JP2021008541A - Vinyl chloride resin composition and its molded product - Google Patents

Abstract

To provide a vinyl chloride resin composition capable of obtaining a molded product that has low linear expansion coefficient, excellent impact resistance, and a surface that is smooth and free from rough surface.SOLUTION: A vinyl chloride rein composition comprising: (A) a vinyl chloride resin, and (B) nepheline syenite, in which the (B) nepheline syenite is contained by 10 to 40 pts.mass relative to 100 pts.mass of the (A) the vinyl chloride resin, and has the linear expansion coefficient smaller than 5×10-5/°C.SELECTED DRAWING: None

Description

The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition and a molded product thereof that can be suitably used for building materials such as sashes.

The sashes attached to the openings of the building frame are used properly for each region. Since resin has higher heat insulation than metal, resin sashes are preferably applied to cold regions, but for areas that do not require much heat insulation, metal sashes made entirely of metal such as aluminum are suitable. It is used. In recent years, the appearance and design of building materials such as window frames and sashes have become more important, and resin sashes, which are easier to give design than metal sashes, are attracting attention. Therefore, there is a desire for resin sashes even in areas where heat insulation is not so required.

A hard vinyl chloride resin having excellent mechanical strength, weather resistance, heat insulating properties, etc. is used for the resin sash. On the other hand, hard vinyl chloride resin has a large coefficient of linear expansion of about 8 × ^10-5 / ° C. Therefore, in areas where the temperature difference is large, it is necessary to use a metal sash with excellent dimensional stability. Stability issues have contributed to the refusal to popularize resin sashes.

By the way, it is known to add a filler as a general means for lowering the coefficient of linear expansion of a resin. For example, in a rigid vinyl chloride resin used for building materials such as rain gutters, the coefficient of linear expansion is reduced by adding an inorganic filler such as talc or calcium carbonate. However, although the coefficient of linear expansion decreases as the amount of the inorganic filler added increases, there is a problem that the physical properties of the resin such as impact resistance decrease.

To solve the above problems, for example, in Patent Documents 1 and 2, for example, by using an inorganic filler having a particle shape having a high aspect ratio, chloride has a reduced coefficient of linear expansion while maintaining impact resistance. Vinyl-based resins have been proposed.

Japanese Unexamined Patent Publication No. 2004-43774 JP-A-2009-97175

As proposed in Patent Documents 1 and 2, etc., the coefficient of linear expansion can be reduced while maintaining impact resistance by using a specific inorganic filler, but the addition of the inorganic filler deteriorates the processability. May affect the appearance of the molded product. In particular, among building materials, the appearance and design of sashes and the like are regarded as important, and rough skin on the surface of molded products due to deterioration of processing suitability becomes a problem.

Therefore, an object of the present invention is to provide a vinyl chloride-based resin composition capable of obtaining a molded product having a low coefficient of linear expansion, excellent impact resistance, a smooth surface, and no rough skin.

As a result of diligent studies to solve the above problems, the present inventor has a low coefficient of linear expansion, excellent impact resistance, and a smooth surface by adding a specific aluminosilicate to a vinyl chloride resin. It was found that a molded product without rough skin can be obtained. The present invention is based on such findings.

That is, the gist of the present invention is as follows.
[1] (A) Vinyl chloride resin and
(B) Neferin Sianite and
Including,
The (B) neferin sialite is contained in an amount of 5 to 40 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A).
A vinyl chloride-based resin composition having a coefficient of linear expansion of less than 5 × ^10-5 / ° C.
[2] The (B) neferin sialite has a cumulative frequency of 50% (D ₅₀ ) of 3 to 3 in a number-based cumulative frequency distribution curve measured using a laser diffraction / scattering particle size distribution measuring device. The vinyl chloride resin composition of [1], which has a particle size of 10 μm.
[3] A molded product made of the vinyl chloride resin composition according to [1] or [2].
[4] The molded product of [3] obtained by extrusion molding.
[5] The molded product of [3] or [4] used for building materials.
[6] The molded product of [5], wherein the building material is a sash.

According to the present invention, by adding a predetermined amount of neferin sianate, which is a kind of aluminosilicate, to a vinyl chloride resin, the coefficient of linear expansion is low, the impact resistance is excellent, the surface is smooth, and the skin is not roughened. A vinyl resin molded product can be obtained.

The vinyl chloride resin composition according to the present invention contains (A) a vinyl chloride resin and (B) neferin sianate as essential components. Hereinafter, each component constituting the vinyl chloride resin composition according to the present invention will be described.

<(A) Vinyl chloride resin>
Used in vinyl chloride resin composition according to the invention (A) a vinyl chloride resin refers to any polymer having a group represented by -CH ₂ -CHCl-, homopolymer of vinyl chloride; chloride A copolymer of a vinyl monomer and another monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer; a graft copolymer obtained by graft-copolymerizing a vinyl chloride monomer with a polymer other than a polyvinyl chloride resin, etc. Can be mentioned. One type of the polyvinyl chloride resin may be used alone, or two or more types may be used in combination. Further, the polyvinyl chloride resin may be further chlorinated. Examples of the chlorination method for the polyvinyl chloride resin include a thermal chlorination method and a photochlorination method.

Other monomers having an unsaturated bond copolymerizable with the vinyl chloride monomer include, for example, α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; butyl vinyl ether and cetyl vinyl ether. Vinyl ethers such as; (meth) acrylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl acrylate; aromatic vinyls such as styrene and α-methylstyrene; N-phenylmaleimide, N-cyclohexyl Examples thereof include N-substituted maleimides such as maleimide. One of the other monomers may be used alone, or two or more of them may be used in combination.

Examples of the polymer for graft-copolymerizing the vinyl chloride monomer include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate-monooxide. Examples thereof include carbon copolymers, ethylene-methylmethacrylate copolymers, ethylene-propylene copolymers, acrylonitrile-butadiene copolymers, polyurethanes, chlorinated polyethylenes and chlorinated polypropylenes. One of these polymers may be used alone, or two or more of these polymers may be used in combination.

In the present invention, from the viewpoint of improving impact resistance, the above-mentioned (meth) acrylate monomer graft-polymerized can be preferably used. The (meth) acrylate constituting the vinyl chloride-based graft copolymer is not particularly limited as long as it improves the impact resistance, but from the viewpoint of improving the impact resistance, the glass transition temperature of the homopolymer thereof is -140. An acrylic copolymer composed of a radically polymerizable monomer containing a (meth) acrylate as a main component and a polyfunctional monomer having a temperature of ° C to less than 0 ° C is preferable. In addition, (meth) acrylate means acrylate or methacrylate. Examples of such (meth) acrylates include n-butyl acrylate (Tg: -4 ° C., hereinafter only the temperature is shown in parentheses), n-hexyl acrylate (-57 ° C.), and 2-ethylhexyl acrylate (-85 ° C.). ℃), n-octyl acrylate (-85 ° C), n-nonyl acrylate, isononyl acrylate (-85 ° C), n-decyl acrylate (-70 ° C), lauryl acrylate, lauryl methacrylate (-65 ° C), ethyl Acrylate (-24 ° C), n-propyl acrylate (-37 ° C), n-butyl acrylate (-54 ° C), isobutyl acrylate (-24 ° C), sec-butyl acrylate (-21 ° C), n-hexyl acrylate ( −57 ° C.), n-octyl methacrylate (-25 ° C.), isooctyl acrylate (−45 ° C.), n-nonyl methacrylate (−35 ° C.), n-decyl methacrylate (−45 ° C.) and the like. These can be used alone or in combination of two or more.

For the vinyl chloride resin graft-polymerized with the (meth) acrylate monomer described above, an emulsified monomer solution containing a mixed monomer, an emulsifying dispersant, etc. is prepared in advance, and then the emulsified monomer solution is mixed with the vinyl chloride monomer and polymerized. Can be obtained by The method for graft polymerization is not particularly limited, and examples thereof include a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and a bulk polymerization method. Among these, the suspension polymerization method is preferable.

Further, the polyvinyl chloride resin may be crosslinked. Examples of the method for cross-linking the polyvinyl chloride resin include a method of adding a cross-linking agent and a peroxide, a method of irradiating an electron beam, and a method of using a water-crosslinkable material.

The average degree of polymerization of the polyvinyl chloride resin is preferably 400 to 1600 or less, and more preferably 600 to 1400, from the viewpoint of mechanical strength and moldability of the molded product. The average degree of polymerization was determined by using a resin obtained by dissolving a polyvinyl chloride resin in tetrahydrofuran (THF), removing insoluble components by filtration, and then drying and removing THF in the filtrate as a sample, and JIS K-6721. It is the average degree of polymerization measured according to the "vinyl chloride resin test method".

As the (A) vinyl chloride resin in the present invention, a commercially available resin may be used. For example, polyvinyl chloride "ZEST 1000Z" (average degree of polymerization 1000) of Shin-Daiichi PVC Co., Ltd., Shin-Etsu Chemical Co., Ltd. The company's polyvinyl chloride "TK-800" (average degree of polymerization 800), "TK-1000" (average degree of polymerization 1000) and the like can be used.

<(B) Neferin Sianite>
The vinyl chloride resin composition according to the present invention contains (B) neferin cyanite as a filler. Conventionally, inorganic fillers such as talc and calcium carbonate have been added to vinyl chloride resins in order to reduce the coefficient of linear expansion of the molded product, but when the amount of the inorganic filler added increases, the molded product Impact resistance tends to decrease. Further, as a filler capable of maintaining impact resistance while reducing the coefficient of linear expansion, wallathnite containing β-calcium metasilicate as a main component is known, but even with the filler, when the amount of the filler added increases. It affected the processability, and the surface of the obtained molded product sometimes caused so-called rough skin. In the deformed extrusion molding for obtaining molded products such as resin sashes and window frames, which require particularly high designability, a higher molding temperature is required. Therefore, the above-mentioned filler has a low linear expansion coefficient. It has been difficult to obtain a molded product having excellent impact resistance, a smooth surface, and no rough skin. In the present invention, it has been found that by using neferin sialite as a filler, a molded product having a low coefficient of linear expansion, excellent impact resistance, a smooth surface and no rough skin can be obtained.

Nepheline syenite (nepheline syenifera) is a powdery rock that constitutes a fine-grained silica-deficient silicate in the form of sodium-potassium-aluminosilicate. Neferin sianites are naturally occurring rocks composed of a mixture of sodium feldspar, potassium feldspar, and nepheline (55% sodium feldspar, 20% potassium feldspar, and 25% nepheline) and have a chemical composition. (Na, K) A compound represented by AlSiO ₄ .

Neferin sialite is in the form of fine particles as described above, but from the viewpoint of moldability such as dispersibility in resin and processability, the particle size is measured using a laser diffraction / scattering particle size distribution measuring device. In the cumulative frequency distribution curve based on the number of particles, it is preferable that the value (D ₅₀ ) of the cumulative frequency of 50% is 3 to 10 μm. The cumulative frequency distribution curve can be measured using, for example, a laser diffraction / scattering particle size distribution measuring device (SALD-2100, manufactured by Shimadzu Corporation).

From the viewpoint of maintaining impact strength, the particle size of neferin sialite is preferably 20 μm or less, more preferably 15 μm, in the cumulative frequency distribution curve, where the cumulative frequency is 90% (D ₉₀ ). is there. In order to adjust the particle size of neferin sialite within the above range, it can be appropriately adjusted according to the crushing conditions when crushing (crushing) the raw material. When the crushing time is short, the particle size of the object to be crushed tends to be large, and when the crushing time is long, the particle size tends to be small.

The particle shape of neferin sialite preferably has an aspect ratio of 2 or less, and more preferably a particle shape having an aspect ratio close to 1. The aspect ratio is a value obtained by dividing the major axis of the particle by the minor axis, and the closer to a true sphere, the closer to 1. For the aspect ratio of neferin sialite particles, for example, 100 particles are randomly selected by electron microscope observation, the aspect ratio is calculated from the major axis and the minor axis of each particle, and the average value thereof is used. ..

As the neferin sialite having the above-mentioned shape, a commercially available product may be used. For example, the trade name "Nesper" (D ₅₀ = 5.2 μm, D ₉₀ = 11.8 μm, aspect ratio) manufactured by Toyo Fine Chemical Co., Ltd. 1) etc. can be used.

(B) Neferin sialite is contained in an amount of 5 to 40 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A). If it is less than 5% by mass, the processability of the molded product such as rough skin is excellent, but the effect of reducing the coefficient of linear expansion is insufficient. On the other hand, if it exceeds 40 parts by mass, the impact resistance deteriorates. The preferable blending amount of (B) neferin sialite is 10 to 30 parts by mass.

<Other ingredients>
The vinyl chloride resin composition according to the present invention may be added with a heat stabilizer, a stabilizing aid, a lubricant, a processing aid, an antioxidant, a light stabilizer, a colorant, a filler and the like, if necessary. ..

The heat stabilizer is not particularly limited, and for example, dimethyl tin mercapto, dibutyl tin mercapto, dioctyl tin mercapto, dibutyl tin malate, dibutyl tin malate polymer, dioctyl tin malate, dioctyl tin malate polymer, dibutyl tin laurate, dibutyl. Organic tin stabilizers such as tin laurate polymer, lead-based stabilizers such as lead stearate, lead dibasic phosphite, and tribasic lead sulfate, calcium-zinc stabilizers, barium-zinc stabilizers, barium -Cadmium-based stabilizers and the like can be mentioned. These may be used alone or in combination of two or more.

The stabilizing aid is not particularly limited, and examples thereof include epoxidized soybean oil, epoxidized soybean oil epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphoric acid ester. These may be used alone or in combination of two or more.

The lubricant is not particularly limited, and examples thereof include montanic acid wax, paraffin wax, polyethylene wax, stearic acid, stearyl alcohol, and butyl stearate. These may be used alone or in combination of two or more.

The processing aid is not particularly limited, and examples thereof include an acrylic processing aid which is an alkyl acrylate / alkyl methacrylate copolymer having a weight average molecular weight of 100,000 to 2 million. Specific examples thereof include n-butyl acrylate. / Methyl methacrylate copolymer, 2-ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymer and the like can be mentioned. These may be used alone or in combination of two or more.

The antioxidant is not particularly limited, and examples thereof include a phenolic antioxidant and the like. These may be used alone or in combination of two or more.

The light stabilizer is not particularly limited, and examples thereof include ultraviolet absorbers such as salicylic acid ester-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based light stabilizers, and hindered amine-based light stabilizers. These may be used alone or in combination of two or more.

The present invention is not particularly limited, and for example, organic pigments such as azo-based, phthalocyanine-based, slene-based, and dye lake-based pigments, oxide-based, molybdenum chromate-based, sulfide / serene-based, and ferrocyanide-based inorganic pigments are used. Can be mentioned. These may be used alone or in combination of two or more.

In the present invention, (B) neferin sialite is contained as an essential component as a filler, but other conventional fillers may be contained as long as the effects of the present invention are not impaired. For example, calcium carbonate, etc. It may contain talc and the like.

In the vinyl chloride resin composition according to the present invention, the above component (A), the above component (B) and any component used as desired can be used in any melt kneader (for example, a single screw extruder, a twin screw extruder, etc.). It can be obtained by melt-kneading using a roll, a mixer, various kneaders, etc.). The obtained vinyl chloride resin composition (compound) has a coefficient of linear expansion of less than 5 × ^10-5 / ° C and is excellent in dimensional stability. Therefore, it should be suitably used for building materials such as sashes as described later. Can be done. In the present invention, the coefficient of linear expansion is measured under the measurement conditions of a measurement temperature range of 0 to 50 ° C. and a heating rate of 5 ° C./min in accordance with JIS K 7197 (a plastic linear expansion coefficient test method). Means the value.

<Molded product>
A desired molded product can be obtained from the vinyl chloride resin composition according to the present invention. The method for obtaining a molded product is not particularly limited, and conventionally known methods such as an extrusion molding method, an injection molding method, a calender molding method, and a press molding method can be applied. In particular, it is preferable to obtain a molded product by an extrusion molding method. Among the extrusion molding methods, the modified extrusion molding method for obtaining molded products such as resin sashes and window frames, which require high designability, requires a high molding temperature, but the vinyl chloride-based resin of the present invention is required. According to the composition, a molded product having a low linear expansion coefficient, excellent impact resistance, a smooth surface, and no rough skin can be obtained.

Next, embodiments of the present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples.

In the present specification, the coefficient of linear expansion, Charpy impact strength, processability, and appearance were evaluated by the following methods.

<Coefficient of linear expansion>
According to JIS K 7197 (plastic linear expansion coefficient test method), a tape-shaped extruded product having a thickness of 4 mm was measured under measurement conditions of a measurement temperature range of 0 to 50 ° C. and a heating rate of 5 ° C./min.

<Charpy impact strength>
In accordance with JIS K 7111, a sample having a tape-shaped extruded product having a thickness of 4 mm and a notch of 2 mm was prepared, and the Charpy impact strength at 23 ° C. was measured.

<Processing suitability (during compound molding)>
Each of the following raw materials is mixed according to the composition shown in Table 1, and compound molding is performed using PLASTIC EXTRUDER (screw diameter 20 mm manufactured by Nakatani Machinery Co., Ltd.) under the conditions of screw temperature 150 to 170 ° C and die temperature 180 ° C, and extrusion load. The measurement of (A) was performed.

<Processing suitability (during extrusion molding)>
Using the compound composition obtained by the above compound molding, a kneading / extrusion molding evaluation test device (Laboplast Mill 30 ml manufactured by Toyo Seiki Co., Ltd.) was used under the conditions of preheating time 2 min, test temperature 170 ° C., and test rotation speed 30 rpm. The gelling time and torque load (Nm) when kneaded in the above were measured.

<Appearance>
The appearance of the tape-shaped extruded product having a thickness of 4 mm was visually observed and evaluated according to the following criteria.
◯: The surface of the molded product is smooth and no rough skin is observed.
Δ: Some rough skin is observed on the surface of the molded product.
X: Rough skin is observed on the surface of the molded product.

The materials used are as follows.

Ingredient (A)
TK-1000 (polyvinyl chloride, average degree of polymerization 1000, Shin-Etsu Chemical Co., Ltd.)
Ingredient (B)
(B-1): Nesper (neferin sialite particles, particle size D ₅₀ = 5.2 μm, D ₉₀ = 11.8 μm, aspect ratio 1, manufactured by Toyo Fine Chemicals Co., Ltd.)
(B-2): KK600 (calcium bicarbonate particles, particle size D ₅₀ = 4.0 μm, aspect ratio 1, manufactured by Shimizu Kogyo Co., Ltd.)
(B-3): MS-Z (talc particles, particle diameter D ₅₀ = 15 μm, aspect ratio 8, manufactured by Japan Talc Co., Ltd.)
(B-4): AB-25S (Muscovite, particle size D ₅₀ = 24 μm, aspect ratio 80, manufactured by Yamaguchi Mica Industry Co., Ltd.)
Other Ingredients RX-210 (Ca / Zn Stabilizer, ADEKA STAB RX-210, ADEKA CORPORATION)

Each of the above raw materials was mixed according to the composition shown in Table 1, and the resin composition temporarily kneaded using a single-screw extruder and a flat die at a die outlet resin temperature of 180 ° C. was obtained in a width of 20 mm and a thickness of 20 mm. Extrusion molding was performed so as to have a tape shape of 4 mm, and a molded product was obtained. The linear expansion coefficient, Charpy impact strength, and appearance of the obtained molded product were evaluated. The evaluation results are as shown in Table 1.

As is clear from the evaluation results in Table 1, the vinyl chloride resin composition (Example 4) containing no filler has a good impact resistance and processability, but has a coefficient of linear expansion of 7.8 × 10. ^It is as large as ^-5 / ° C. Further, in the conventional vinyl chloride resin composition to which a filler is added (Examples 6 to 8), although the coefficient of linear expansion and the impact resistance can be compatible to some extent, the processing suitability is insufficient, particularly talc (Example 6 to 8). Rough skin is observed in the appearance of those using 7) or mica (Example 8). On the other hand, in the vinyl chloride resin composition containing a specific amount of neferin sialite (Examples 2 and 3), a molded product having a low coefficient of linear expansion, excellent impact resistance, a smooth surface and no rough skin is obtained. It turns out that it can be obtained.

Claims (6)

(A) Vinyl chloride resin and
(B) Neferin Sianite and
Including,
The (B) neferin sialite is contained in an amount of 5 to 40 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A).
A vinyl chloride-based resin composition having a coefficient of linear expansion of less than 5 × ^10-5 / ° C. The (B) neferin sialite is a particle having a cumulative frequency of 50% (D ₅₀ ) of 3 to 10 μm in a number-based cumulative frequency distribution curve measured using a laser diffraction / scattering particle size distribution measuring device. The vinyl chloride-based resin composition according to claim 1, which has a diameter. A molded product made of the vinyl chloride resin composition according to claim 1 or 2. The molded product according to claim 3, which is obtained by extrusion molding. The molded product according to claim 3 or 4, which is used as a building material. The molded product according to claim 5, wherein the building material is a sash.