JP2000037765A - Method for molding resin composition containing glass fiber, and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the dispersion properties of glass fibers and increase the length of the residual glass fiber by setting a temperature for mixing the glass fibers which are coated with a resin below the resin melting temperature level and at the same time, setting a part of the intradevice temperature for kneading above the resin melting temperature level. SOLUTION: The temperature at which resin-coated glass fibers are mixed with a molten and kneaded matrix resin composition is set below the melting temperature of a coating resin. In addition, in the step to knead the resin-coated glass fibers with the matrix resin composition and mold the mixture, a part of the temperature in the kneading part of a device is set above the temperature at which the melting of the coating resin is initiated. Under this constitution, the resin-coated and bundled glass fibers are fed to a following step without being splitted by setting temperature conditions in the mixing step, so that the glass fibers are not ruptured against an external stress. Further it is possible to uniformly disperse the glass fibers in the matrix resin composition under temperature setting conditions in the kneading and molding steps.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding method for extruding a glass fiber-containing resin composition to obtain a molded article having excellent strength, impact resistance, modulus of elasticity, water resistance, surface appearance, and the like. Related to molded articles.

[0002]

2. Description of the Related Art It is known that a resin is mixed with glass fiber to enhance and improve the properties of the resin. In this case, the two points of (1) increasing the dispersibility of the glass fiber in the final molded product and (2) increasing the length of the remaining glass fiber are extremely large in strengthening and improving the resin properties. One of the factors that have an effect. If the material is strongly kneaded to increase the dispersibility, the glass fibers will break, and if the degree of kneading is reduced to keep the length of the glass fibers long, the dispersibility of the glass fibers will decrease. It is considered to be.

To solve this problem, for example, (1)
Lowering the viscosity of the resin and wetting with the glass fiber by a method of increasing the molding temperature and (2) a method of adding a lubricant, a surface modifier or a resin having excellent fluidity and being miscible with the resin. To improve dispersibility.

However, in the method (1) of increasing the molding temperature, strict temperature control is generally required because the decomposition temperature of the resin and the molding temperature are close to each other, which is not practical.
In addition, in the method (2) of adding a resin that lowers the viscosity of the resin, a large amount of resin is required to obtain a desired viscosity level, and the inherent properties of the resin are significantly changed.
The advantage of increasing the mechanical strength by adding glass fibers is offset. Either method is not sufficient in that the glass fibers are broken if sufficient dispersibility of the glass fibers is obtained, and the glass fibers remain long.

[0005] In addition, (3) glass fibers previously coated with a resin (hereinafter, referred to as resin-coated glass fibers) are blended with a resin (hereinafter, referred to as a matrix resin) constituting a matrix resin, and are melted and kneaded to form a glass. It has been proposed to improve the fiber dispersibility and to produce a molded product by extrusion of a glass fiber-containing resin composition (JP-A-8-319390, JP-A-8-225).
700). The resin-coated glass fiber referred to here is one obtained by bundling two or more glass single fibers into one form using a resin. This method is characterized in that single fibers are dispersed in a matrix resin with low kneading force. But,
When the glass fiber-containing resin composition according to this method is applied to extrusion molding, if the entire kneading step of the step (3) is maintained at a temperature equal to or higher than the melting temperature of the coating resin, the bundled glass fibers are defibrated and mixed from the beginning of the kneading step. As a result, the resin-coated glass fiber is broken as in the case of the uncoated glass fiber, and there is a problem that it is difficult to leave the glass fiber length sufficiently long.

[0006]

The object of the present invention is to increase the dispersibility of glass fibers in a molded article obtained by molding a glass fiber-containing resin composition and to increase the length of remaining glass fibers. It is an object of the present invention to provide a molding method for enhancing and improving resin properties and a molded product thereof.

[0007]

SUMMARY OF THE INVENTION According to the present invention, there are provided a step (1) of melting and kneading a composition containing a matrix resin not containing glass fibers coated with a resin (hereinafter referred to as a matrix resin composition). Step (2) of mixing the glass fiber coated with the resin with the matrix resin composition melted and kneaded in 1), and the step (3) of kneading and molding the composition obtained in step (2) Wherein the temperature at which the glass fibers coated with the resin in the step (2) are mixed is equal to or lower than the melting temperature of the resin coating the glass fibers, and
An extrusion molding method of a glass fiber-containing resin composition, characterized in that a part of the temperature in an apparatus for kneading in the step (3) is equal to or higher than a melting temperature of a resin coating the glass fiber, and a molded product thereof.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the step (1) of melting and kneading a matrix resin composition containing no resin-coated glass fiber, the supplied matrix resin composition may be melted and kneaded. The extruder used is not limited to a single-screw configuration or a multi-screw configuration having two or more shafts,
In order to more reliably perform melting and kneading, it is preferable to use a molding machine having two or more shafts. The melting and kneading temperature may be a temperature at which the matrix resin is sufficiently kneaded and does not cause decomposition.

The shape of the apparatus in the step (2) of mixing the resin-coated glass fiber with the matrix resin composition melted and kneaded in the step (1) is not particularly limited, but the resin-coated glass fiber can be added stably. Preferably, it can be mixed with the matrix resin composition. When a general extruder is used in step (1), resin-coated glass fibers can be added through a side feed port, a vent port, or the like of the extruder. The internal pressure of the apparatus for adding the resin-coated glass fiber is preferably low in order to stably add the resin-coated glass fiber.
The degree of the low pressure is preferably 300 mmHg or less, particularly 5 mmHg.
0 mmHg or less is preferable. The lower the pressure, the better.

In this step (2), the temperature at which the glass fibers coated with the resin are mixed with the melted and kneaded matrix resin composition must be lower than the melting temperature of the coating resin. By setting the temperature conditions, the resin-coated and bundled glass fibers are carried to the next step (3) without being defibrated. The bundled resin-coated glass fibers in a state in which they are not defibrated do not break due to external stress such as kneading, or break very little.

In the step (3) of kneading and molding the resin-coated glass fiber and the matrix resin composition, the step (1)
What is necessary is just to disperse | distribute a glass fiber uniformly to the discharge matrix resin composition from this. For that purpose, it is necessary to set the temperature of one part of the kneading part of the apparatus in the step (3) to be equal to or higher than the melting start temperature of the coating resin. One part of the kneading section of the apparatus in the step (3) for setting the temperature to be equal to or higher than the melting start temperature of the coating resin is preferably the latter half of the kneading section.
A range from any point of ~ 90% to 100% is preferable, and a range from any point of 70 to 90% to 100% is particularly preferable. The temperature above the melting start temperature of the coating resin may be any temperature at which the resin-coated glass fiber and the matrix resin are sufficiently kneaded and no decomposition occurs. The shape of the molded product of the composition extruded in the step (3) is not particularly limited, but is preferably a plate, a bar, a tube, or the like. From the pellet-shaped molded product obtained in the step (3), a molded product can be obtained through a further molding step.

The kneading apparatus of the step (3) does not particularly require a screw constituting mechanism for applying a high shearing force such as kneading or mixing. The extruder used for kneading in the step (3) is not particularly limited to the shape of the apparatus, the shaft configuration, the screw shape, etc. In order to significantly reduce the breakage of the glass fiber and leave the glass fiber length longer, What is necessary is just to knead by applying the minimum shearing force that can disperse the glass fiber. Specifically, a single-screw extruder that is less kneaded than a twin-screw extruder is preferable. In the case of a single-screw extruder, the compression ratio is preferably small and the screw groove is preferably deep.

Although the steps (1) to (3) may be operated separately, it is preferable to continuously operate the three steps in terms of production efficiency. If the three steps cannot be performed continuously, the matrix resin composition containing no resin-coated glass fiber is melted and kneaded in step (1) to produce pellets and the like, and then the hopper is used in step (3). Step (1)
It is preferable to supply the composition obtained by mixing the matrix resin composition and the resin-coated glass fiber melt-kneaded in the above, and to continuously operate the steps (2) and (3). It is preferable that the operations of the steps (2) and (3) are simultaneously performed under reduced pressure. By performing the treatment under reduced pressure, the air between the resin-coated glass fibers easily escapes, the adhesion between the glass fibers and the resin is improved, and the obtained molded product is excellent in physical properties and surface appearance.

The matrix resin composition of the present invention may contain various compounding agents in addition to the matrix resin. The resin used as the matrix resin is not particularly limited as long as it is a thermoplastic resin generally used for extrusion molding, but is preferably a thermoplastic chlorine-containing resin, and particularly preferably a vinyl chloride polymer. Specifically, vinyl chloride polymers, polystyrene,
Polyamide, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinylidene fluoride, polyphenylene sulfide, polyphenylene oxide, polyether sulfone, polyether ether ketone, and the like are exemplified, and a vinyl chloride polymer is preferable.

The vinyl chloride polymer can be obtained by a known production method, that is, a suspension polymerization method, an emulsion polymerization method, or a bulk polymerization method. The average degree of polymerization of the vinyl chloride polymer is 400 to 150.
A range of 0 is preferred, and a range of 450 to 1000 is particularly preferred. If the average polymerization degree 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 remarkably reduced and molding becomes too difficult, which is not preferable.

The term "vinyl chloride polymer" as used herein means that the polymer is substantially a vinyl chloride polymer, and that at least 60% by weight of the constituents are composed of polymerized units based on vinyl chloride. Specifically, a vinyl chloride homopolymer,
Ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, a graft copolymer obtained by graft-polymerizing an ethylene-vinyl acetate copolymer to a vinyl chloride polymer, and the like, and also a post-chlorinated polyvinyl chloride. These include those used alone or in combination of two or more.

As the various compounding agents, stabilizers for vinyl chloride resins, impact modifiers, lubricants, pigments, antistatic agents, antioxidants, fillers, foaming agents, flame retardants and the like can be used as required. The following are typical examples of these compounding agents. Organic tin heat stabilizers such as dibutyltin mercaptide, dibutyltin dilaurate, dibutyltin distearate, etc .; stabilizers of aliphatic carboxylic acid salts such as barium stearate, calcium stearate, zinc stearate; inorganic stabilizers; epoxidized soybean oil, etc. Stabilizers such as epoxy compounds, organic phosphates and organic phosphites, MBS
Impact modifiers such as resin and acrylic rubber, waxes, metallic soaps, lubricants of higher fatty acids such as stearic acid, phenolic antioxidants, phosphite stabilizers, antioxidants such as ultraviolet absorbers, carbon black, water Fillers such as calcium silicate, silica, calcium carbonate, talc, wollastonite and mica.

The total amount of these additives is preferably 50 parts by weight or less based on 100 parts by weight of the vinyl chloride polymer excluding the filler. The total amount of these additives, including fillers, is 10 parts by weight per 100 parts by weight of the vinyl chloride polymer.
0 parts by weight or less is preferred.

As the glass fiber, it is preferable to use various commercially available forms, for example, a relatively long glass fiber such as a roving or chopped strand. The average fiber diameter of the glass fibers is preferably 1 to 20 μm.

The glass fibers may have been subjected to ordinary surface treatment with a coupling agent, a film former, a lubricant, and other surface treatment agents. For example, as the coupling agent, there is a silane compound in which a hydrolyzable group called a silane coupling agent is bonded to a silicon atom. The following compounds can be exemplified as specific silane coupling agents.

Methacrylsilane-based compounds such as 3-methacryloyloxypropyltriethoxysilane and 3-methacryloyloxypropylmethyldiethoxysilane;
-Epoxysilane compounds such as glycidoxypropyltrimethoxysilane, aminosilane compounds such as 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, vinyltrimethoxysilane and the like And chlorosilane compounds such as 3-chloropropyltrimethoxysilane.

The method of coating the glass fiber with the coating resin is not particularly limited. Usually, a method of impregnating a glass fiber with a coating resin in a molten state is preferable. Specifically, a method in which roving-like glass fiber is continuously passed through a resin tank containing a coating resin in a molten state to impregnate the glass fiber with the coating resin, and then cut.
In this case, a method in which glass fibers are continuously passed through a coating resin tank in which a molten coating resin is continuously transferred using an extruder is preferable from the viewpoint of productivity. The amount of extrusion from the extruder is determined by the amount of glass fiber supplied to the coating resin tank.

The resin for coating the resin tank has a melt viscosity of 1000
It is preferable to adjust the poise to not more than 500 poise. If the melt viscosity of the coating resin is more than 1000 poise, it is difficult for the coating resin to impregnate the roving-like glass fiber, and when the resin-coated glass fiber is blended with the resin, the dispersion of the glass fiber becomes insufficient, and the No improvement is observed, and the surface appearance and the like of the molded article are unfavorably impaired.

The resin-coated glass fiber obtained by the above method is preferably cut into an average length of 1 to 50 mm, especially 1 to 20 mm in terms of handling. Regarding the number of bundled glass fibers, it is desirable that the fiber bundle strength of the resin-coated glass fibers in an undefibrated state is a strength that cannot be broken in a normal kneading step, and specifically, 3 or more, preferably 8 It is desired that more than one glass fiber be bundled. In addition, when the number of bundles increases, the amount of resin for coating hardly impregnates the glass fiber, and the preferred number of bundles is 3 to 10.

The amount of coating resin in the resin-coated glass fiber is
It is preferably at least 5% by weight. When the amount of the coating resin is less than 5% by weight, the glass fibers are not completely covered, and when kneaded with the matrix resin composition, the dispersibility of the glass fibers and the adhesion of the matrix resin composition to the resin become insufficient. Cheap. Also, if the amount of the coating resin is too large,
In the present invention, the ratio of the coating resin to all the polymer components in the glass fiber-containing resin composition is increased, which may cause a decrease in physical properties and may be disadvantageous in terms of economy. The amount of the coating resin in the resin-coated glass fiber is preferably at most 60% by weight, particularly preferably at most 40% by weight.

The coating resin is not particularly limited, but it is desirable that the melting start temperature of the coating resin be within the molding temperature range of the matrix resin composition. When the matrix resin is a polyvinyl chloride composition, the melting start temperature is 80
It is preferable that it is in the range of -200 ° C. As the coating resin, a polymer (a) miscible with a vinyl chloride polymer,
A resin obtained by melting a component containing a polymer (b) and a peroxide (c) that is immiscible with the vinyl chloride polymer and is crystalline is preferable.

[Polymer (a) Miscible with Vinyl Chloride Polymer] The term “miscibility” as used herein means that a vinyl chloride polymer and a miscible polymer are in a thermodynamically stable state on a molecular order. Or a property in which some affinity acts on the interface to form a stable microphase separation state. Therefore, when the polymer (a) is a vinyl chloride polymer, it is mixed substantially uniformly. When the polymer (a) has a certain degree of miscibility with the vinyl chloride-based polymer, the polymer (a) is stably dispersed in a continuous layer of the vinyl chloride-based polymer in a particle state having a particle diameter of, for example, 0.01 to 10 μm. sell.

That is, when the coated glass fiber containing the polymer (a) is blended with the vinyl chloride polymer and melt-kneaded, the effect is obtained that the glass fiber is rapidly and uniformly dispersed in the vinyl chloride polymer together with the glass fiber. In addition, since the interface with the vinyl chloride polymer as the matrix resin has an affinity, it can exert an effect of remarkably improving mechanical strength such as impact resistance, strength, elastic modulus and water resistance. The molecular weight of the polymer (a) is not particularly limited, but if the molecular weight is too large, kneadability with other components is insufficient, which is not preferred, and the average molecular weight is preferably from 1,000 to 400,000.

The polymer (a) is entirely composed of the polymer (a)
May contain other polymerized units as long as the polymer is miscible with the vinyl chloride polymer. Specific examples of the polymer (a) may be the above-mentioned vinyl chloride polymer, a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer, an alkyl acrylate polymer, and methacrylic acid. An acid alkyl ester polymer, a vinyl acetate polymer or the like may be used.
Preferred examples of the polymer (a) include a copolymer of a vinyl cyanide-based monomer and an aromatic vinyl-based monomer, and an alkyl methacrylate-based polymer.

More specifically, as a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile and styrene, α-methyl Styrene, vinyl toluene,
It is a copolymer obtained by copolymerizing a monomer in combination with an aromatic vinyl monomer such as chlorostyrene, and the proportion of polymerized units based on the vinyl cyanide monomer in the copolymer is , Preferably 5 to 80% by weight, and 10 to 50% by weight.
It is particularly preferred that the amount is by weight.

If the proportion of the vinyl cyanide-based polymer unit is small, the miscibility with the vinyl chloride-based polymer becomes poor,
It cannot disperse sufficiently in the vinyl chloride polymer which is the matrix resin, the mechanical strength of the obtained molded product decreases, and the affinity with the glass fiber is not enough, and the water resistance of the obtained molded product is poor. It is not preferable because it deteriorates. A particularly preferred copolymer is an acrylonitrile-styrene copolymer.

As the alkyl acrylate polymer and the alkyl methacrylate polymer, a polymer of a monomer having 4 or less carbon atoms in the alkyl portion is preferable. When the number of carbon atoms in the alkyl moiety is 5 or more, the polymer becomes poor in miscibility with the vinyl chloride polymer, which is not preferable for the same reason as described above. Particularly, a methacrylic acid alkyl ester monomer is preferable.

At least one polymer of the alkyl methacrylate monomer, a copolymer of a combination of the alkyl methacrylate monomer and another alkyl methacrylate monomer, A copolymer of a combination of an acid alkyl ester monomer and a monomer other than the alkyl methacrylate monomer is preferred. Specific examples include polymethyl methacrylate, methyl acrylate-ethyl methacrylate copolymer, and methyl methacrylate-styrene copolymer. A particularly preferred polymer is polymethyl methacrylate.

Examples of the vinyl acetate-based polymer include a vinyl acetate homopolymer and an ethylene-vinyl acetate copolymer. In the case of the ethylene-vinyl acetate copolymer, the ratio of the polymerization unit based on the vinyl acetate monomer is 10%. % By weight or more is preferred. If the amount is less than 10% by weight, the miscibility with the vinyl chloride polymer becomes poor, which is not preferable for the same reason as described above.

Among the polymers (a), those having a higher glass transition temperature than the vinyl chloride polymer are more preferable from the viewpoint of heat resistance typified by the heat distortion temperature when blended with a vinyl chloride resin, and acrylonitrile is preferred. -Styrene copolymers or polymethyl methacrylate are particularly preferred.

[About the crystalline polymer (b) which is immiscible with the vinyl chloride polymer] The polymer (b) has no affinity at the interface with the vinyl chloride polymer and has stable microphase separation. It has the property of not being able to form a state and exhibits crystallinity. The crystallinity as referred to herein means a clear crystal melting point, for example, a substance showing an endothermic peak by a thermal analysis method such as DSC, and having a property that the melt viscosity is rapidly lowered at the temperature, and is not necessarily a crystallization. Does not mean 100%.

The melting point of the crystal is preferably 250 ° C. or less, which is close to the processing temperature of the vinyl chloride polymer.
Particularly, the temperature is preferably 200 ° C. or lower. Furthermore, mechanical strength,
From the viewpoint of heat resistance, the lower limit is preferably a glass transition temperature higher than that of the vinyl chloride-based polymer,
Particularly, the temperature is preferably 100 ° C. or higher.

When the resin-coated glass fiber is blended with the vinyl chloride polymer and melt-kneaded, the polymer (b) in the coating resin is essentially not miscible with the vinyl chloride polymer. It shows a so-called lubricating property of sliding on a molecular chain of a vinyl chloride polymer without being entangled with the molecular chain. In particular, it is remarkable when the crystal melting point is lower than the processing temperature. Therefore, the melt viscosity of the system can be reduced, and the effect of significantly improving the moldability and surface appearance can be exhibited, and the shearing force generated by kneading can be reduced. Improve.

The molecular weight of the polymer (b) is not particularly limited. However, if the molecular weight is too large, the kneadability with other components is insufficient, which is not preferable, and the average molecular weight is from 1,000 to 4,000.
00 is preferred. The polymer (b) may contain other polymer units as long as the polymer (b) shows immiscibility with the vinyl chloride polymer as a whole. For example, a homopolymer of ethylene, propylene, and other α-olefins, or a combination of these monomers may be used. Specifically, polyethylene and polypropylene are preferred, and polypropylene is particularly preferred.

The mixing ratio of the polymer (a) and the polymer (b) is in the range of 95 to 5% by weight, the latter in the range of 5 to 95% by weight, and the former in the range of 80 to 20% by weight. % By weight, the latter being particularly preferred in the range of 20% to 80% by weight. If any one of the proportions is less than 5% by weight, any of the effects of the polymer (a) and the polymer (b) cannot be exhibited.

[Regarding Peroxide (c)] The peroxide (c) can be decomposed by heat to generate free radicals, and known organic peroxides can be used. Specifically, the following can be exemplified.

Ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide;
Hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide and t-hexyl hydroperoxide; dialkyls such as dicumyl peroxide and 1,3-bis (t-butylperoxyisopropyl) benzene Peroxides, benzoyl peroxide, diacyl peroxides such as lauroyl peroxide, diisopropyl peroxy dicarbonate, peroxy dicarbonates such as di-n-propyl peroxy dicarbonate, etc., peroxy esters, peroxy Ketals and the like.

The decomposition temperature is a temperature at which free radicals can be generated under the temperature conditions for obtaining the coating resin, and varies depending on the conditions. However, a 10-hour half-life temperature in the range of 70 to 150 ° C. is preferable in handling. .

Free radicals generated from these peroxides during melting cause (1) polymer (a) and / or polymer (b) to break molecular chains, reduce the melt viscosity of the system, and reduce the viscosity of the glass fibers. (2) Simultaneously with the polymer (a) starting from a radical newly generated in the molecular chain by a reaction for abstracting hydrogen and the like from the polymer (a) and the polymer (b), The copolymer which is considered to be formed by the reaction with the polymer (b) acts as a compatibilizer for the remaining polymer (a) and the polymer (b),
It can be expected that mixing will be easier.

When a coating resin obtained by melting a component containing the polymer (a), the polymer (b) and the peroxide (c) is coated on the glass fiber, the resin is easily impregnated into the glass fiber. The melt viscosity of the coating resin in the molten state is 10
00 poise or less, especially 500 poise or less is preferable.

Various components may be added to the component containing the polymer (a), the polymer (b) and the peroxide (c). For example, a surface treatment agent for glass fibers such as a silane coupling agent and a lubricant described below can be blended.
The amount of peroxide (c) added may be determined according to the melt viscosity of the coating resin in a molten state. If the amount of peroxide (c) is too large, the reaction becomes complicated, which is not preferable from the viewpoint of workability, safety and economy. The amount of the peroxide (c) to be added is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the polymer (a) and the polymer (b).

[Regarding Copolymer (d)] The copolymer (d) can be used together with the polymer (a), the polymer (b) and the peroxide (c). The polymer chain (X), which is a component of the copolymer (d), is immiscible with the vinyl chloride polymer similarly to the polymer (b), and the polymer chain (Y) is a polymer (a). ) Has miscibility with a vinyl chloride-based polymer as in the case of (a), so that the polymer (a) is substantially used.
And a polymer (b) in one molecule. Therefore, it is considered that the copolymer which is considered to be produced by partially reacting the polymer (a) and the polymer (b) has the same structure as the copolymer (d).

However, the polymer (a) and the polymer (b)
It has completely opposite properties to vinyl chloride polymers, and both are essentially poorly miscible, and when the difference in melt viscosity between the two is significantly different when coating glass fibers, It becomes difficult to mix uniformly, and the coated state of the glass fiber becomes extremely uneven, and the reproducibility of the characteristics may be reduced.

Therefore, when the above phenomenon is remarkable due to the combination of the selected polymer (a) and polymer (b), use of the copolymer (d) to obtain a coating resin is required. Makes it act as a compatibilizer for the polymer (a) and the polymer (b), and can be very easily and uniformly mixed at the initial stage of melt-kneading.

In this case, the polymer chain (X) is a polymer (b)
And the polymerization chain (Y) is a polymer (a)
It is more preferable that it has the same structure as that described above, since such an effect can be remarkably exhibited. Therefore, it is not necessary to use the copolymer (d) in a large amount, and the amount of the copolymer (d) added is
Polymer (a), polymer (b) and peroxide (c)
0.1 to 2 with respect to a total of 100 parts by weight of the
0 parts by weight is an appropriate amount.

The length of the polymerization chain (X) in the copolymer (d) is not particularly limited as long as it is immiscible with the vinyl chloride polymer. Similarly, the length of the polymerization chain (Y) is not particularly limited as long as it is miscible with the vinyl chloride polymer. However, a polymer obtained by alternately polymerizing the polymer units constituting the immiscible polymer with the vinyl chloride polymer and the polymer units constituting the miscible polymer is not preferred as the copolymer (d). A polymer in which polymerization units are randomly polymerized is not preferred as the copolymer (d).

Therefore, as the copolymer (d), a block copolymer or a graft copolymer having at least one polymer chain (X) and one polymer chain (Y) is preferable, and the polymer chain (X) is a polymer (X). A combination having the same structure as that of b) and having the same structure as the polymer chain (Y) is more preferable. In the case of a graft copolymer, the polymerization chain (X) may be either a trunk chain or a branch chain. However, a graft copolymer in which the polymerization chain (X) is a trunk chain and the polymerization chain (Y) is a branch chain is preferable in terms of the effects of the invention, ease of production, and the like.

The polymerization chain (X) constituting the copolymer (d)
And the proportion of the polymerization chain (Y) is 95 to 5% by weight of the former,
The latter is in the range of 5 to 95% by weight and the former is in the range of 80 to 20% by weight.
% By weight, the latter being particularly preferred in the range of 20 to 80% by weight.

The above range is preferable because it exhibits an effect as a compatibilizer for the polymer (a) and the polymer (b). The molecular weight of the copolymer (d) is not particularly limited, and is preferably 1,000 to 400,000 in terms of average molecular weight,
200,000 is particularly preferred.

The method for producing the copolymer (d) is not particularly limited, and a known method can be employed.

The shape of the molded article of the composition of the present invention is not particularly limited, but is preferably an extruded molded article such as a plate, a rod, or a tube having various cross-sectional shapes. Typical applications include building materials such as rain gutters, eaves, outer wall siding materials, and window frames.

[0057]

The present invention will be described in detail below, but the present invention is not limited to these. In the following, parts mean parts by weight.

[Manufacturing Apparatus] Manufacturing apparatuses in Examples and Comparative Examples are shown below.

(Twin-screw extruder) Twin-screw extruder (Pike, Ikegai)
CM30) was set to rotate in the same direction, and the screw portion was divided into eight zones of approximately equal length to control the temperature in the extruder shown in FIG. The screw configuration is shown in FIG. A mixing zone is arranged in the center, and the kneading disk has an RNL configuration, and a vent port is arranged downstream of the mixing zone.

(30 mmΦ single screw extruder) A single screw extruder (FS30, manufactured by Ikegai Co., Ltd.)
D is 25, screw compression ratio (C
R) is 2.6, the tip groove depth is 1.4 mm, the solid transport section is 4 ridges, the metering section is 5 ridges, and a 3 mm-thick and 30 mm-wide die for forming a flat plate is provided downstream of the dies through an adapter. Was attached. Further, the screw portion was divided into three zones of substantially equal length to control the temperature in the extruder 1 shown in FIG.

(65 mmΦ single screw extruder) A single screw extruder (FS65, manufactured by Ikegai Co., Ltd.)
D is 8, CR is 1.4, tip groove depth is 8mm, solid transporting section is 3 ridges, metering section is 3 ridges, and downstream thereof is formed with a 3mm thick and 80mm wide flat plate via an adapter. Dice was attached. The temperature inside the extruder 2 was controlled by dividing the screw portion into two zones of approximately equal length. Next, raw materials used in Examples and Comparative Examples are shown below.

[Coating resin] The coating resin components are as follows. (A1) Acrylonitrile-styrene copolymer (acrylonitrile content: 28% by weight, melt index (hereinafter referred to as MI) 25 g / 10 minutes) (b1) Polypropylene (crystal melting point: 165 ° C., MI:
(C1) dicumyl peroxide (10-hour half-life temperature:
117 ° C) [Production of resin-coated glass fiber]
It was manufactured by the following method. The above component (a1) 40
Parts, component (b1) 60 parts and component (c1) 2.5 parts were blended using a Henschel mixer, and then blended with 50 mm
Using a single screw extruder, the mixture was extruded at a cylinder temperature of 250 ° C., a die temperature of 300 ° C. and a rotation speed of 75 rpm, and supplied to a coating resin tank kept at 300 ° C. Component (a1),
The melt viscosity of the coating resin according to (b1) and (c1) was determined using a capillary having a length of 2.5 mm and a diameter of 0.25 mm.
When measured at 00 ° C. and a shear rate of 1000 sec ⁻¹ , 9
It was 5 poise. The melting point of this coating resin is 16
3 ° C. On the other hand, a roving-like glass fiber having an average fiber diameter of 13 μm is continuously passed through a molten coating resin tank, and the coating resin is impregnated between monofilaments, and then passed through a 2.2 mm-diameter die. Amount of resin was removed, and the weight ratio of resin component to glass fiber was 3
It was adjusted to 0/70. The obtained resin-coated glass fiber was cut into an average length of 6 mm by a rotary cutter. Hereinafter, this is referred to as a glass fiber (GF-A) coated with a resin. The defibration temperature of this GF-A was 163 ° C., which was equivalent to the melting point of the coating resin.

Example 1 In the formulation shown in Table 1, G
Powder materials except FA are charged into a Henschel mixer,
The mixture was stirred and mixed at 1000 rpm from room temperature until the powder temperature rose to 115 ° C. to obtain a powder mixture A. Mixture A
Was put into a twin-screw extruder, and melted and kneaded to produce pellets A. FIG. 1 shows the temperature settings of the twin-screw extruder. The rotation number of the screw was 50 rpm. The charging rate of the mixture A was 5 kg / hr.

10.35 kg of the pellet A and 2 kg of GF-A were put into a cooling mixer for mixing powder, and mixed at room temperature at 500 rpm for 1 minute to obtain a mixture B.
The mixture B is put into the hopper of the single screw extruder 1 and the thickness is 3
A flat plate having a width of 30 mm and a width of 30 mm was formed. As shown in FIG. 3, the extruder 1 has a solid transport section (zone 1) of 155 ° C., a compression section (zone 2) of 165 ° C., and a measuring section (zone 3) of 175.
C. and 180 ° C. were set from the breaker plate to the die. The resin temperature in each zone was equal to the set temperature in each zone of the extruder, and the temperature above the melting point (163 ° C.) of the coating resin was 40 to 100% after the extruder 1. The discharge rate at a screw rotation speed of 20 rpm was 65 g / min. The glass fiber length in the obtained flat molded product is 1.2 m
m. The specific gravity of the molded product was 97% of the theoretical specific gravity calculated from the composition.

[Example 2] The die portion of the twin-screw extruder was removed, and the extruder 2 was arranged at the tip of the twin-screw extruder. To fall. As shown in FIG. 4, the screw portions (zones 9 and 10) in the extruder 2 were set at 160 ° C. and 190 ° C., and the temperature from the adapter to the die was set at 180 ° C. The temperature above the melting point of the coating resin is 50-100% higher than after the extruder 2.
Met. Mix A in the hopper of the twin screw extruder
Inject at a speed of 5 kg / hr, screw at 100 rpm
m. Next, GF-A was placed in the hopper of the extruder 2.
At a rate of 2 kg / hr, and simultaneously a mixture from a twin-screw extruder. The screw rotation speed of the extruder 2 was 12.5 rpm. The resin temperature in each zone of the extruder 2 was equal to the set temperature in each zone of the extruder. The residual fiber length of the obtained flat molded product was 1.2 mm.
The specific gravity of the molded product was 97% of the theoretical specific gravity calculated from the composition.

Example 3 In order to remove the die portion of the twin-screw extruder, dispose the extruder 2 at the tip of the twin-screw extruder, and reduce the pressure in the hopper portion of the extruder 2 With a metal float. As shown in FIG. 5, the screw portion (zones 9 and 10) in the extruder 2 is 1
60 ° C / 190 ° C, 180 from adapter to die
Set to ° C. Extruder 2 is the temperature above the melting point of the coating resin.
50 to 100% after. The mixture A was charged into the twin-screw extruder at a rate of 10.35 kg / hr, and the screw was kneaded at 100 rpm. Next, GF-A was introduced into the vent of the twin screw extruder at a rate of 2 kg / hr. The screw rotation speed of the extruder 2 was 12.5 rpm. The resin temperature in each zone of the extruder 2 was equal to the set temperature in each zone of the extruder. The residual fiber length of the obtained flat molded product was 1.5 mm. Moreover, the specific gravity of the molded product showed the same value as the theoretical specific gravity calculated from the composition.

Comparative Example 1 The mixture B was charged into the hopper of the extruder 1 to form a flat plate having a thickness of 3 mm and a width of 30 mm. As shown in FIG. 3, the solid transport section 155 in the extruder 1
C., 160 ° C. in the compression section, 160 ° C. in the weighing section, and 160 ° C. up to the die after the breaker plate. Further, the resin temperature in each zone of the extruder 1 was equal to the set temperature in each zone of the extruder, and there was no temperature zone higher than the melting point of the coating resin. The discharge rate at a screw rotation speed of 20 rpm was 57 g / min. In addition, many GF fibers in the obtained flat molded product were not defibrated. The specific gravity of the molded product was 94% of the theoretical specific gravity calculated from the composition.

Comparative Example 2 The mixture B was charged into the hopper of the extruder 1, and a flat plate having a thickness of 3 mm and a width of 30 mm was formed. As shown in FIG. 3, the solid transport section 170 in the extruder 1
The temperature was set to 180 ° C. in the compression section, 170 ° C. in the compression section, 170 ° C. in the measurement section, and up to the die after the breaker plate. Extruder 1
The resin temperature in each zone was equal to the set temperature in each zone of the extruder, and the entire extruder 1 was at a temperature equal to or higher than the melting point of the resin for coating. The discharge rate at a screw rotation speed of 20 rpm is 66
g / min. In addition, G in the obtained flat molded product
The F fiber length was 0.6 mm. The specific gravity of the molded product was 97% of the theoretical specific gravity calculated from the composition.

[Comparative Example 3] The die portion of the twin-screw extruder was removed, and the extruder 2 was arranged at the tip of the twin-screw extruder.
The kneaded and discharged material of the twin-screw extruder was dropped on the hopper of the extruder 2. As shown in FIG. 4, the screw part in the extruder 2 was set at 160 ° C./160° C., and the temperature from the adapter to the die was set at 160 ° C. The mixture A was charged into the hopper of the twin-screw extruder at a rate of 10.35 kg / hr, and the screw was kneaded at 100 rpm. Next, GF-A was charged into the hopper of the extruder 2 at a rate of 2 kg / hr, and simultaneously the mixture from the twin screw extruder was charged. The screw rotation speed of the extruder 2 was 12.5 rpm. Further, the resin temperature in each zone of the extruder 2 was equal to the set temperature of each zone of the extruder, and the temperature of the entire extruder 2 was equal to or lower than the melting point of the coating resin. Many unfibrillated glass fibers were present in the obtained flat molded product. The specific gravity of the molded product was 94% of the theoretical specific gravity calculated from the composition.

[Comparative Example 4] The die portion of the twin-screw extruder was removed, and the extruder 2 was arranged at the tip of the twin-screw extruder.
The discharge product of the twin-screw extruder was dropped on the hopper of the extruder 2. As shown in FIG. 4, the screw portion in the extruder 2 was set at 190 ° C./190° C., and the temperature from the adapter to the die was set at 180 ° C. Powder mixture A was charged into a hopper of a twin-screw extruder at a rate of 10.35 kg / hr, and the screws were mixed at 100 rpm. Next, GF-A was 2
It was introduced into the hopper of the extruder 2 at a rate of kg / hr. Extruder 2 was also charged with the mixture from the twin screw extruder at the same time. The screw rotation speed of the extruder 2 was 12.5 rpm. The resin temperature in each zone was equal to the set temperature in each zone of the extruder, and the temperature of the entire extruder 2 was equal to or higher than the melting point of the coating resin. The residual fiber length of the obtained flat molded product was 0.8 mm. The specific gravity of the molded product was 97% of the theoretical specific gravity calculated from the composition.

[Comparative Example 5] The die portion of the twin-screw extruder was removed, the extruder 2 was arranged at the tip of the twin-screw extruder, and the hopper portion of the extruder 2 could be depressurized. Bonded with a metal float. As shown in FIG. 5, the screw part in the extruder 2 is 160 ° C./160° C.
The temperature from the adapter to the die was set at 160 ° C. The mixture A was charged into the hopper of the twin-screw extruder at a rate of 10.35 kg / hr, and the screws were mixed at 100 rpm.
Next, GF-A was charged into the vent of the twin-screw extruder at a rate of 2 kg / hr. The screw rotation speed of the extruder 2 is 1
It was 2.5 rpm. The resin temperature in each zone was equal to the set temperature in each zone of the extruder, and the temperature of the entire extruder 2 was lower than the melting point of the coating resin. Many unfibrillated glass fibers were present in the obtained flat molded product. The specific gravity of the molded product was 97% of the theoretical specific gravity calculated from the composition.

[Comparative Example 6] The die portion of the twin-screw extruder was removed, the extruder 2 was arranged at the tip of the twin-screw extruder, and the hopper portion of the extruder 2 could be depressurized. Bonded with a metal float. As shown in FIG. 5, the screw part in the extruder 2 is 190 ° C./190° C.
The temperature from the adapter to the die was set at 180 ° C. 10.35 kg of powder mixture A in a hopper of a twin screw extruder
/ Hr and the screw was mixed at 100 rpm. Next, GF-A was charged into the vent of the twin-screw extruder at a rate of 2 kg / hr. The screw rotation speed of the extruder 2 was 12.5 rpm. The resin temperature in each zone was equal to the set temperature in each zone of the extruder, and the temperature of the entire extruder 2 was equal to or higher than the melting point of the coating resin. The residual fiber length of the obtained flat molded product was 0.8 mm. Moreover, the specific gravity of the molded product showed the same value as the theoretical specific gravity calculated from the composition.

[Evaluation of molded article] The following items were evaluated for the obtained molded article. The results are shown in Tables 2 and 3. Glass fiber dispersibility: Visually evaluated by three-level evaluation (（: No glass fiber bundle at all. ×: Many glass fiber bundles). Surface appearance: Visually evaluated by three-level evaluation (○: Uneven surface gloss, rough, No swell. ×: Uneven surface gloss, rough, swell.), Tensile strength (102 kg / cm ² ); JIS K7113
Bending strength (102 kg / cm ² ); JIS K7203
Bending elastic modulus (102 kg / cm ² ); JIS K720
3, Izod impact strength (with notch) (kJ / m ² ); J
Heat deformation temperature (° C) in accordance with IS K7110; JIS K7207 (load 1
8.5 kg / cm), water resistance (%); evaluated by tensile strength retention after immersing a flat molded product in warm water at 50 ° C. for 7 days.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

According to the method for molding a glass fiber-containing resin composition of the present invention, glass fibers are uniformly dispersed in a resin,
In addition, since the glass fiber can be left for a long time, a molded product having excellent strength, impact resistance, elastic modulus, water resistance, and surface appearance can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing zones and set temperatures of an extruder for performing a step (1) in one embodiment of the present invention.

FIG. 2 is a schematic diagram showing zones, set temperatures and screw configurations of the extruder of FIG.

FIG. 3 is a schematic diagram showing zones and set temperatures of an extruder according to an embodiment of the present invention.

FIG. 4 is a schematic diagram showing zones and set temperatures of an extruder according to an embodiment of the present invention.

FIG. 5 is a schematic diagram showing zones and set temperatures of an extruder according to an embodiment of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshitaka Matsuyama 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd. (72) Inventor Hideki Nakagawa 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Asahi Glass Co., Ltd. Term (reference) 4F207 AA03 AA10 AA11 AA13 AA15 AA21E AB05 AB07 AB09 AB12 AB25 KA01 KA17 KF02 KJ08 KK13 KL43 4J002 BD041 BD061 BD081 BN031 DL006 FA046 FB106 FB136 FB146 FB266 FD016

Claims (13)

[Claims] 1. A step (1) of melting and kneading a matrix resin composition containing no glass fiber coated with a resin, and a glass coated with a resin on the matrix resin composition melted and kneaded in the step (1). Step (2) of mixing fibers, and step (3) of kneading and molding the composition obtained in step (2), and the temperature at which glass fibers coated with resin in step (2) are mixed. Is a temperature not higher than the melting temperature of the resin for coating the glass fiber, and a temperature in a part of the kneading apparatus in the step (3) is higher than the melting temperature of the resin for coating the glass fiber. Extrusion molding method for a resin composition containing the resin. 2. An apparatus according to claim 3, wherein said 40 is provided after the kneading section of the apparatus in step (3).
The molding method according to claim 1, wherein the temperature from any point of up to 90% to 100% is equal to or higher than the melting temperature of the resin coating the glass fiber. 3. The molding method according to claim 1, wherein the steps (1), (2), and (3) are sequentially performed. 4. A method according to claim 1, wherein the matrix resin composition melt-kneaded in step (1) and the glass fibers coated with the resin are mixed in step (2).
The molding method according to claim 1 or 2, wherein the composition obtained by mixing in (1) is supplied to step (3) and kneaded. 5. The molding method according to claim 1, wherein the matrix resin of the glass fiber-containing resin composition is a vinyl chloride polymer. 6. The glass fiber coating resin is a polymer (a) which is miscible with a vinyl chloride polymer, a polymer (b) which is immiscible with a vinyl chloride polymer and is crystalline, and a peroxide. The molding method according to any one of claims 1 to 5, which is a resin obtained by melting a component containing (c). 7. A resin for coating a glass fiber comprising a polymer (a), a polymer (b) and a peroxide (c), a polymer chain (X) which is immiscible with a vinyl chloride polymer, and vinyl chloride. The molding method according to any one of claims 1 to 5, wherein the resin is a resin obtained by melting a component containing a copolymer (d) having a polymer chain (Y) miscible with a system polymer in the same molecule. 8. The molding method according to claim 6, wherein the polymer (a) is a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer or an alkyl methacrylate polymer. . 9. The molding method according to claim 6, wherein the polymer (b) is an olefin polymer. 10. The molding method according to claim 6, wherein the peroxide (c) is a peroxide capable of generating free radicals under a temperature condition for obtaining a resin for coating glass fibers. 11. The polymer chain (X) is a polymer chain obtained by polymerizing an olefin monomer, and the polymer chain (Y) is obtained by copolymerizing a vinyl cyanide monomer and an aromatic vinyl monomer. The molding method according to any one of claims 7 to 10, which is a polymerization chain or a polymerization chain obtained by polymerizing an alkyl methacrylate monomer. 12. The molding method according to claim 1, wherein the coating resin has a melt viscosity of 1,000 poise or less. 13. A molded product obtained by the molding method according to claim 1.