

The average diameter of the glass monofilament is 1 to
20 μm is preferred, and 6 to 17 μm is particularly suitable. The number of convergence is preferably 200 to 2,000
And more preferably 400 to 1,200. If the number of bundles is less than 200, it is necessary to divide one bushing into many packages when manufacturing glass fiber strands, which complicates the operation, lowers production efficiency, and increases costs. In addition, in the production of a wire rod, the content of the reinforcing fibers is small, so that the production efficiency is poor, which is not preferable. On the other hand, if the number of bundles exceeds 2,000, the strand becomes thicker, so that it becomes difficult to impregnate the resin between the monofilaments, and the obtained base material becomes thicker, resulting in poor flexibility.

It is preferable that the glass fiber strands are bundled without splitting. In this case, the lengths of the strands are not irregular, and when the wire is manufactured, clogging of the nozzle due to the irregularity is eliminated, thereby facilitating pulling out of the nozzles. for that reason,
The glass fiber content in the obtained wire can be increased, the yield can be improved, and an appearance with less fluff can be obtained.

The polymer (a) miscible with the vinyl chloride resin used in the present invention may be a polymer which is thermodynamically stable and is mixed with the vinyl chloride resin in a molecular order, A polymer in which an affinity acts on the interface with the resin and a stable microphase separation state is obtained. When the polymer (a) is the vinyl chloride resin itself, it is mixed uniformly. When the polymer (a) has a certain degree of miscibility with the vinyl chloride resin, the polymer (a) can be stably dispersed in a continuous layer of the vinyl chloride resin, for example, in a particle state having a particle diameter of 0.01 to 10 μm. Since the polymer (a) has such properties, the polymer (a) has an effect of remarkably improving mechanical strength such as impact resistance and strength of the obtained molded article. If the molecular weight of the polymer (a) is too large, the kneadability with other components is insufficient, so that the weight average molecular weight is 1000 to 40.
10,000 is preferred.

The polymer (a) may be a vinyl chloride polymer, but may be an acrylic acid monomer such as an alkyl acrylate monomer, or a methacrylic acid such as an alkyl methacrylate monomer. Homopolymers or copolymers obtained from a vinyl monomer or a vinyl cyanide monomer. Among them, vinyl cyanide-based monomers form polymers that are highly miscible with vinyl chloride-based polymers in particular. It is preferable to form a polymer (a) by copolymerization.

Preferred specific examples of the polymer (a) include:
Vinyl chloride polymer, copolymer of vinyl cyanide monomer and aromatic vinyl monomer, alkyl acrylate polymer, alkyl methacrylate polymer,
A vinyl acetate polymer is exemplified. Among them, a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer is preferable.

Examples of such a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and styrene, α-methylstyrene and vinyl. It is a copolymer obtained by copolymerizing an aromatic vinyl monomer such as toluene and chlorostyrene, and the content of the polymerized unit based on the vinyl cyanide monomer in the copolymer is from 5 to 80. % By mass, and particularly preferably 10 to 50% by mass. When the content is less than 5% by mass, the miscibility with the vinyl chloride polymer becomes poor, and it cannot be sufficiently dispersed in the vinyl chloride polymer as a matrix, and the mechanical strength of the obtained molded article decreases. In addition, the affinity with the glass fiber is not sufficient, and the water resistance of the obtained molded product is deteriorated.

Among them, the polymer (a) preferably has a higher glass transition temperature than the vinyl chloride polymer from the viewpoint of heat resistance represented by the heat distortion temperature when blended with the vinyl chloride resin. Acrylonitrile-styrene copolymer or polymethyl methacrylate is particularly preferred.

The crystalline polymer (b), which is immiscible with the vinyl chloride resin and has no affinity at the interface with the vinyl chloride resin, has a property that a stable microphase separation state cannot be formed. And a polymer exhibiting crystallinity. The crystallinity means a melting point, for example, showing an endothermic peak by a thermal analysis method such as DSC, and having a property that the melt viscosity sharply decreases at the temperature, and necessarily means a crystallinity of 100%. do not do.

The melting point of the polymer (b) is preferably 250 ° C. or less, which is close to the processing temperature of the vinyl chloride polymer, and particularly preferably 200 ° C. or less. On the other hand, such a melting point is preferably 120 ° C. or higher from the viewpoint of mechanical strength and heat resistance.

When the polymer (b) is contained, the polymer (b) does not have miscibility with the vinyl chloride resin, and thus exhibits a so-called lubricating property. In particular, it is remarkable when the crystal melting point is lower than the processing temperature. Thereby, the melt viscosity of the resin at the time of manufacturing a molded article can be reduced, and the effect of significantly improving moldability and surface appearance can be exhibited. If the molecular weight of the polymer (b) is too large, the kneadability with other components becomes insufficient.
0 to 400,000 is preferable.

Examples of the polymer (b) include a polymer of an α-olefin monomer or a polymer containing these monomers. Preferred specific examples include polyethylene and polypropylene, and polypropylene is particularly preferred. Further, the polymer may contain a functional group such as an acrylic acid group or a carboxylic acid group in order to improve the adhesiveness with the glass fiber.

The proportions of the polymer (a) and the polymer (b) are preferably in the range of 95 to 5% by mass of the former and 95 to 5% by mass of the latter, and particularly preferably in the range of 5 to 95% by mass. The appropriate range is 80 to 20% by mass for the former and 20 to 80% by mass for the latter. If any one of the ratios is less than 5% by mass, any of the effects of the polymer (a) and the polymer (b) cannot be exerted.

In the present invention, in addition to the polymer (a) and the polymer (b), a peroxide which decomposes at a melting temperature of a resin formed from these polymers to generate free radicals may be used. preferable. This is because, when peroxide is present, free radicals generated by its decomposition cause the molecular chains of the polymer (a) and / or the polymer (b) to be cut, thereby reducing the melt viscosity and impregnating the glass fiber. Improve. At the same time, the polymer (a)
And a copolymer which is considered to be formed by a reaction between the polymer (a) and the polymer (b) starting from a newly generated radical by a reaction of abstraction of hydrogen or the like from the polymer (b). It acts as a compatibilizer for the union (a) and the polymer (b) and facilitates mixing.

If the peroxide is used in an excessively large amount, the reaction becomes complicated, which is not preferable in terms of workability, safety and economy. The range is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total of the polymer (a) and the polymer (b).

Preferred specific examples of the peroxide used in the present invention include the following. Ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide;
3,3-tetramethylbutyl hydroperoxide, t
Hydroperoxides such as -hexyl hydroperoxide, dicumyl peroxide, 1,3-bis (t-
Dialkyl peroxides such as butylperoxyisopropyl) benzene, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, peroxydicarbonates such as diisopropylperoxydicarbonate and di-n-propylperoxydicarbonate; Peroxyesters, peroxyketals and the like.

The composition comprising polymer (a), polymer (b) and optionally used peroxide is melted,
The glass fiber strands described above are impregnated. In this case, in order to facilitate the impregnation of the molten resin into the glass fiber, the resin in the molten state preferably has a melt viscosity of 400 to 1000 poise. If it is smaller than the above range, the impregnated resin is not sufficiently retained, while if it is larger, the impregnation cannot be sufficiently performed. Particularly, the viscosity is suitably from 500 to 800 poise. In the present invention, the viscosity is a viscosity measured by a Koka flow tester. Further, the polymer (a),
Various additives such as an adhesive and a processing aid for suppressing thermal deterioration may be added to the component containing the polymer (b) and the peroxide.

The glass fiber strand impregnated with the molten resin may be treated with a coupling agent, a film former, a lubricant, or another surface treating agent. Examples of the coupling agent include a silane compound in which a hydrolyzable group called a silane coupling agent is bonded to a silicon atom. Preferred specific silane coupling agents include, for example, the following compounds. methacrylsilane compounds such as γ-methacryloxypropyltriethoxysilane and γ-methacryloxypropylmethyldiethoxysilane, epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N −
aminosilane compounds such as β-aminoethyl-γ-aminopropyltriethoxysilane; vinylsilane compounds such as vinyltrimethoxysilane; and chlorosilane compounds such as γ-chloropropyltrimethoxysilane.

The method of impregnating the glass fiber strand with the above resin is not particularly limited. Usually, the polymer (a),
A method is used in which a mixture containing the polymer (b) and, if necessary, a peroxide is melt-mixed to form a resin in a molten state, and this is impregnated into a glass fiber strand. Preferably, the glass fiber strand is continuously passed through a bath containing the resin in a molten state, so that the strand is impregnated with the resin, coated with the resin, and then continuously wound without cutting the strand. Can be

At this time, a method in which the polymer (a) and the polymer (b) are mixed in advance before heating, the mixture is melted and kneaded at an appropriate temperature using an extruder, and introduced into a tank. Is preferred from the viewpoint of continuous production. Further, it is preferable that one glass fiber strand is impregnated with a resin and pulled out from one nozzle. Thereby, it becomes easy to pull out from the nozzle at a high speed, and it is possible to increase the glass fiber content and to make the appearance less fuzzy.

The glass fiber continuous wire thus obtained preferably has a circular or elliptical cross section, and the average diameter is suitably from 0.2 to 1.5 mm, more preferably from 0.4 to 1.5 mm. 1.0 mm is preferred. The average diameter is 0.
If it is less than 2, productivity will be poor, and if it exceeds 1.5 mm, flexibility will be poor, and handling will be poor. When the cross section is rectangular or the like, the average diameter is calculated by dividing the sum of the major axis and the minor axis into two. In addition, the longer the glass fiber continuous wire is, the longer it is preferable, because the longer the length of the obtained molded body is, the higher the strength and the like are. However, in the case of extrusion molding or compression molding, the length is usually limited due to molding problems. However, even in such a case, in order to sufficiently obtain the advantage of using the above-described continuous wire, the length of the wire is preferably 20 mm or more, and particularly preferably 50 mm or more.

The glass fiber continuous wire according to the present invention preferably has an impregnation ratio of 95% or more of the molten resin. If it is less than 95%, the strength of the molded article obtained due to stress concentration in the voids is undesirably reduced. The impregnation rate of the molten resin as used herein means that the cross section of the glass fiber continuous wire is 20
Observation with a 0 × electron microscope, a 20 μm mesh was placed. If any voids (bubbles of air) were found in the mesh, this mesh was added as a void area, and the observed total cross-sectional area and void area were calculated. It is obtained by the following formula. ｛(Total cross-section-void area) / total cross-section｝ × 100
(%)

The amount of glass fibers in the glass fiber continuous wire is preferably from 10 to 60% by volume, and more preferably from 20 to 55% by volume. When the amount of the glass fiber exceeds 60% by volume, the glass fiber is not completely covered, and the adhesion between the glass fiber and the vinyl chloride resin tends to be insufficient when the glass fiber is combined with the vinyl chloride resin. Further, when the amount of glass fiber is less than 10% by volume,
The ratio of the coating resin to all the polymer components in the composition is increased, which is disadvantageous in terms of physical properties and economy. The glass fiber content as referred to herein means that the obtained glass fiber continuous wire was 6
After heating in an electric furnace at 00 ° C. to burn off the resin, the glass fiber content (% by mass) was calculated from the weight of the remaining glass, and this value was used as the polymer (a) and polymer ( Using the specific gravity of the resin and the specific gravity of the glass fiber (2.54) determined in consideration of the type and ratio of b), the conversion was made to% by volume.

Further, when the buckling limit when the continuous glass fiber wire is bent is represented by curvature, R, the curvature R is
It is preferable to satisfy the following expression. R ≦ 30D × V × I
² (D = average diameter, V = glass fiber content: volume% / 10
0, I = resin impregnation rate: volume% / 100, unit of R and D: mm). This makes it possible to obtain a continuous fiber rod that is flexible and easy to handle.

As a method for obtaining a vinyl chloride resin molded article using the glass fiber continuous wire of the present invention,
Examples thereof include a method using an extrusion molding device or a drawing molding machine having a crosshead die. For example, when using an extrusion molding apparatus having a crosshead die, it is preferable that a glass fiber continuous wire is passed through the crosshead and shaped with a sizing die together with a vinyl chloride resin.

By using such a method, it becomes possible to uniformly disperse the glass fiber continuous wire in a molded article obtained, and to cover the surface of the molded article with a vinyl chloride resin. As a result, the adhesion between the wire and the vinyl chloride resin increases due to the compatibility effect with the resin, the thermal expansion property is improved, and the mechanical strength of the long molded body is particularly improved. And the glass fiber is uniformly dispersed in the molded body,
It is possible to obtain a molded body having no surface protrusion.

The content of glass fibers derived from the continuous glass fiber wire in the vinyl chloride resin molded article obtained in the present invention is preferably 5 to 50% by mass. If the amount is less than 5% by mass, the reinforcement and improvement of the properties of the vinyl chloride resin cannot be sufficiently achieved. If the amount exceeds 50% by mass, the strength decreases due to a decrease in the ratio of the vinyl chloride resin in the molded article. I do. The content of the glass fiber is particularly preferably from 10 to 30% by mass.

The vinyl chloride resin molded article of the present invention contains various compounding agents, that is, a stabilizer for vinyl chloride resin, an impact resistance improver, a lubricant, a pigment, an antistatic agent, an antioxidant, a filler, and a foam. Agents, flame retardants and the like can be used as needed. The following are typical examples of these compounding agents. Organotin heat stabilizers such as dibutyltin mercaptide, dibutyltin dilaurate, dibutyltin distearate, barium stearate, calcium stearate,
Stabilizers of aliphatic carboxylate salts such as zinc stearate, inorganic stabilizers, epoxy compounds such as epoxidized soybean oil, stabilizers such as organic phosphate and organic phosphite, MB
Impact modifiers such as S resin and acrylic rubber, wax,
Anti-aging agents such as metal soaps, lubricants of higher fatty acids such as stearic acid, phenolic antioxidants, phosphite stabilizers, ultraviolet absorbers, carbon black, hydrated calcium silicate, silica, calcium carbonate, talc, etc. Fillers and so on.

The content of these additives, excluding the filler, is preferably 50 parts by mass or less based on 100 parts by mass of the vinyl chloride resin in the molded article. In addition, when the filler is included, the content of these compounding agents is 10%.
It is preferably 100 parts by mass or less with respect to 0 parts by mass.

Although the shape of the molded article of the present invention is not particularly limited, it is a long-sized extruded or drawn article such as a plate-shaped article having various cross-sectional shapes, a molded article having a large dimension, a rod-shaped article, or a tubular article. Is preferred. Typical applications include building materials such as rain gutters, eaves, outer walls, siding materials, and window frames.

Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. However, it is needless to say that the present invention should not be construed as being limited to such examples.

[0044]

Example 1 60 parts by mass of an acrylonitrile-styrene copolymer as a polymer (a), 40 parts by mass of a maleic acid-modified polypropylene as a polymer (b), and 1,3-bis ( 0.15 parts by mass of (t-butylperoxy-isopropyl) benzene is blended and formed into a melt through an extruder at 250 ° C., and an average diameter of 13 bundles of 600 monofilaments bundled in a bath containing the molten resin.
μm glass fiber strands were introduced and impregnated, and 30 m / min. It was pulled out at the speed of and wound on a bobbin.

The glass fiber continuous wire thus obtained is
The cross section has a circular shape, the average diameter is 0.53 mm, the glass fiber content is 43% by volume, and the resin impregnation rate is 100 on average from the results of measurement at five places (n = 5) since no voids were found.
%Met. Also, the radius of curvature of the wire rod when buckling, R, is n
= 5 and 5.0 mm on average, indicating excellent flexibility.

The fiber continuous wire 40 wound on a bobbin
The pieces were introduced into a guide, arranged in the width direction, drawn into a crosshead connected to an extruder, and combined with a vinyl chloride resin melted at 180 ° C. In the vinyl chloride resin, 1 part by weight of dibutyltin mercaptide (stabilizer) was blended with respect to 100 parts by weight of the vinyl chloride resin.

Further, after cooling the above-mentioned composite, it is drawn into a sizing device and sized to obtain a 2 mm thick and 25 mm wide glass fiber continuous wire.
A 2000 mm long vinyl chloride resin molded product was obtained. The glass fiber content in the molded article was 12.6% by mass.

Example 2 As a polymer (a), 80 parts by mass of an acrylonitrile-styrene copolymer, as a polymer (b), 20 parts by mass of maleic acid-modified polypropylene, and as a peroxide,
1,3-bis (t-butylperoxy-isopropyl)
0.15 parts by mass of benzene was blended and made into a melt through an extruder at 250 ° C., and 600 monofilaments were bundled in a tank containing the molten resin, having an average diameter of 13 μm.
m glass fiber strands are introduced and impregnated, and a nozzle having a diameter of 0.53 mm is used for impregnation at 15 m / min. It was pulled out at the speed of and wound on a bobbin. The fiber continuous wire thus obtained had a circular cross section, an average diameter of 0.53 mm, a glass fiber content of 43% by volume, a resin impregnation rate of 100%, and a radius of curvature R of 5.5 mm.

Using the obtained fiber continuous wire, Example 1
2mm thickness, 25m width
m, a vinyl chloride resin molded article having a length of 2000 mm was obtained.
The glass fiber content in this molded product was 12.6% by mass.
Met.

Example 3 As a polymer (a), 60 parts by mass of an acrylonitrile-styrene copolymer, as a polymer (b), 40 parts by mass of maleic acid-modified polypropylene, and as a peroxide,
0.15 parts by mass of 1,3-bis (t-butylperoxyisopropyl) benzene was blended and melted at 250 ° C. through an extruder, and four monofilament glass fiber strands having an average diameter of 13 μm and 600 monofilaments were introduced. 10 m from a nozzle with a diameter of 0.65 mm
/ Min. It was pulled out at the speed of and wound on a bobbin.

The glass fiber continuous wire thus obtained is
The cross section was circular, the average diameter was 0.65 mm, the glass fiber content was 59% by volume, and the resin impregnation rate was 95%. The radius of curvature R of the wire at the time of buckling was 15 mm. By performing the above 10 wires wound on a bobbin in the same manner as in Example 1, a 2 mm thick, 25 mm wide, and 2,000 mm long vinyl chloride resin molded product using a glass continuous fiber wire as a core material was obtained. The glass fiber content in the molded article was 12.6% by mass.

Comparative Example 1 The same glass fiber strands as in the example were introduced into 40 guides, arranged in the width direction, drawn into a crosshead connected to an extruder, and combined with a vinyl chloride resin melted at 180 ° C. . For vinyl chloride resin, vinyl chloride resin 1
1 part by mass of dibutyltin mercaptide (stabilizer) was added to 00 parts by mass.

Further, after cooling the above-described composite, the composite is drawn into a sizing device and sized to obtain a 2 mm thick and 25 m wide glass fiber strand as a core material.
m, a vinyl chloride resin molded article having a length of 2000 mm was obtained.
The glass fiber content in the molded article was 12.1% by mass.

Comparative Example 2 A continuous fiber rod produced in the same manner as in Example 1 was cut into a length of 6 mm, and 100 parts by weight of a vinyl chloride resin, 1 part by weight of dibutyltin mercaptide (stabilizer), and 25 parts by weight of the cut wire were used. Blend, L / D24, compression ratio 2.3, 30m
Using a single screw extruder having a diameter of m, a molded product similar to the example was obtained at a melting temperature of 180 ° C. The glass fiber content in this molded product was 13.0% by mass.

Comparative Example 3 As a polymer (a), 60 parts by mass of an acrylonitrile-styrene copolymer, as a polymer (b), 40 parts by mass of maleic acid-modified polypropylene, and as a peroxide, 1,3-bis (t 0.15 parts by mass of (-butylperoxyisopropyl) benzene was blended into a melt through an extruder, and the average diameter was 13 μm and the number of bundles was 60.
0 glass fiber strands were introduced and impregnated, and 15 m / min. , And wound on a bobbin with a large diameter.

The continuous fiber reinforced wire thus obtained had an average diameter of 2.2 mm, a glass fiber content of 43% by volume, and an impregnation rate of 100%.

Curvature radius R at the time of buckling of continuous glass fiber wire
Was 400 mm, lacked in flexibility, and was difficult to work when aligned through a guide, and a satisfactory vinyl chloride resin molded article could not be obtained.

Table 1 shows various physical properties of the glass fiber continuous wire and the obtained vinyl chloride resin molded product in the above Examples and Comparative Examples. The linear expansion coefficient in Table 1 is
It was calculated from the dimensional change in the longitudinal direction of the molded product from -20 ° C to 60 ° C. The absolute amount of dimensional change is as follows: temperature difference 80 ° C, 20
The amount of change in the longitudinal direction of the molded product having a length of 00 mm was determined. The bending strength was measured by setting the longitudinal direction of the molded body as the longitudinal direction of the test body.

[0059]

[Table 1]

[0060]

The continuous glass fiber wire of the present invention has good drawing and productivity, has excellent flexibility, and has a high glass fiber content.

Therefore, according to the present invention, a fiber-reinforced vinyl chloride resin molded article excellent in mechanical strength such as impact resistance, thermal expansion resistance, and surface appearance, particularly a molded article having a large size, and a pultruded article The present invention provides a glass fiber continuous wire suitable for producing a fiber-reinforced vinyl chloride resin molded article for a long molded article obtained by the above method and a vinyl chloride resin molded article using the same.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C08L 27/06 C08L 27/06

Claims (8)

[Claims] A continuous glass fiber strand obtained by bundling a plurality of monofilaments comprises a polymer (a) which is miscible with a vinyl chloride resin and a polymer which is immiscible and crystalline with a vinyl chloride resin ( b) impregnated with a molten resin containing: a) a molded article of vinyl chloride resin having an average cross-sectional diameter of 0.2 to 1.5 mm and a glass fiber content of 10 to 60% by volume. Glass fiber continuous wire for use. 2. The glass fiber continuous wire rod has an impregnation ratio of the molten resin of 95% by volume or more, and a curvature R of a buckling limit when bent is R ≦ 30D × V × I ² (D = average). Diameter, V
The glass fiber continuous wire according to claim 1, which satisfies = glass fiber content: volume% / 100, and I = impregnation rate of molten resin: volume% / 100, units of R and D: mm. 3. The glass fiber continuous wire according to claim 1, wherein the content ratio of the polymer (a) and the polymer (b) is from 95 to 5: 5 to 95 by mass ratio. 4. A method according to claim 1, wherein said peroxide is decomposed at a melting temperature of said molten resin to generate free radicals, and contains 0.1 to 5 parts by mass per 100 parts by mass of said molten resin.
The glass fiber continuous wire according to the above. 5. The method according to claim 1, wherein the polymer (a) is acrylonitrile-
The glass fiber continuous wire according to any one of claims 1 to 4, which is a styrene copolymer. 6. The glass fiber continuous wire according to claim 1, wherein the polymer (b) is polypropylene. 7. A vinyl chloride resin molded article reinforced by the glass fiber continuous wire according to any one of claims 1 to 6, wherein the glass fiber continuous wire is substantially contained in the vinyl chloride resin molded article. A vinyl chloride resin molded product characterized by being continuously arranged in a longitudinal direction. 8. The vinyl chloride resin molded article according to claim 7, wherein the glass fiber based on the glass fiber continuous wire in the vinyl chloride resin molded article is 5 to 50% by mass.