JPH10292079A - Vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride resin compsn. which gives a molded article excellent in uniform pearlescent appearance in the fields of profile extrudates, coextrudates, and laminates with other materials by compounding a vinyl chloride resin with a plasticizer, calcium carbonate having a specified average particle size, and a pearlescent pigment. SOLUTION: The vinyl chloride resin used may be a vinyl chloride homopolymer or a copolymer formed mainly from vinyl chloride, and one having an average degree of polymn. of 500-3,000 is pref. in terms of moldability and mechanical properties. Phthalic esters (e. g. dioctyl phthalate) and polyester plasticizers are the examples of the plasticizer used, and 20-200 pts.wt. plasticizer is compounded into 100 pts.wt. resin. 5-20 pts.wt. calcium carbonate having an average particle size of 1 μm or lower is used per 100 pts.wt. resin. A titanium-coated natural mica having an average particle size of 1-200 μm is esp. pref. as the pearlescent pigment in terms of surface properties, weatherability, and heat resistance, and the amt. of it compounded is 0.1-5 pts.wt. per 100 pts.wt. resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition suitable as a raw material for products having a pearl-like appearance, and in particular, is co-extruded with a profile-extruded product or another material, or is used in combination with another material. The present invention relates to a vinyl chloride resin composition capable of providing a product having a good appearance even in a product to be bonded to a part.

[0002]

2. Description of the Related Art Heretofore, as a vinyl chloride resin composition used as a raw material of a product having a pearly tone, a vinyl chloride resin mixed with a pearl pigment has been used. Since this pearl pigment produces a pearl tone by regular multiple reflection of light, the base vinyl chloride resin has good transparency, but a pearl tone can be obtained even with a small amount of pearl pigment added. Therefore, it is common not to add a material that hinders transparency, such as calcium carbonate.

[0003] However, a product molded with such a composition is not particularly problematic when it is flat and used alone, but partially when it is a profile extruded product. Since the wall thicknesses are different, there is a problem that the pearly feeling looks different between the thin portion and the thick portion. Also, in the case of products that are co-extruded with other materials or bonded with other parts, products that are formed of materials with low hiding power are affected by the color of the base material of other materials or parts. Then, there was a problem that the appearance was different from the original color tone.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a uniform pearly appearance even in a profile-extruded product or a product coextruded with another material or bonded to another part. An object of the present invention is to provide a vinyl chloride-based resin composition capable of molding a product that is not inferior to the original product appearance.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the plasticizer, calcium carbonate, and pearl pigment were each added to a vinyl chloride resin in a specific amount. By blending, vinyl chloride that can be extruded with deformed extruded products and other materials, or can be molded into products that are excellent in pearl tone and are not inferior to the original product appearance even in products that are bonded to other parts The present inventors have found a system resin composition and have reached the present invention. That is, the vinyl chloride-based resin composition of the present invention has a plasticizer of 20 to 200 parts by weight, and an average particle size of calcium carbonate of 5 to 20 parts by weight based on 100 parts by weight of the vinyl chloride-based resin.
Parts by weight and 0.1 to 5 parts by weight of pearl pigment. Further, the pearl pigment is obtained by coating the surface of natural mica with titanium oxide and having an average particle diameter of 1
A vinyl chloride resin composition having a thickness of from 200 to 200 μm is preferred.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the vinyl chloride resin composition of the present invention will be described in detail. As the vinyl chloride resin used in the present invention, a vinyl chloride homopolymer, a copolymer of 50% by weight or more of a vinyl chloride monomer and a vinyl monomer copolymerizable therewith, or Examples thereof include a graft copolymer obtained by graft-polymerizing vinyl chloride to a polymer other than the above. Among them, a vinyl chloride homopolymer is preferable. These vinyl chloride resins are
Usually, those having an average degree of polymerization of 300 to 8000 are used, but those having an average degree of polymerization of 500 to 3000 are preferable in consideration of the balance between moldability and mechanical properties.

The vinyl monomers copolymerizable with the vinyl chloride monomer include, for example, α-olefins such as ethylene, propylene and butylene; vinyl acetate, vinyl caproate, vinyl laurate and stearin Vinyl esters such as vinyl acid; vinyl ethers such as butyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether and phenyl vinyl ether; acrylic acid or methacryl such as ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and stearyl methacrylate Acid esters; aromatic vinyls such as styrene and α-methylstyrene; vinylidene chloride, vinyl fluoride, vinyl bromide,
Halogenated olefins such as propylene chloride; N such as N-phenylmaleimide and N-cyclohexylmaleimide;
-Substituted maleimides; acrylic acid, methacrylic acid, acrylonitrile; acrylic derivatives such as maleic anhydride and itaconic anhydride; and these may be used alone or in combination of two or more.

Examples of the polymer which can be graft-polymerized with a vinyl chloride monomer include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene Ethyl acrylate / carbon monoxide copolymer, ethylene / methyl methacrylate copolymer, ethylene / propylene copolymer, acrylonitrile / butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated polypropylene, methyl methacrylate / butadiene / styrene copolymer Coalescing,
Examples include acrylonitrile / butadiene / α-methylstyrene copolymer, polybutyl acrylate, butyl rubber, polystyrene, styrene / butadiene copolymer, and acrylic rubber, and these are used alone or in combination of two or more. These may be used in combination with a monomer having at least one unsaturated group copolymerizable with the vinyl chloride monomer.

In the vinyl chloride resin composition of the present invention, the plasticizer used as the second component may be any plasticizer that is compatible with the vinyl chloride resin. Examples of the plasticizer include dimethyl phthalate and phthalate. Diethyl phosphate, dibutyl phthalate, dioctyl phthalate (DOP), di-n-octyl phthalate (n-DOP), diisodecyl phthalate, diisononyl phthalate (hereinafter referred to as DINP),
Phthalates such as butylbenzyl phthalate; dibasic aliphatic esters such as dibutyl adipate, di-n-hexyl adipate and dibutyl sebacate; tributyl phosphate, tri-2-n-ethylhexyl phosphate; Phosphoric esters such as tricresyl phosphate and triphenyl phosphate; trimellitic esters such as trimellitic acid-tri-2-ethylhexyl and tributyl trimellitate; glycol esters such as pentaerythritol ester and diethylene glycol benzoate; epoxy Esters such as petroleum soybean oil and epoxidized linseed oil; citrates such as acetyl tributyl citrate, acetyl trioctyl citrate and tri-n-butyl citrate; tetra-n-octyl pyromellitate, polypropylene A Pies, etc. Other polyester plasticizers and the like, which are used in one or more combinations. These plasticizers are 20 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin,
Preferably, it is added in the range of 30 to 100 parts by weight. If the amount is less than 20 parts by weight, melting cannot be sufficiently performed, and molding becomes difficult. If the amount exceeds 200 parts by weight, it becomes too soft and molding becomes difficult, which is not preferable.

In the present invention, the calcium carbonate used as the third component includes heavy calcium carbonate, light calcium carbonate, precipitated calcium carbonate, and the like.
These are used alone or in combination of two or more. The average particle size is an important requirement, and the average particle size is 1 μm or less, particularly 0.05 to 0.5 μm.
It is more preferably in the range of 8 μm, and if it is larger than 1 μm, there is a disadvantage that the hiding power is too strong and the pearl tone is impaired. These exemplified calcium carbonates are used in an amount of 5 to 2 parts per 100 parts by weight of the vinyl chloride resin.
Used in the range of 0 parts by weight. If the amount is less than 5 parts by weight, the hiding power will be insufficient and the effect of the color of the base will be exerted. If the amount is more than 20 parts by weight, the hiding power will be too strong and the pearl tone will be impaired.

In the present invention, the pearl pigment used as the fourth component is not particularly limited as long as it is a commonly used one. However, from the viewpoints of surface properties, weather resistance, heat resistance and the like, the surface of natural mica is particularly preferred. Those coated with titanium oxide are preferably employed, and those having a coverage of 14 to 38% are more preferably used. The average particle diameter of the pearl pigment is preferably in the range of 1 to 200 μm.
If this is less than 1 μm, a pearly tone cannot be obtained, and 200 μm
If it is larger, not only the surface smoothness is lost but also the moldability deteriorates, such being undesirable. The pearl pigment is added in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If this is less than 0.1 part by weight, a pearly tone cannot be obtained,
If it is more than 5 parts by weight, not only does the moldability deteriorate, but also
This is economically disadvantageous because a pearly tone cannot be obtained in proportion to the amount added.

In the vinyl chloride resin composition of the present invention, in addition to the above four components, if necessary, stabilizers, modifiers, fillers, coloring agents and the like generally used for vinyl chloride resins are used. Can be appropriately selected and added within a range that does not impair the object of the present invention. As the stabilizer, for example, tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite,
Lead-based stabilizers such as dibasic lead phthalate, lead white, lead laurate or stearate; butyltin malate, octyltin malate, di-n-alkyltin mercaptide, di-n
Alkyl tin dilaurate, dibutyl tin dimaleate, dibutyl tin lauryl mercaptide, di-octyl tin S,
Tin-based stabilizers such as S'-bis- (isooctyl-mercaptoacetate), dibutyltin-bis-isooctylthioglycolate, di (n-octyl) tin malate polymer, dibutyltin mercaptopropionate; calcium, Organic metal salt stabilizers such as cadmium, barium and zinc laurate or stearate and metal soap stabilizers; antimony stabilizers such as antimony mercaptocarboxylate or ester salts; phosphate stabilizers; Soybean oil, epoxidized oil stabilizers such as epoxidized linseed oil, BHT, sulfur, ultraviolet absorbers such as hindered phenols such as bisphenol dimerized with methylene group, salicylic acid ester, benzophenone, benzotriazole, These are one or two
Used in combinations of more than one species.

As the modifier, for example, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, chlorinated polyethylene, methyl methacrylate / butadiene / styrene copolymer, acrylonitrile / butadiene / styrene copolymer Impact modifiers such as acrylonitrile, butadiene and α-methylstyrene copolymers, methyl methacrylate / acrylate copolymers, and other heat-resistant modifiers such as copolymers using maleimide; antimony trioxide , Aluminum hydroxide,
Flame retardants such as sodium antimonate, phosphate esters and phosphate compounds, chlorinated paraffins, chlorinated olefins, hexabromobenzene; elasticity imparting agents such as partially cross-linked NBR, acrylic rubber, polyurethane; They are arbitrarily selected from inhibitors, surfactants, conductivity-imparting agents and the like, and are used alone or in combination of two or more.

As the filler, for example, carbonates such as magnesium carbonate and dawsonite; oxides such as silica, diatomaceous earth and titanium oxide; hydroxides such as aluminum hydroxide and magnesium hydroxide; calcium sulfate Sulphate such as talc, barium sulfate, etc .; silicates such as talc, clay, mica and calcium silicate; carbons such as carbon black and graphite; short glass fibers, metal fibers, short carbon fibers, carbon fibers And the like; metal powders such as iron powder and copper powder; heat-resistant resins such as polyimide and silicone; and the like, and these are used alone or in combination of two or more.

The coloring agent can be arbitrarily selected from those commonly used for coloring plastics. Examples of such a coloring agent include metal powders such as aluminum powder and bronze powder, carbon salts such as carbon black, titanium oxide, zinc oxide, oxides such as porcelain, sulfates such as precipitated barium sulfate, and the like. Inorganic pigments such as carbonates such as calcium carbonate and basic magnesium carbonate, silicates such as clay and ultramarine, chromates such as graphite, aluminates such as cobalt blue, and ferrocyanide compounds such as dark blue; toluidine Azo pigments such as red, permanent carmine FB, disazo yellow AAA and lake red C; polycyclic pigments such as phthalocyanine blue, indanthrone blue and quinacridone red; dyed lakes such as Victoria Pure Blue BO lake and alkali blue toner. Pigments, azine pigments, fluorescent pigments and other organic pigments and basic dyes, acidic Fee, solvent dye, include dyes such as disperse dyes, which are used in combination one or more kinds.

[0016] The vinyl chloride resin composition of the present invention comprising the above components can be used in the same manner as a conventional vinyl chloride resin composition.
After mixing with a mixer such as a super mixer or a ribbon blender, the mixture can be kneaded with a Banbury mixer, a mixing roll, a single-screw or twin-screw extruder, and granulated and molded. The granulated vinyl chloride resin composition of the present invention is commercialized by extrusion molding, injection molding, blow molding or the like, but extrusion molding in which pearl pigments are uniformly oriented is most suitable.

[0017]

EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these descriptions. The components (parts by weight) of the formulations shown in Tables 1 and 2 were put into a 20-liter Henschel mixer and mixed, and the mixture was subjected to a full flight screw having an L / D of 22 and a compression ratio of 3.0. 50mm used
A sample (pellet) was obtained by granulation with a single screw extruder. This was tested by the following method, and the results are shown in Tables 1 and 2. The details of each component used are shown below.

[Test Method] Molding test: A sample (pellet) was L / D = 22, 50 mm using a full flight screw with a compression ratio of 3.0.
A T-shaped sample was extruded with a single screw extruder under the following conditions. The sample was evaluated for pearl tone and streaks at the joint. (Pearl-like) The surface of the extruded sample was visually observed and evaluated according to the following criteria. A: Strong pearl tone is shown. ：: Pearl tone is shown. ×: No pearl tone was exhibited. (Stripe of Joint) The joint of the extruded sample was visually observed and evaluated according to the following criteria. A: Surface condition similar to that of the site other than the joint. ：: The joined portion looks slightly dark, but is hardly noticeable. ×: The joint appears black like a streak. Bonding property: A 0.4 mm extruded belt was prepared in the same manner as in the molding test. Under the same conditions, the Munsell No. An extruded belt having a color tone of N-1 was also prepared, and using this as a base, the previously prepared sample was adhered and the surface was visually observed and evaluated according to the following criteria. A: There is no influence of the color of the base. ：: The effect of the background color is hardly felt. ×: The influence of the background color is strong, and the color tone looks different from the original color tone.

[Specification of components]-Vinyl chloride resin (referred to as PVC in the table): "TK-
1300 "(trade name, manufactured by Shin-Etsu Chemical Co., Ltd., average polymerization degree 13
00 vinyl chloride homopolymer)-Vinyl chloride resin (same as above): "TK-2500LS"
(Shin-Etsu Chemical Co., Ltd., vinyl chloride homopolymer having an average degree of polymerization of 2250)-Calcium carbonate A: "MSK-P" (trade name, Maruo Calcium Co., average particle size 0.55 µm)-Calcium carbonate B: "Whiteton SB" (trade name, manufactured by Shiraishi Calcium Co., average particle diameter 1.85 μm) Pearl pigment A: "Iriodin 100 Pearl" (trade name, manufactured by Merck Japan Co., average particle diameter 10-60 μm) [Surface of natural mica・ Pearl pigment B: “Iriodin 120 Pearl” (trade name, manufactured by Merck Japan, average particle diameter 5 to 25 μm) [Titanium oxide is coated 38% on the surface of natural mica]

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

According to the vinyl chloride resin composition of the present invention, even in a profile extruded product, a product coextruded with another material, or a product to be bonded to other parts, it has good surface properties and a pearly tone. It is possible to obtain a molded product excellent in quality.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C08K 9/02 C08K 9/02

Claims (2)

[Claims] [Claim 1] 100 parts by weight of a vinyl chloride resin,
20 to 200 parts by weight of a plasticizer, 5 to 20 parts by weight of calcium carbonate having an average particle size of 1 μm or less, and 0.1 to 5 of a pearl pigment
A vinyl chloride resin composition containing parts by weight. 2. A pearl pigment comprising a surface of natural mica coated with titanium oxide, and having an average particle diameter of 1 to 200 μm.
The vinyl chloride resin composition according to claim 1, wherein m is m.