JP3517309B2 - PVC resin molding material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent antibacterial and antifungal properties and is useful as a soft vinyl chloride resin molded article used for kitchens, bathrooms, toilets and the like. The present invention relates to a vinyl chloride resin molding material having no bleed-out due to a lubricant and having a good touch feeling. [0002] Conventionally, soft vinyl chloride resin molded articles have been widely used in kitchens, bathrooms, toilets, etc. because of their good moldability and flexibility. However, since these molded articles are likely to be used under high humidity or wet with water, mold may be formed and the appearance of the molded articles may be impaired. In addition, since this mold is not preferable from the viewpoint of hygiene, a method of adding and mixing an antibacterial / antifungal agent to a soft vinyl chloride resin and suppressing the generation of mold has been adopted. However, it is necessary to use a large amount of antibacterial and antifungal agents in order to increase the antibacterial and antifungal power.
There was an economic constraint due to the high cost of the fungicide. Moreover, large-scale use is not preferable because of problems such as moldability, color tone and toxicity. On the other hand, a method has been proposed in which a lubricant such as silicone oil or fatty acid amide is added to impart water repellency and the amount of an antibacterial / antifungal agent added is suppressed, but it is necessary to add a large amount of a lubricant. A water repellent effect was not obtained, and the use of a large amount of a lubricant deteriorated the moldability, or the bleed out of the lubricant sometimes impaired the appearance of a molded product. Accordingly, an object of the present invention is to provide a vinyl chloride resin molding material excellent in moldability which does not cause appearance defects of molded articles due to generation of mold and bleed-out of a lubricant or the like. To provide. [0004] The vinyl chloride resin molding material according to the present invention comprises (1) 100 parts by weight of vinyl chloride resin, (2) 10 to 200 parts by weight of a plasticizer, and (3) )
(A) a polyorganosiloxane represented by the following general formula (Formula 3) and (b) an acrylate ester or a mixture of an acrylate ester and a monomer copolymerizable therewith,
1 to 100 parts by weight of an acrylic-modified polyorganosiloxane obtained by emulsion graft polymerization, and (4) zeolite
Silver zeolite in which metal ions in the silver zeolite are replaced with silver ions .
1 to 5 parts by weight. [0005] [Wherein R ¹ , R ² and R ³ are the same or different and are each a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, Y is a radical reactive group, an organic group having an SH group or both, Z ¹ and Z ² are the same or different hydrogen atoms, lower alkyl groups or groups represented by the following general formula (Formula 4), m is a positive integer of 10,000 or less, and n is a positive integer of 1 or more] Formula 4 (Wherein R ⁴ and R ⁵ are the same or different, each having 1 to 20 carbon atoms, a hydrocarbon group or a halogenated hydrocarbon group,
R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or an organic group having a radical reactive group, an SH group or both.) The present invention will be described in detail below. The vinyl chloride resin used as the component (1) in the vinyl chloride resin molding material of the present invention includes a vinyl chloride homopolymer, a vinyl chloride monomer of 50% by weight or more, and a vinyl chloride copolymerizable with the vinyl chloride monomer. Examples thereof include a copolymer with a monomer and a graft polymer obtained by graft-polymerizing vinyl chloride to a polymer other than these. Among them, a vinyl chloride homopolymer is preferable. These vinyl chloride resins usually have an average degree of polymerization of 300 to 8,000, but the average degree of polymerization is 700 to 3,0 in view of the balance between moldability and mechanical properties.
00 is preferred. 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; alkyl vinyl ethers such as butyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether and phenyl vinyl ether; acrylic acid such as ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate; Esters of methacrylic acid; aromatic vinyls such as styrene and α-methylstyrene; halogenated olefins such as vinylidene chloride, vinyl fluoride, vinyl bromide and propylene chloride;
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; acrylic acid, methacrylic acid, crotonic acid, acrylonitrile, maleic anhydride,
Acrylic derivatives such as itaconic anhydride may be mentioned, 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, which 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. The plasticizer used as the component (2) in the vinyl chloride resin molding material of the present invention may be any plasticizer that is compatible with the above vinyl chloride resin, such as dimethyl phthalate and phthalate. Phthalates such as diethyl phosphate, di-n-octyl phthalate (hereinafter referred to as DOP), dibutyl phthalate, diisodecyl phthalate, and butylbenzyl phthalate; dibutyl adipate, di-n-hexyl adipate, sebacine Aliphatic dibasic acid esters such as dibutyl acid; tributyl phosphate and tri-phosphate
Phosphates such as 2-n-ethylhexyl, tricresyl phosphate and triphenyl phosphate; trimellitates such as tri-2-ethylhexyl trimellitate and tributyl trimellitate; pentaerythritol esters and diethylene glycol benzoate Glycol esters; epoxidized oils such as epoxidized soybean oil and epoxidized linseed oil; citrate esters such as acetyl tributyl citrate, acetyl trioctyl citrate and tri-n-butyl citrate; tetra-n-octyl Examples include pyromellitate, polypropylene adipate, and other polyester plasticizers, which are used alone or in combination of two or more. These plasticizers are used in an amount of 10 to 2 parts per 100 parts by weight of the vinyl chloride resin.
00 parts by weight, preferably in the range of 30 to 100 parts by weight. If the amount is less than 10 parts by weight, the flexibility unique to the soft vinyl chloride resin cannot be obtained, and if it exceeds 200 parts by weight, the appearance of the product is impaired due to the bleed out of the plasticizer. In the vinyl chloride resin molding material of the present invention, the acrylic-modified polyorganosiloxane used as the component (3) is, as described above, (a) a polyorganosiloxane represented by the above general formula (Formula 3). , (B)
An acrylic ester or a mixture of an acrylic ester and a monomer copolymerizable therewith is subjected to emulsion graft copolymerization. The weight ratio of the two components (a) / (b) in the emulsion graft copolymerization is 2%.
/ 8 to 8/2, particularly preferably 4/6 to 7/3. The acrylic-modified polyorganosiloxane is used in an amount of 1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 1 part by weight, the antibacterial and antifungal effect is insufficient, and if it exceeds 100 parts by weight, the antibacterial and antifungal effect is not improved in proportion to the amount added, which is uneconomical. R ¹ , R ² and R ³ in the general formula (Chemical Formula 3) of the component (a) each represent an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a phenyl group, a tolyl group or a xylyl group. Group, a hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as a naphthyl group, or a hydrocarbon group having 1 to 20 carbon atoms in which at least one of the hydrogen atoms bonded to the carbon atoms of these hydrocarbon groups is substituted with a halogen atom. Halogenated hydrocarbon groups, which may be the same or different from each other. Y is a radical reactive group such as a vinyl group, an allyl group, a γ-acryloxypropyl group, a γ-methacryloxypropyl group, a γ-mercaptopropyl group, S
An organic group having an H group or both. Z ¹ and Z
² is a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a triorganosilyl group represented by the above general formula (Formula 4), which may be the same or It may be different. In the general formula (Chemical Formula 4), R ⁴ and R ⁵ are the same or different, each having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. Specific examples of the hydrocarbon group or the halogenated hydrocarbon group include a hydrogen group, a radical reactive group, an organic group having an SH group or both, and specific examples of the radical reactive group in R ¹ , R ² and R ³ above. Examples are the same as those described above for Y. m is a positive integer of 10,000 or less, preferably an integer in the range of 500 to 8,000, and n is a positive integer of 1 or more, preferably in the range of 1 to 500. On the other hand, the acrylate of the component (b) includes, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, Alkyl acrylates such as stearyl acrylate; alkoxyalkyl acrylates such as methoxyethyl acrylate and butoxyethyl acrylate; cyclohexyl acrylate, phenyl acrylate, and benzyl acrylate; and the like, used alone or in combination of two or more. The monomer copolymerizable with the acrylate ester used as a mixture with the acrylate ester includes, for example, a hydroxy group-containing monomer such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate. Examples thereof include unsaturated monomers and the like, which are used alone or in combination of two or more. In the vinyl chloride resin molding material of the present invention, the metal ions in the zeolite are replaced with silver ions as the component (4).
An on-substituted silver zeolite is used . This silver zeo
Light is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.1 part by weight, the antibacterial and antifungal effects are insufficient, and even if the amount exceeds 5 parts by weight, the antibacterial and antifungal effects are not improved depending on the added amount, and it is uneconomical. The vinyl chloride resin molding material of the present invention includes:
If necessary, commonly used for vinyl chloride resin,
Stabilizers, lubricants, modifiers, fillers, coloring agents, and the like can be added and mixed as long as the object of the present invention is not impaired. As the stabilizer, for example, tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, dibasic lead phthalate, lead white,
Lead-based stabilizers such as lead laurate or stearate; butyltin maleate, octyltin maleate, di-n-alkyltin mercaptide, di-n-alkyltin dilaurate, dibutyltin dimaleate, dibutyltin lauryl mercaptide, di-octyl Tin-based stabilizers such as tin-S, S'-bis- (isooctyl-mercaptoacetate), dibutyltin bis-isooctylthioglycolate, di (n-octyl) tin maleate polymer, dibutyltin mercaptopropionate Organic metal salt stabilizers such as laurate or stearate of calcium, cadmium, barium or zinc and metal soap stabilizers; antimony stabilizers such as antimony mercaptocarboxylate or ester salts; phosphate stabilizers; Soybean oil, epoxidized Epoxidized oil-based stabilizers such as two oil;
Hindered phenols such as bisphenols dimerized with BHT, sulfur, methylene groups, etc., salicylates,
Examples include ultraviolet absorbers such as benzophenone and benzotriazole, which are used alone or in combination of two or more. As the lubricant, for example, low molecular wax,
Aliphatic hydrocarbon lubricants such as polyethylene wax, paraffin wax and liquid paraffin; higher aliphatic alcohol lubricants such as stearyl alcohol; fatty acid lubricants such as stearic acid, palmitic acid and myristic acid; stearamide, palmitamide; Aliphatic amide-based lubricants such as methylene bis-stearamide; fatty acid ester-based lubricants such as glycerin monostearate, ethyl diaminostearate, and butyl stearate; or metallic soaps;
And silicone oils and the like.
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 acrylic rubber and the like; gelling accelerators such as polymethyl methacrylate; acrylonitrile / butadiene / α-methylstyrene copolymer, methyl methacrylate / acrylate copolymer, and other copolymers using maleimide Flame retardants such as antimony trioxide, aluminum hydroxide, sodium antimonate, phosphate esters and phosphate compounds, chlorinated paraffins, chlorinated polyolefins, hexabromobenzene, etc .; partially crosslinked NBR, acrylic Rubber,
Elasticity-imparting agents such as polyurethane; further, arbitrarily selected from foaming agents, antistatic agents, surfactants, and conductivity-imparting agents, and used alone or in combination of two or more. Examples of the filler include carbonates such as heavy calcium carbonate, light calcium carbonate, precipitated calcium carbonate, magnesium carbonate and dawsonite; silica,
Oxides such as diatomaceous earth and titanium oxide; hydroxides such as aluminum hydroxide and magnesium hydroxide; (sulfites) such as calcium sulfate and barium sulfate; talc, clay, mica, calcium silicate, etc. Silicate type; carbon type such as carbon black and graphite; hollow or solid glass beads, inorganic fiber type such as short glass fiber, metal fiber, short carbon fiber and carbon fiber; metal powder such as iron powder and copper powder System; heat-resistant resins such as polyimide and silicone are used, and these are used alone or in combination of two or more. As the coloring agent, any one can be selected from those conventionally used for coloring plastics. Examples of such coloring agents include, for example, aluminum powder, metal powders such as bronze powder, carbons such as carbon black, titanium oxide, zinc oxide, oxides such as red iron oxide, sulfates such as precipitated barium sulfate, Inorganic pigments such as carbonates such as calcium carbonate and basic magnesium carbonate, silicates such as clay and ultramarine blue, 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, acid dyes, oil dyeing , It includes dyes such as disperse dyes, which are used alone or in combination of two or more. The vinyl chloride resin molding material of the present invention comprising the above components is mixed with a mixer such as a super mixer, a ribbon blender or the like, like a conventional vinyl chloride resin composition, and then mixed with a Banbury mixer, a mixing roll,
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of the present invention will be described below with reference to Examples and Comparative Examples, which can be kneaded and granulated using a single-screw or twin-screw extruder. It is not limited to these descriptions. Examples 1 to 8 and Comparative Examples 1 to 8 The components (parts by weight) in the formulations shown in Tables 1 and 2 were
Pour the mixture into a 20-liter Henschel mixer, mix the mixture, and use a 3.5-inch test roll (two).
The mixture was kneaded at 150 ° C. for 7 minutes to obtain a roll sheet molded product. After holding this with a mirror plate and preheating at 170 ° C for 4 minutes,
120 mm × 120 mm × 1.0 mm under pressure for 4 minutes at a pressure of kg / cm ²
A sample (sheet) having a size of was prepared. 100g of the above mixture
Was evaluated by the following criteria while observing the condition when kneaded with a 3.5-inch test roll, and the obtained samples were tested for antibacterial and bleeding properties by the following method. Are also shown in Tables 1 and 2. (Evaluation criteria) A: Can be kneaded without any problem. B: It can be kneaded with some time. C ‥ It can be kneaded if it takes a considerable time. D ‥ Cannot be kneaded because it does not wrap around the roll. The details of each component used in the test and the test method for antibacterial activity and bleeding property are as follows. (Specifications of components) (1) Component: vinyl chloride resin: TK-1300 (Shin-Etsu Chemical Co., Ltd., trade name, vinyl chloride homopolymer having an average degree of polymerization of 1300) (2) Component: DOP-Epoxidized soybean oil (3) Component: Acrylic-modified polyorganosiloxane: Charine R
(Trade name, manufactured by Nissin Chemical Industry Co., Ltd.) Structure of polyorganosiloxane of component (a): Mixture of acrylic acid ester of component (b) and a monomer copolymerizable therewith: acrylic acid ester: methyl acrylate: 98% by weight monomer copolymerizable with acrylic acid ester: 2 -Hydroxyethyl methacrylate: 2% by weight (a), (b) Blending ratio of both components: (a) / (b) = 7
/ 3 (4) Ingredients ・ Antibacterial / antifungal agent A: Bactekiller BM-502 (Kanebo Co., Ltd.) ・ Antibacterial antifungal agent B: Novalon AG300 (Toagosei Chemical Co., Ltd.) ・ Antibacterial / antifungal agent C: Vinadine IT-3020 (trade name, manufactured by Morton, USA) [Escherichia coli] [Test method] A small amount of a test bacterium cultured at 36 ° C. for 24 hours on a grain heart infusion agar medium is collected with a platinum loop, suspended in a sterilized dispersion, and has a bacterial concentration of about 10 ⁶ cells / ml. Dilute with the same dispersion liquid to make a test bacterial suspension, drop it into a test piece cut into a size of about 50 mm x 40 mm (thickness: about 1 mm) 0.2 ml at a time and sterilize Coated with polyethylene film (50mm x 35mm x 0.1mm) and kept at high humidity and 36 ℃ for 20 hours After examined the viable cell count by and washed out with sterile buffered saline pour agar method (SCD agar medium used). As the dispersion, 1/1000 broth was used for Staphylococcus aureus, and a phosphate buffer was used for Escherichia coli. Bleedability: The molded product was irradiated with a sunshine weatherometer at 63 ° C. for 800 hours to observe the surface stickiness and evaluated according to the following criteria. (Evaluation criteria) A: No bleed out. B ‥ Bleed out slightly. C @ bleed out. D ‥ I'm bleeding out quite a bit. [Table 1] [Table 2] According to the vinyl chloride resin molding material of the present invention, it is possible to obtain a molded article excellent in moldability which does not cause appearance defects due to generation of mold and bleed-out of a lubricant or the like.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Ryozo Amano 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Japan Inax Corporation (56) References JP-A-7-102146 (JP, A) JP-A Heihei 7-18140 (JP, A) JP-A-7-16998 (JP, A) JP-A-6-179788 (JP, A) JP-A-6-136132 (JP, A) JP-A-6-122800 (JP, A A) JP-A-4-353550 (JP, A) JP-A-3-281556 (JP, A) JP-A-1-115311 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C08L 27/06 C08L 51/08

Claims (1)

(57) [Claims] (1) 100 parts by weight of a vinyl chloride resin, (2) 10 to 200 parts by weight of a plasticizer, and (3)
(A) a polyorganosiloxane represented by the following general formula (Formula 1) and (b) an acrylate ester or a mixture of an acrylate ester and a monomer copolymerizable therewith,
1 to 100 parts by weight of an acrylic-modified polyorganosiloxane obtained by emulsion graft polymerization, and (4) zeolite
Silver zeolite in which metal ions in the silver zeolite are replaced with silver ions .
1 to 5 parts by weight of a vinyl chloride resin molding material. Embedded image [Wherein R ¹ , R ² and R ³ are the same or different hydrocarbon groups having 1 to 20 carbon atoms or halogenated hydrocarbon groups, Y is a radical reactive group, an SH group or an organic group having both of them, Z ¹ and Z ² are the same or different hydrogen atoms, lower alkyl groups or groups represented by the following general formula (Formula 2), m is a positive integer of 10,000 or less, and n is a positive integer of 1 or more. . ] Wherein R ⁴ and R ⁵ are the same or different and each have 1 carbon atom
To 20 hydrocarbon groups or halogenated hydrocarbon groups, R ⁶
Is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or an organic group having a radical reactive group, an SH group, or both. ]