JPH11106582A - Vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. excellent in moldability and mechanical strengths such as impact strength by compounding a vinyl chloride resin with glass fibers coated with a resin having specified solubility parameter and melt viscosity. SOLUTION: Glass fibers are coated with 5-60 wt.% thermoplastic resin selected from among vinyl cyanide/arom. vinyl copolymers, alkyl (meth)acrylate polymers, vinyl acetate polymers, polyamide polymers, polyurethane polymers, and polyester polymers and having a solubility parameter of 8.5 or higher and a melt viscosity of 50,000 P or lower. 100 pts.wt. vinyl chloride resin is compounded with 10-200 pts.wt. glass fibers coated as above, thus giving the objective compsn. Various known ingredients may be compounded into the compsn. as required.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to strength, impact resistance,
The present invention relates to a vinyl chloride resin composition which provides a molded article having excellent elastic modulus, water resistance and the like and has excellent moldability.

[0002]

2. Description of the Related Art A vinyl chloride resin and a vinyl chloride resin composition comprising a plasticizer and the like are relatively excellent in mechanical strength and can be produced at low cost. For this reason, the molded article of the resin composition is used for a wide range of uses such as building members, industrial members, and electric device members. But,
Some applications have disadvantages such as poor heat resistance, mechanical strength, dimensional stability, and thermal expansion.

On the other hand, it has been known that glass fibers are filled and blended with a vinyl chloride resin to enhance and improve its properties. In this way, stiffness and tensile strength are generally significantly improved, but impact strength is often reduced.

[0004] Since vinyl chloride resins are particularly inferior in melt flow properties as compared with other thermoplastic resins, they have poor wettability with glass fibers, are difficult to disperse glass fibers uniformly, and have vinyl chloride containing glass fibers. The melt flow characteristics of the system resin are remarkably reduced, and the glass fiber is damaged during kneading and the resin is thermally degraded.

[0005] In order to solve the above-mentioned drawbacks, for example, there is a method of increasing the forming temperature. However, since the molding temperature and the decomposition temperature of vinyl chloride resin are close to each other, strict temperature control is necessary, and a slight rise in temperature causes the resin to decompose, resulting in the mechanical strength of the molded product. Is not practical because it decreases.

Further, in order to avoid breakage of the glass fiber generated during molding and to improve the mechanical strength of the molded product,
There is known a method of adding glass fiber from an extruder vent hole or a die portion. According to this method, breakage of the glass fiber is avoided, but there is a drawback that the mechanical strength, particularly water resistance, is significantly impaired because the wettability between the resin and the glass fiber is not sufficient.

In order to improve these drawbacks, (1) JP-B-49-6830, JP-B-49-13209 and JP-B-49-27663 disclose vinyl chloride, vinyl acetate and vinyl aromatic compounds in the presence of glass fiber. It has been proposed to polymerize a vinyl monomer such as, coat a glass fiber with a polymer comprising the monomer, obtain a molded product by melt-kneading the polymer-coated glass fiber and a vinyl chloride resin. ing. According to these methods, the dispersibility of the glass fiber and the adhesion between the resin and the glass fiber are improved, and the appearance of the molded product and various mechanical strengths are said to be improved. In some cases, the fiber may be damaged, and a sufficient effect cannot be exerted from the viewpoint of impact resistance.

(2) Japanese Patent Application Laid-Open No. 6-65427 proposes a method for improving the properties of an alloy resin by adding a compatibilizer. This method is effective when the matrix resin is essentially composed of a vinyl chloride resin and an olefin resin, and when the matrix resin is a vinyl chloride resin, the inherent properties of the vinyl chloride resin are impaired, The balance of impact resistance, elastic modulus, water resistance and moldability is not always sufficient.

(3) JP-A-8-225700 discloses glass fibers obtained by coating a vinyl chloride resin with a thermoplastic resin;
Incorporates a vinyl chloride resin with a thickener consisting of an immiscible polymerization chain and a miscible polymerization chain to reduce the viscosity of the vinyl chloride resin and to promote the opening of glass fibers to prevent breakage of glass fibers. Methods aiming at this have been proposed. However, in this method, a sufficient effect cannot be exhibited because the viscosity reducing agent does not exist near the glass fiber and the compatibility with the vinyl chloride resin is low.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a vinyl chloride resin composition having excellent mechanical strength such as moldability and impact resistance. I do.

[0011]

The inventors of the present invention have made intensive studies and have found that coated glass fibers obtained by coating with a coating resin having a solubility parameter of 8.5 or more and a melt viscosity of 50,000 poise or less are converted to chlorides. It has been found that the vinyl chloride resin composition blended with the vinyl resin has improved mechanical strength such as impact resistance, strength, elastic modulus and water resistance, and has significantly improved moldability.

That is, the present invention is obtained by coating a vinyl chloride polymer with 100 parts by weight of a coating resin having a solubility parameter of 8.5 or more and a melt viscosity of 50,000 poise or less. 10-20 coated glass fibers
It is a vinyl chloride resin composition containing 0 parts by weight.

In the present invention, the coating resin is preferably a thermoplastic resin, and is a resin obtained by melting a thermoplastic resin containing a peroxide and a reactive monomer for improving the adhesion to glass fibers. Is preferred.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION

[Regarding vinyl chloride polymer] The vinyl chloride polymer used in the present invention 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 preferably in the range of 400 to 1500, particularly preferably 450 to 1000. 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.

[0015] In the present specification, the term "vinyl chloride-based polymer" refers to a polymer which is substantially a vinyl chloride-based polymer, wherein at least 60% by weight of the constituent polymerized units are composed of polymerized units based on vinyl chloride. . Specifically, vinyl chloride homopolymer, ethylene / vinyl chloride copolymer, vinyl acetate /
A vinyl chloride copolymer, a graft copolymer of an ethylene / vinyl acetate copolymer and a vinyl chloride polymer, and the like,
In addition, post-chlorinated polyvinyl chloride is also included, and those alone or in combination of two or more thereof are used.

[Regarding Coating Resin] The solubility parameter is the square root of the cohesive energy density of a molecule. This value is an index indicating the compatibility between the substances, and indicates that substances having similar solubility parameters tend to be compatible with each other. Compatibility refers to the miscibility in the molecular order in which the vinyl chloride polymer and the coating resin are mixed.

Therefore, having compatibility means a state in which a vinyl chloride polymer and a coating resin are mixed in a molecular order in a thermodynamically stable state. , Both of which are in a macro phase-separated state, meaning a thermodynamically unstable state. Specifically, even if the vinyl chloride polymer and the incompatible coating resin are melted and kneaded,
The vinyl chloride polymer serving as a matrix and the coating resin undergo phase separation, and a so-called sea-island structure is observed.

When a coated glass fiber containing a coating resin is blended with a vinyl chloride polymer and melted and kneaded, the coating resin has compatibility with the vinyl chloride polymer, so that it is promptly accompanied by the glass fiber. It has the effect of being uniformly dispersed in a vinyl chloride polymer. For this reason, breakage of the glass fiber during kneading is suppressed, and an effect of significantly improving mechanical strength such as impact resistance, strength, elastic modulus, and water resistance can be exerted. Since the solubility parameter of the vinyl chloride homopolymer is 9.5, a coating resin having a solubility parameter of 8.5 or more is used, and a coating resin having a solubility parameter of 8.5 or more and 12 or less is used. Particularly preferred.

The melt viscosity represents the flowability of the resin during melting,
It is calculated from the pressure at which the resin in the molten state is passed through the capillary. The capillary length is 10 mm, the diameter is 1 mm, and the measurement temperature is a value under the conditions of a molding temperature of 190 ° C., which is a molding temperature of the vinyl chloride resin, and a shear rate of 100 sec ⁻¹ . The melt viscosity value is 5
It is important that it is less than or equal to 0000 poise. In addition, from the viewpoint of coating the glass fiber with the resin, it is preferably 100 poise or more. When kneading and dispersing the coated glass fiber in the vinyl chloride resin, the lower the melt viscosity of the coating resin, the better the fiber opening properties of the glass fiber and the more the glass fiber can be prevented from being damaged.

Examples of the coating resin include a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer, an alkyl acrylate polymer, an alkyl methacrylate polymer, and a vinyl acetate polymer. A thermoplastic resin selected from coalesced, polyamide-based, polyurethane-based, and polyester-based polymers is preferred.

The copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer includes vinyl cyanide monomers such as acrylonitrile and methacrylonitrile and styrene, α
-A copolymer obtained by copolymerizing a monomer in combination with an aromatic vinyl monomer such as methylstyrene, vinyltoluene and chlorostyrene, and an acrylonitrile-styrene copolymer is particularly preferred. The proportion of polymerized units based on the vinyl cyanide monomer in the copolymer is preferably from 5 to 80% by weight, particularly preferably from 10 to 50% by weight. If the proportion of the vinyl cyanide-based polymer unit is small, the compatibility with the vinyl chloride-based polymer becomes poor, the polymer cannot be sufficiently dispersed in the vinyl chloride-based polymer as a matrix, and the mechanical strength of the obtained molded article is low. descend.

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

At least one kind of the alkyl methacrylate monomers, for example, a single monomer other than the alkyl methacrylate monomers and the alkyl methacrylate monomer and the alkyl methacrylate monomer Combinations with the body are preferred. Specific examples include a methyl acrylate polymer, a methyl methacrylate polymer, an ethyl acrylate polymer, and an ethyl methacrylate polymer. A particularly preferred polymer is a methyl methacrylate polymer.

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

As the polyamide polymer, nylon 6, nylon 6-6, nylon 6-10, nylon 6
12, nylon 11, nylon 12, or a polymer containing two or more thereof, and nylon MXD6, 1,4- obtained from meta-xylenediamine and adipic acid.
Nylon 4- obtained from diaminobutane and adipic acid
6 and the like are also preferable. When the coating glass fiber is mixed with the vinyl chloride polymer serving as the matrix, the coating resin must be sufficiently melted and melted, and must be uniformly dispersed in the vinyl chloride polymer with the glass fiber. Nylon 12, which melts and melts at the molding temperature of the vinyl polymer, for example, 160 to 200 ° C, is particularly preferred.

As the polyurethane polymer, a thermoplastic polymer comprising a polyol and an isocyanate is preferable. Examples of the polyol include a polyether polyol and a polyester polyol. Examples of the polyether polyol include polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

Examples of the polyester polyol include a ring-opening polymerization type polyester polyol obtained by ring-opening polymerization of a polycondensation type polyester polyol obtained from a dibasic acid and a dihydric alcohol and a cyclic compound. Examples of the dibasic acid include adipic acid, phthalic acid, and maleic acid. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, hexylene glycol, and neopentyl glycol. Examples of the compound include ε-caprolactone, β-methyl-δ-valerolactone, and the like, and two or more of these may be used in combination.

As the isocyanate, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), xylene diisocyanate (X
DI), hexamethylene diisocyanate (HDI),
4,4-dicyclohexylmethane diisocyanate (H
MDI), isophorone diisocyanate (IPDI) and the like. Particularly, a urethane-based polymer obtained by combining a polyester diol composed of neopentyl glycol and hexylene glycol as a dihydric alcohol and adipic acid as a dibasic acid and hexamethylene diisocyanate (HDI) is preferable.

As the polyester polymer, a thermoplastic polyester polymer comprising a dibasic acid or its anhydride and a dihydric alcohol is preferable. Specific examples of the dibasic acid include aromatic dibasic acids such as terephthalic acid, isophthalic acid, tetrachlorophthalic anhydride, hexachloroendomethylenetetrahydrophthalic acid, and dimethylenetetrahydrophthalic acid; and aliphatic acids such as maleic acid and fumaric acid. Unsaturated 2
Examples include aliphatic saturated dibasic acids such as basic acid, succinic acid, and adipic acid, and acid anhydrides thereof.

As the dihydric alcohol, ethylene glycol, propylene glycol, diethylene glycol,
Triethylene glycol, neopentyl glycol, hexylene glycol, 1,4-butylene glycol and the like. Two or more of dibasic acids and dihydric alcohols may be used in combination. In particular, a polymer comprising terephthalic acid, isophthalic acid, adipic acid as a dibasic acid and neopentyl glycol as a dihydric alcohol is preferred.

Among the coating resins, those having a glass transition temperature higher than that of the vinyl chloride polymer are more preferable from the viewpoint of heat resistance typified by the heat distortion temperature when blended with the vinyl chloride resin, and acrylonitrile-styrene is preferred. Copolymers or methyl methacrylate polymers are particularly preferred. The molecular weight of the coating resin is not particularly limited. However, if the molecular weight is too large, kneadability with other components is insufficient, which is not preferable, and the average molecular weight is preferably from 1,000 to 400,000.

[Reactive monomer] The reactive monomer can be used for improving the adhesion between the glass fiber and the vinyl chloride polymer and improving the physical properties of the composition of the present invention.
The reactive monomer reacts with the vinyl chloride polymer and / or the coating resin to form a copolymer that can firmly adhere to the glass fiber. The reactive monomer is preferably a vinyl monomer containing a functional group. As a functional group,
For example, an epoxy group, a carboxyl group, a carboxylic acid anhydride group, an amino group, a hydrolyzable group-bonded silyl group, an amide group, a hydroxyyl group, and the like, in particular, an epoxy group,
Carboxyl groups and carboxylic anhydride groups are preferred.

Examples of the epoxy group-containing vinyl monomer include unsaturated acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate and glycidyl itaconate, and alkenyl glycidyl ethers such as vinyl glycidyl ether and allyl glycidyl ether. Particularly, glycidyl methacrylate and vinyl glycidyl ether are preferable.

Examples of the carboxyl group-containing vinyl monomer include acrylic acid, methacrylic acid, itaconic acid and maleic acid, and methacrylic acid and maleic acid are particularly preferable. Examples of the carboxylic anhydride group-containing vinyl monomer include anhydrides of polycarboxylic acids having a polymerizable unsaturated group, maleic anhydride, unsaturated polycarboxylic anhydrides such as itaconic anhydride, Particularly, maleic anhydride is preferred.

If the amount of the reactive monomer is too large, secondary reactions tend to occur with respect to the vinyl chloride-based polymer and the coating resin, which is not preferable. In addition, as a result of forming a network structure by a crosslinking reaction, the reactive monomer becomes insoluble. It is not preferable because the dispersibility of the glass fiber is significantly impaired. Therefore, the amount used is 0.1 to 100 parts by weight of the total of the vinyl chloride resin and the coating resin.
20 parts by weight are suitable.

[Peroxides] Peroxides are decomposed by heat to generate free radicals, and known organic peroxides can be used. Specifically, the following can be exemplified. Cyclohexanone peroxide,
Ketone peroxides such as methyl ethyl ketone peroxide, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene Dialkyl peroxides such as benzoyl peroxide and lauroyl peroxide; peroxydicarbonates such as diisopropylperoxydicarbonate and di-n-propylperoxydicarbonate; peroxyesters and peroxyketals.

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 of 70 to 150 ° C. is preferable for handling.

The reactive monomer to which the free radical generated from the above peroxide is added at the time of melting reacts with the vinyl chloride polymer and / or the coating resin to form a copolymer which can firmly adhere to the glass fiber. Let me know. If peroxide is added in too large an amount, the reaction becomes complicated, workability,
It is not preferable from the viewpoint of safety and economy. The content is preferably 0.1 to 10% by weight based on the coating resin.

[Coated Glass Fiber] As the glass fiber, various commercially available forms, for example, chopped strand-shaped or roving-shaped glass fibers are used. The coating method is not particularly limited, for example, a method of polymerizing and coating a monomer in the presence of glass fiber, a method of impregnating glass fiber with a coating resin in a molten state, or a method of coating resin solution or emulsion. A method of removing the solvent after impregnation is preferable.

When chopped strand glass fibers are used, suspension polymerization is performed in the presence of the glass fibers and a monomer. In the case of using roving-like glass fiber, a method of impregnating the glass fiber with the resin by continuously passing the glass fiber through the molten resin and cutting the glass fiber is preferable.
In any case, the length is preferably 1 to 50 mm in terms of handling, and particularly preferably 1 to 20 mm. Further, the glass fiber diameter is preferably 1 to 20 μm.

Further, the glass fiber is a coupling agent,
Ordinary surface treatment with a film former, a lubricant, or another surface treatment agent may be performed. For example, examples of the coupling agent include a silane coupling agent in which a hydrolyzable group is bonded to a silicon atom. Specific examples of the silane coupling agent include the following compounds.

Methacrylsilane-based compounds such as γ-methacryloyloxypropyltriethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane;
-Epoxysilane compounds such as glycidoxypropyltrimethoxysilane, aminosilane compounds such as γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, vinyltrimethoxysilane, etc. And chlorosilane compounds such as γ-chloropropyltrimethoxysilane.

The amount of the coated glass fiber in the composition is 10 to 200 parts by weight based on 100 parts by weight of the vinyl chloride polymer. If the amount is less than 10 parts by weight, the properties of the vinyl chloride resin cannot be satisfactorily enhanced or improved. If the amount is more than 200 parts by weight, the glass fiber addition efficiency does not improve so much, and conversely, the moldability decreases extremely.

The amount of the coating resin in the coated glass fiber is preferably at least 5% by weight in the coated glass fiber. If the amount of the coating resin is less than 5% by weight, the glass fibers are not completely covered, and when kneaded with the vinyl chloride polymer, the dispersibility of the glass fibers and the adhesion to the vinyl chloride polymer become insufficient. Cheap. On the other hand, if the amount of the coating resin is too large, the ratio of the coating resin to all the polymer components in the composition increases, which is disadvantageous in terms of physical properties and economy. The amount of the coating resin is preferably 60% by weight or less, particularly preferably 40% by weight or less.

The amount of the glass fiber in the composition of the present invention is 5 to 100 parts by weight of the vinyl chloride polymer.
190 parts by weight are preferred. If the amount is less than 5 parts by weight, the reinforcement and improvement of various properties of the vinyl chloride resin cannot be sufficiently achieved.
If the amount exceeds 190 parts by weight, the efficiency of glass fiber addition is not so improved, and conversely, the moldability is extremely reduced. The amount of the resin coating the glass fibers in the composition is 120 parts by weight or less, especially 8 parts by weight, based on 100 parts by weight of the vinyl chloride polymer.
It is preferably 0 parts by weight or less.

The composition of the present invention is preferably used as a molding composition to be subjected to molding. That is, the composition is used for molding alone or with the addition of various additives. Examples of a method for molding the vinyl chloride resin composition include injection molding, extrusion molding, press molding, calendering, and the like, which are generally applied to thermoplastic resins.

More specifically, each powder or pellet of the composition is blended using a Henschel mixer or the like, and melt-kneaded at 150 to 190 ° C. using a single-screw or twin-screw extruder to obtain a molded product. In particular, it is preferably used for the production of a molded product by extrusion molding.

The composition of the present invention may contain various known additives such as stabilizers for vinyl chloride resins, impact modifiers, lubricants, pigments, antistatic agents, antioxidants, fillers, foaming 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 and dibutyltin distearate; aliphatic carboxylic acid salts such as barium stearate, calcium stearate and zinc stearate; inorganic stabilizers; epoxidation Epoxy compounds such as soybean oil, stabilizers such as organic phosphates and organic phosphites, M
Impact modifiers such as BS 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, etc.

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. In addition, the total amount of these additives is preferably 100 parts by weight or less based on 100 parts by weight of the vinyl chloride-based polymer, including the filler.

The shape of the molded product of the composition of the present invention is not particularly limited, but is preferably an extruded molded product such as a plate, a rod, or a tube having various cross-sectional shapes. In addition to its properties such as strength, impact resistance, and elastic modulus, it has a very low linear expansion coefficient, so its expansion and contraction is extremely small, and it is used for building materials such as rain gutters, eaves, outer wall siding materials, and window frames. Are typical examples.

[0052]

EXAMPLES The present invention will be specifically described below with reference to Examples (Examples 1 to 7) and Comparative Examples (Examples 8 to 11), but the present invention is not limited thereto.

[Preparation of vinyl chloride polymer] 3 parts (parts by weight, hereinafter the same) of partially saponified polyvinyl alcohol (manufactured by Nippon Gohsei Kagaku), 0.5 parts of azobisisobutyronitrile, and 3000 parts of pure water was added into a pressure reaction reactor, and after replacement with nitrogen gas, 1000 parts of a vinyl chloride monomer was charged. After reacting at 65 ° C. for 6 hours, unreacted monomers are recovered, and then dehydrated and dried.
950 parts of a powdery polymer were obtained. The polymerization degree of the obtained polymer was 800. Hereinafter, this is referred to as polymer A.

[Preparation of Coated Glass Fiber] (1) Acrylonitrile / styrene copolymer (polymerization unit content based on acrylonitrile: 28% by weight) was 50 mm
Using a single screw extruder, the mixture was extruded at a cylinder temperature of 250 ° C., a die temperature of 250 ° C. and a rotation speed of 75 rpm, and supplied to a coating resin tank kept at 250 ° C. On the other hand, fiber
m of roving-shaped glass fiber is continuously passed through a molten resin bath for coating, the resin is impregnated between monofilaments, and then passed through a 2.2 mm diameter die to remove an excessive amount of resin. Then, the weight ratio between the resin component and the glass fiber was adjusted to 30/70.

The obtained coated glass fiber was cut into a length of 6 mm by a rotary cutter. Hereinafter, this is referred to as coated glass fiber (B1). Table 1 shows the solubility parameter ((cal / cm ³ ) ^1/2 ) and the melt viscosity (Poise) of the coating resin. Solubility parameters are described in J. Org. Appl. Ch
em. , 3, 71 (1953). The melt viscosity was measured at 190 ° C. at a shear rate of 100 sec ⁻¹ using a capillary having a length of 10 mm and a diameter of 1 mm.

(2) Coating resins were obtained from methyl methacrylate polymer (molecular weight: 25,000) and polyurethane (neopentyl glycol, hexylene glycol, adipic acid) by the same production method as that for obtaining (B1). A polymer comprising a reaction product of polyester diol and hexamethylene diisocyanate (HDI)), nylon 12, and a thermoplastic polyester (a polymer obtained from terephthalic acid, isophthalic acid, adipic acid and neopentyl glycol, molecular weight 15,000). After impregnating and cutting glass fiber roving, coated glass fiber (B2) having a length of 6 mm and a weight ratio of resin component to glass fiber of 30/70
To (B5). Table 1 shows the solubility parameter and the melt viscosity (Poise) of these coating resins.

(3) In the same manner as in obtaining (B1),
To 100 parts of the acrylonitrile / styrene copolymer, 5 parts of maleic anhydride and 0.5 part of dicumyl peroxide (10-hour half-life temperature of 117 ° C.) were added,
After impregnating and cutting glass fiber roving, length 6mm,
A coated glass fiber (B6) having a weight ratio of the resin component to the glass fiber of 30/70 was obtained.

(4) 280 parts of chopped strand glass fibers of 3 mm in length and 13 μm in fiber system are sufficiently impregnated with a mixed solution of 40 parts of acrylonitrile, 60 parts of styrene, 1 part of benzoyl peroxide and 1 part of mercaptoethanol as a chain transfer agent. After that, 1800 parts of water was added and 8
Polymerization was carried out at 0 ° C. for 5 hours. After completion of the polymerization, the resultant was sufficiently washed with water and dried at 60 ° C. The glass fiber content in the obtained coated glass fiber was 80% by weight, and the weight ratio of the polymerization unit based on acrylonitrile to the polymerization unit based on styrene was 28/72. Hereinafter, this is referred to as coated glass fiber (C1).

For comparison, polypropylene (molecular weight: 100,000) and styrene / butadiene copolymer (polymerized unit content based on butadiene: 85% by weight) were coated as a coating resin in the same manner as in the preparation of (B1). Coated glass fibers (D1) and (D2) were obtained. The coated glass fiber obtained by the reaction in the same manner as in obtaining (B6) without adding mercaptoethanol as a chain transfer agent is referred to as (D3). Table 1 shows the compatibility parameters and melt viscosities of these coating resins.

Example 1 Polymer A, coated glass fiber (B
1) was mixed with the amount (unit: parts) shown in Table 2, 3 parts of dibutyltin mercaptide, and 0.5 part of stearic acid, and blended using a Henschel mixer. continue,
Using a 30 mm single screw extruder with L / D = 24, compression ratio = 2.3, cylinder temperature 165 ° C., die temperature 185 ° C.
A flat plate having a thickness of 3 mm and a width of 30 mm was extruded at a rotation speed of 20 rpm. The extrusion moldability, the glass fiber dispersibility of the obtained flat plate, various physical properties, and the dispersibility of the resin for coating in the polymer A were evaluated by the following methods. Table 3 shows the results.

Extrusion moldability: Evaluated by screw load (unit: ampere) and extrusion amount (unit: g / min). Tensile strength (unit: kgf / mm ² ); JIS K711
Conforms to 3. Flexural strength (unit: kgf / mm ² ) and flexural modulus (unit: kgf / mm ² ): based on JIS K7203. Izod impact strength (with notch) (unit: kJ / m
² ): Conforms to JIS K7110.

Heat deformation temperature (unit: ° C.): JIS 207
Compliant (load 18.5kg). Water resistance (unit:%): 7
Evaluated by tensile strength retention after immersion for one day. Glass fiber dispersibility: visually evaluated in three stages (（: no glass fiber bundle at all. Δ: some glass fiber bundles. ×: many glass fiber bundles). Dispersibility of coating resin in polymer A: electron microscope (magnification: 20
(× 00)) and evaluated in two steps (○: no phase separation; ×: phase separation present).

Examples 2 to 6 Polymer A and coated glass fibers (B2) to (B6) were each in the amounts (unit:
Parts), 3 parts of dibutyltin mercaptide, and 0.5 part of stearic acid were blended, and a flat molded product was prepared in the same manner as in Example 1 and various evaluations were made. Table 3 shows the results.

Example 7: Polymer A, coated glass fiber (C
1) was blended in the amounts (units: parts) shown in Table 2, 3 parts of dibutyltin mercaptide, and 0.5 part of stearic acid, and flat molded articles were prepared in the same manner as in Example 1 and various evaluations were made. Table 4 shows the results.

Examples 8 to 10 The amounts of polymer A and coated glass fibers (D1) to (D3) shown in Table 2 (unit:
Parts), 3 parts of dibutyltin mercaptide, and 0.5 part of stearic acid were blended, and a flat molded product was prepared in the same manner as in Example 1 and various evaluations were made. Table 4 shows the results.

Example 11 Polymer A and chopped strand-like glass fibers (E) which were not coated with a coating resin obtained by cutting the roving-like glass fibers used for the coating glass fibers to 6 mm (unit: parts) ) And 3 parts of dibutyltin mercaptide and 0.5 stearic acid
Parts were blended, and a flat plate was produced in the same manner as in Example 1, and various evaluations were made. Table 4 shows the results.

From Tables 3 and 4, it can be seen that the tensile strength, tensile modulus, flexural strength, flexural modulus and water resistance are all superior to the comparative examples. In particular, the effect of improving the impact strength is high,
Shows excellent mechanical properties. Furthermore, it has excellent moldability.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

[0072]

As described above, a coated glass fiber coated with a component compatible with a vinyl chloride polymer having a solubility parameter of 8.5 or more and a melt viscosity of 50,000 poise or less, and a vinyl chloride polymer By blending
With the synergistic effect of improving the dispersibility of glass fibers in the vinyl chloride polymer as a matrix resin and enhancing the interfacial adhesion with glass fibers, strength, impact resistance, elastic modulus, A vinyl chloride resin composition having significantly improved water resistance and moldability can be obtained. The composition of the present invention is extremely useful as a composition for extrusion molding and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Yamamoto 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi

Claims (4)

[Claims] 1. A coated glass fiber obtained by coating with a coating resin having a solubility parameter of 8.5 or more and a melt viscosity of 50,000 poise or less based on 100 parts by weight of a vinyl chloride polymer. A vinyl chloride resin composition containing 10 to 200 parts by weight. 2. A coating resin comprising a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer, an alkyl acrylate polymer, an alkyl methacrylate polymer, and a vinyl acetate resin. The composition according to claim 1, which is a thermoplastic resin selected from a polymer, a polyamide-based polymer, a polyurethane-based polymer, and a polyester-based polymer. 3. The composition according to claim 1, wherein the coating resin is a resin obtained by melting a thermoplastic resin containing a reactive monomer for improving adhesion to glass fibers and a peroxide. 4. The coating resin according to claim 1, wherein the amount of the coating resin is 5 to 60% by weight based on the coated glass fiber and 120 parts by weight or less based on 100 parts by weight of the vinyl chloride polymer. A composition as described.