JPH03160045A - Fiber-reinforced chlorinated resin composition, molded article thereof, and production of the molded article - Google Patents

Abstract

PURPOSE:To prepare the title compsn. giving a molded article excellent in the mechanical strengths and durability under a repeated loading of stress by compounding a specific copolymer (mixture) with a specific fiberglass. CONSTITUTION:The title compsn. is prepd. by compounding: 100 pts.wt. copolymer comprising 50-99.5wt.% vinyl chloride and 50-0.5wt.% N-substd. maleimide (e.g. cyclohexylmaleimide), or 100 pts.wt. mixture of the copolymer with a vinyl chloride resin (e.g. a polyvinyl chloride); with 5-70 pts.wt. fiberglass having a length of 3mm or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application! F) The present invention relates to a fiber-reinforced chlorine-containing resin and molded product, a molded article using the composition, and a method for manufacturing the same. (Prior Art) It has been well known to reinforce chlorine-containing resins such as polyvinyl chloride resins with fibers such as glass fibers, and is disclosed in, for example, Japanese Patent Laid-Open No. 134140/1983. ．． (Problem to be Solved by the Invention) However, when using chlorine-containing resin and chlorine-containing resin, the physical properties deteriorate due to poor adhesion and wettability between glass fiber and chlorine-containing resin and nitride. However, there was a problem in that the glass fibers came out on the surface of the molded product during the heating stage. The present invention has been made in order to solve the problems of the prior art described above and to obtain a molded article that has high mechanical strength and excellent durability performance such as creep performance and fatigue performance. (Means for Solving the Problem) 1 of the present invention is a vinyl chloride K% fat. 50-99.5% by weight and N-i! To 100 parts by weight of a copolymer consisting of 50 to 0.5% by weight of maleic acid imide or a mixture of the copolymer and a vinyl chloride resin, 5 to 5 parts by weight of glass fibers having a length of 3 strands or more are added.
70 parts by weight of the fiber-reinforced chlorine-containing resin composition, and the second aspect of the present invention is a fiber-reinforced chlorine-containing resin composition made of the above-mentioned fiber-reinforced chlorine-containing resin composition. 3 of the present invention is a copolymer consisting of 50 to 99.5% by weight of vinyl chloride thread 1 resin and 50 to 0.5% by weight of N-substituted maleic acid imide; 100 parts by weight of a mixture of the copolymer and vinyl chloride resin is fluidized with air to form a fluidized bed, and a roving-shaped glass fiber is passed through the fluidized bed to adhere the mixture to the glass fiber. to obtain a fiber-reinforced chlorine-containing resin composition, and then this fiber-reinforced chlorine-containing resin composition is charged into a hollow mold, heated and pressurized. The gist of this paper is the method for manufacturing molded objects. The vinyl chloride resin used in the present invention includes:
Polyvinyl chloride, post-chlorinated polyvinyl chloride, vinyl chloride-vinylacetate copolymer, vinyl chloride-vinylidene chloride copolymer, ethylene-hinyl chloride copolymer, propylene-vinyl chloride copolymer, vinyl chloride-acrylic acid ester copolymer , vinyl chloride-methacrylic acid ester copolymer, etc. can be used.

The average degree of polymerization of the vinyl chloride resin is preferably 200 to 1,200. If it is less than 200, good physical properties will not be obtained, and if it exceeds 1200, the viscosity at the melting temperature will be extremely high, and it will be close to 1, making stamping difficult.

In the present invention, vinyl chloride type ■. The N-substituted maleic imide to be copolymerized with the fat has the general formula (Rl and Rz are the same or different atoms or groups selected from hydrogen, chlorine, bromine, fluorine, a cyan group, or an alkyl group having 1 to 3 carbon atoms). and R3 is an unsubstituted or substituted aliphatic, cycloaliphatic, or aromatic group having 1 to 30 carbon atoms, and preferable examples include a methyl group, an L-butyl group,
Cyclohexyl group, bicyclo-2.2.1-hebutyl 2
-methyl group, 9. Examples include IO-ethanol 9,10-dihydroanthracene residue, triphenylmethylbenzyl group, and phenyl group. If the amount of N-substituted maleic acid imide added is less than 0.5% by weight, the adhesion to glass fibers,
ati! If it is added in an amount exceeding 50% by weight, the melting temperature will increase and the 230%
Fluidity deteriorates below ℃, and decomposition of vinyl chloride resin occurs at higher temperatures. The glass fiber used in the present invention may be continuous or cut into lengths of 3 meters or more, but if the length is less than 3 meters, the elastic modulus will not improve. However, almost no improvement in strength can be expected. In addition, vinyl silane and substituted alkyl silane,
Pretreatment may be performed using a surface treatment agent containing an adhesion aid such as diaξnoalkylsilane. If the amount of glass fiber added is less than 5 parts by weight, the reinforcing effect will not be sufficient, and if it exceeds 70 parts by weight, it will be difficult to impregnate the glass fiber with the resin, and the physical properties will deteriorate. Glass fibers are usually used in the form of strands or rovings made up of several hundred to several thousand filaments with a diameter of about 5 to 30 microns, but in a molded product, they are opened into filament units, and there are gaps between the filaments. Since it is desirable that the resin be sufficiently impregnated with the resin, the amount of the binding agent attached is preferably 1% by weight or less, more preferably 0.5% by weight or less, from the viewpoint of openability.

In the present invention, other additives commonly used when molding vinyl chloride resins, such as alkyltin mercapto compounds, alkyltin carboxylates, metal soaps, eboxidized oils or esters, aryl, alkyl heat stabilizers such as phosphites or aryl/alkyl mixed phosphites, internal lubricants such as glycerin monomers, g-tree esters, higher alcohols, neutral or basic metal soaps, higher fatty acids, fatty acid esters, polyethylene waxes, fatty acid amides. , external lubricants such as silicone oil, antioxidants such as sterically hindered phenol or bisphenol,
UV absorbers such as salicylic acid esters, penzophenone, penzotriazole, and cyanoacrylates, metal oxides, pigments such as carbon black, plasticizers such as dioctyl phthalate and dicyclohexyl fucrate, ethylene-vinyl acetate copolymers, and chlorinated polyethylene. , acrylonitrile-butadiene-styrene copolymer, methacrylo?
Impact modifiers such as tributadiene-styrene copolymer, and fillers such as calcium carbonate, talc, and minerals may be added. PVC resin, and N-
A mixture of a copolymer consisting of a substituted maleic acid imide and a vinyl chloride resin can be obtained by mixing the two and other additives in a type tumbler or Henschel mixer, or by melt-kneading them in an extruder and then pulverizing them. It will be done. Vinyl chloride■■■m1ly and N-r! The particle size of the copolymer consisting of l10 maleic acid imide or the mixture of the copolymer and vinyl chloride resin is preferably 1+nm or less. If the particle size exceeds 1 mm, it becomes difficult for the m-sacred substance to penetrate between the glass fiber filaments, and impregnation tends to be insufficient.

Mixing with glass fibers in the composition is carried out by passing the roving-shaped glass fibers through a fluidized bed in which the resin mixture is fluidized by air, and uniformly attaching the resin mixture to the glass fiber filaments, as in the third aspect of the present invention. However, in the case of 1 and 2 of the present invention, the method is not limited to this, but the glass fibers cut in advance to lengths of 3 or more and the resin mixture are mixed in a V-shaped tumbler or Henschel. It is also possible to use a method of mixing with a mixer, etc., or a method of mixing both with air in a fluidized bed. In the present invention, the method of mixing glass 1a fibers into a resin mixture to form a composition and then molding it by heating and pressurizing it is as follows:
3 of the present invention shown in FIG. 1(A), a glass fiber 2 with a length of 3lI1 or more to which a chlorine-containing resin composition is attached is equipped with a built-in heater 4, as also shown in FIG. 1(B). In addition to the method of heating and pressurizing the press mold 3 consisting of a lower mold 31 and an upper mold 32, as shown in FIG. glass fiber 6
Alternatively, as shown in Fig. 3, roving-shaped glass fibers are passed through a fluidized bed 5 of a resin mixture. ! It is possible to adopt a method of cutting the l16, stacking it on the belt, heating and pressurizing it with the double belt press 9, but it is preferable that the heating temperature be 160 to 230°C. If the heating temperature is less than 160°C, the resin mixture will not be sufficiently integrated, resulting in poor physical properties.
If the temperature exceeds 30°C, the vinyl chloride resin will easily decompose, making it difficult to form a precept. (Function) In I of the present invention, the adhesion between glass fibers and vinyl chloride citrus resin is improved due to the good affinity that N-substituted maleic acid imide has with glass fibers. In addition, when using a mixture of a copolymer made of vinyl chloride and N-substituted maleic acid imide and a vinyl chloride-based resin, the good affinity with glass fibers that N-substituted maleic acid imide has The copolymer's good affinity with vinyl chloride resin improves the adhesion between glass fibers and vinyl chloride resin. In the second aspect of the present invention, since the molded article is made of the fiber-reinforced chlorine-containing resin obtained in the first aspect of the present invention & II Kaimono, it has excellent adhesiveness between the glass fiber and the vinyl chloride resin. You can get something. In the third aspect of the present invention, when obtaining the fiber-reinforced chlorine-containing resin composite sole according to the first aspect of the present invention, roving-shaped glass fibers are used, and a vinyl chloride resin mixture is attached to the glass fibers. Since the glass fibers are charged into the container, the glass fibers will not be cut during the molding process. (Examples) Examples of the present invention will be specifically described below, but the present invention is not limited to the examples. 70% by weight of vinyl chloride and 30% of cyclohexyl maleimide
100 parts by weight of a copolymer composed of 100 parts by weight, 3 parts by weight of butyltin maleate, and 0.3 parts by weight of polyethylene wax were mixed in a super mixer to form a powdered vinyl chloride resin compound with an average particle size of about 200μ. Obtained. Next, filament diameter 23μ, sizing agent adhesion fit 0.3% by weight, count 44
A roving glass fiber of 0.00 tex was cut into a length of 25 a, and 800 g of the powdered vinyl chloride resin assembly and 200 g of glass fiber were opened into filament units using air and hands in a fluidized bed. Mixed evenly.
The mixture was put into a press mold for a flat plate, and the mold was heated for 20 minutes.
Place it between heating plates at 0°C and heat for 5 minutes, then apply a surface pressure of 20°C.
The mold was heated and pressurized for 2 minutes at kg/cd, and then the mold was cooled while being pressurized with a cooling press to obtain a flat plate-shaped molded product with a thickness of 3 mm. Chopstick 1 100 parts by weight of polyvinyl chloride with a degree of polymerization of 400, 15 parts by weight of a copolymer consisting of 40% by weight of vinyl chloride and 60% by weight of cyclohexylmaleimide, 3 parts by weight of butyltin maleate, 0.3 parts by weight of polyethylene wax. were mixed in a super straw mixer to obtain a powdered vinyl chloride resin composition with an average particle size of about 300μ. Next, the filament diameter is 13μ,
Sizing agent adhesion IO. A roving glass fiber having a weight of 3% by weight and a size of 1100 tex was cut into a length of 5 am, and 800 g of the powdered vinyl chloride resin composite and 200 g of glass fiber were mixed into filament units using air and hands in a fluidized bed. The fibers were spread and mixed uniformly. The mixture was put into a press mold for a flat plate, and the mold was placed between heating plates at 210'C and heated for 5 minutes, then heated and pressurized for 2 minutes at a surface pressure of 20 kg/cj, and then the mold was was cooled while being pressurized with a cooling press to obtain a flat plate-shaped molded product with a thickness of 3 lbs. 100 parts by weight of a vinyl acetate-vinyl chloride copolymer with a vinyl acetate content of 13% by weight, 20 parts by weight of a copolymer consisting of 70% vinyl chloride and 30% by weight of t-butyl maleate, butyl 3 parts by weight of tin maleate, 0.0 parts by weight of polyethylene wax.
Mix 3 parts by weight in a super mixer to obtain an average particle size of about 25
A powdered vinyl chloride resin with a particle size of 0μ was obtained. next,
Filament diameter 13μ, sizing agent adhesion 1 0.3% by weight
A roving glass fiber having a count of l100teκ was cut into lengths of 5o and the powdered vinyl chloride resin composition '4k was cut.
700 g and 300 g of glass fiber were uniformly mixed in a fluidized bed while opening the glass fiber into filaments using air and hands. Putting the mixture into a press mold for a flat plate,
The cough mold was sandwiched between heating plates at 190°C and heated for 5 minutes, then heated and pressurized for 2 minutes with a surface pressure of 15 kg/cd, and then cooled while pressurizing the mold with a cooling press to obtain a thickness of 3III.
A flat plate-shaped compact of No. 1 was obtained.亥韮舅1 100 parts by weight of a copolymer consisting of 97% by weight of vinyl chloride and 3% by weight of phenylmaleimide, butyltin maleate 3
parts by weight and 0.3 parts by weight of polyethylene wax were mixed in a super mixer to obtain a powdered polyvinyl chloride composition with an average particle size of about 200 μm. Next, a roving-shaped glass IM with a filament diameter of 23 μ, a sizing agent adhesion amount of 0.3% by weight, and a count of 4400 tex was placed in a fluidized bed in which the &I material was fluidized with air. After dipping and passing the composition through the filaments to uniformly adhere the composition between the filaments, the filaments were cut into a length of 25 m to obtain a mixture with a glass fiber content of 35%, and the mixture was pressed into a flat press metal. Insert into the mold and press the mold for 200
Place it between heating plates at ℃ and heat it for 5 minutes, then apply a surface pressure of 10 kg.
/cd for 2 minutes, and then the mold was cooled while being pressed with a cooling press to obtain a flat plate-shaped body with a thickness of 3 mm.

100 parts by weight of polyvinyl chloride with a degree of polymerization of 400, 15 parts by weight of a copolymer consisting of 40% by weight of vinyl chloride and 60% by weight of cyclohexylmaleimide, 13 parts by weight of butyltin maleate, 0.3 parts by weight of polyethylene wax super ξ
At Kisser? The mixture was combined to obtain a powdered vinyl chloride resin compound with an average particle size of about 200 μm. Next, five roving-shaped glass fibers with a filament diameter of 23μ, a binding agent adhesion amount of 0.3% by weight, and a count of 4400tex were immersed and passed through a fluidized bed in which the composition was fluidized with air. After uniformly adhering the Kumihimo, it was heated and pressed continuously with a roll heated to 220°C to obtain a sheet with a width of 200 m, a thickness of 0.3 mm, and a glass fiber content of 40% by weight. 10 of these sheets were stacked at a temperature of 200°C and a surface pressure of 10
After heating and pressurizing at kg/c+4, the mixture was cooled to obtain a plate-shaped body with a thickness of 3 m.

A flat plate-like molded product with a thickness of 3 mm was obtained in the same manner as in Example 2, except that the vinyl chloride-cyclohexyl maleimide copolymer was not added. Comparative Example 1 A flat plate-like molded product with a thickness of 3 mm was obtained in the same manner as in Example 1, except that the composite material and the glass fiber were melt-kneaded using a kneading roll at 200°C.

Regarding each of the above examples and comparative examples, the following (1) to (5)
), as well as Examples 1 to 4 and Comparative Example 1, the obtained molded bodies were heated and melted to a material temperature of about 200'C with a far infrared heating device, and the mold temperature was 4.
Placed in a press mold at 0'C, surface pressure 120kg/c
Table I summarizes the results of measuring the physical properties in (6) for the molded product obtained by pressurizing in step d.

(1) Burn and remove the resin from the rod and measure the amount and length of glass fibers.

(2) A test piece with a width of 20aw and a length of 120cm was cut out from the molded body, and a three-point bending test was performed with a span distance of 100v to measure the bending strength and bending elastic modulus.

(3) An Izod impact test piece was cut out from the molded article according to JIS-K7110, and the Izod impact strength was measured. (4) In the test (2) above, the initial stress of 6
A bending displacement amount that generates a stress of "IKglmm" was left as it was, and the stress retention rate was measured after 24 hours.

(5) In the test of (2) above, the test piece was loaded with 6 kg/a
Visually observe the condition of the test piece after repeating the application and removal of a bending load that generates a stress of 50 m'' 50 times. (6) Visually observe the presence or absence of protrusion of glass fibers on the surface of the molded object. (See the margins below) (Effects of the Invention) Since the fiber-reinforced chlorine-containing resin composition according to the first aspect of the present invention and the molded article according to the second aspect of the present invention have the configurations described above, molded articles can be manufactured using the compositions. In this case, the adhesion and wettability between the glass fiber and vinyl chloride resin of the composite material are improved, so it has high strength and high durability against stress retention and repeated stress loading. In addition, there is no protrusion of glass fibers on the surface of the molded product,
It also has the advantage of significantly improving the surface condition. The method for producing a molded article using the fiber-reinforced chlorine-containing resin composition according to the third aspect of the present invention is strictly prohibited as described above.
In addition to the effects obtained in the above aspects 1 and 2 of the present invention, since the glass fibers are not cut during molding, the resulting molded product has better strength.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing a third embodiment of the present invention.
A) is a diagram in which the fiber-reinforced chlorine-containing resin & I1 precepts are charged into the mold, (opening) is a diagram in which the upper and lower molds are closed, and Figure 2 is an explanatory diagram showing another example of the same. , FIG. 3 is an explanatory diagram showing still another embodiment of the same. 1. Monochlorine-containing resin composition, 2.-Glass fiber, 3
・-Press mold, 5.--Fluidized bed of chlorine-containing resin composition, 6.1 Roving-shaped glass fiber,

Claims (1)

[Scope of Claims] 1. A copolymer consisting of 50 to 99.5% by weight of a vinyl chloride resin and 50 to 0.5% by weight of an N-substituted maleic acid imide, or a mixture of the copolymer and a vinyl chloride resin. A fiber-reinforced chlorine-containing resin composition comprising 100 parts by weight of glass fibers and 5 to 70 parts by weight of glass fibers having a length of 3 mm or more. 2. A molded article made from the fiber-reinforced chlorine-containing resin composition according to claim 1. 3. 100 parts by weight of a copolymer consisting of 50 to 99.5% by weight of vinyl chloride resin and 50 to 0.5% by weight of N-substituted maleic acid imide or a mixture of the copolymer and vinyl chloride resin is heated in air. to form a fluidized bed, pass roving glass fibers through the fluidized bed, adhere the mixture to the glass fibers to obtain a fiber-reinforced chlorine-containing resin composition, and then obtain a fiber-reinforced chlorine-containing resin composition. A method for producing a molded article using a fiber-reinforced chlorine-containing resin composition, which comprises charging the resin composition into a mold, heating and pressurizing the resin composition.