WO2008062560A1 - Lead-free vinyl chloride resin composition and extruded object based on lead-free vinyl chloride - Google Patents

Lead-free vinyl chloride resin composition and extruded object based on lead-free vinyl chloride Download PDF

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Publication number
WO2008062560A1
WO2008062560A1 PCT/JP2007/001275 JP2007001275W WO2008062560A1 WO 2008062560 A1 WO2008062560 A1 WO 2008062560A1 JP 2007001275 W JP2007001275 W JP 2007001275W WO 2008062560 A1 WO2008062560 A1 WO 2008062560A1
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WO
WIPO (PCT)
Prior art keywords
vinyl chloride
chloride resin
lead
resin composition
weight
Prior art date
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PCT/JP2007/001275
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French (fr)
Japanese (ja)
Inventor
Syoji Ito
Original Assignee
Mitsubishi Plastics, Inc.
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Publication date
Application filed by Mitsubishi Plastics, Inc. filed Critical Mitsubishi Plastics, Inc.
Priority to JP2008545314A priority Critical patent/JPWO2008062560A1/en
Publication of WO2008062560A1 publication Critical patent/WO2008062560A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups

Definitions

  • the present invention provides a lead-free vinyl chloride resin composition capable of producing an extrusion-molded article having excellent thermal stability and does not contaminate the mold during molding, and
  • the present invention relates to a lead-free vinyl chloride extruded product obtained by extrusion molding of the vinyl chloride resin composition.
  • Vinyl chloride resin (hereinafter sometimes referred to as PVC) is not only superior in mechanical strength, weather resistance, and chemical resistance, but also is less expensive than other plastic materials. Therefore, it is used in a wide range of pipes, plates, and joints.
  • a general vinyl chloride resin is easily decomposed thermally, and thus has a drawback of causing dehydrochlorination to cause a decrease in mechanical strength and coloring. Therefore, conventionally, a heat stabilizer such as a lead compound has been added to the vinyl chloride resin.
  • a heat stabilizer such as a lead compound has been added to the vinyl chloride resin.
  • lead toxicity has become a problem, and the need for non-toxic non-lead vinyl chloride resins has increased.
  • Patent Document 1 proposes a vinyl chloride resin composition containing calcium hydroxide and / or calcium oxide and a hydroxy group-containing isocyanurate.
  • Patent Document 2 organic acid calcium salt, organic acid magnesium salt, A vinyl chloride resin composition containing an organophosphorous ester and a hydroxy group-containing isocyanurate has been proposed.
  • Patent Document 1 Special Table 2 0 0 2 _ 5 1 3 0 6 3
  • Patent Document 2 Japanese Patent Laid-Open No. 2 00 0 _ 2 7 3 2 5 9
  • the object of the present invention is to combine excellent “thermal stability” and “mold resistance” in molding, and also “weather resistance” together with “weather resistance” It is another object of the present invention to provide a lead-free vinyl chloride resin composition and an extrusion-molded body that can exhibit excellent characteristics.
  • the present invention is a non-lead characterized by containing 0.001 to 1 part by weight of an isocyanurate having an epoxy group represented by the following general formula with respect to 100 parts by weight of a vinyl chloride resin.
  • a vinyl chloride resin composition is proposed. [Chemical 1] o
  • F ⁇ , 2 and 3 each represent a functional group (including H), and at least one of them is a functional group having an epoxy group.
  • the present invention also proposes a lead-free vinyl chloride extruded product obtained by extrusion molding of the lead-free vinyl chloride resin composition of the present invention.
  • the isocyanurate having an epoxy group is an isocyanurate in which an epoxy group is introduced in place of a hydroxyl group, as compared with the “hydroxy group-containing isocyanurate” proposed in Patent Documents 1 and 2 described above.
  • the present inventor maintains both thermal stability and weather resistance, and has good mold contamination (mold adhesion) and weather resistance.
  • the present invention has been conceived based on this finding.
  • the lead-free vinyl chloride resin composition and the extrusion-molded product thereof according to the present invention have excellent thermal stability and good anti-mold contamination property, despite containing no lead compound. In addition to being excellent in weather resistance, it is also excellent in deterioration resistance (weather and heat resistance) during thermal processing after outdoor storage (exposure).
  • the molded body of the resin composition of the present invention having such excellent characteristics is suitable as a material for pipes, plates, joints, etc., particularly as a material for outdoor use or a material processed secondary after outdoor storage. .
  • the vinyl chloride resin composition (hereinafter referred to as “the present vinyl chloride resin composition") described as an example of this embodiment has an epoxy group with respect to 100 parts by weight of the vinyl chloride resin.
  • Isocyanurate also referred to as “epoxy group-containing isocyanurate”
  • 0.1 to 1 part by weight if necessary, basic inorganic metal salt 0.0 1 to 1 part by weight, further if necessary Titanium oxide
  • the vinyl chloride resin used in the present vinyl chloride resin composition is not particularly limited, and the average polymerization degree in accordance with JISK 6 72 1 is in the range of 600 to 200, particularly average polymerization. Those having a degree in the range of 700 to 1450, particularly those having an average degree of polymerization in the range of 80 to 1300 can be suitably used.
  • This vinyl chloride resin may be a polyvinyl chloride resin that is a homopolymer, or may be a polyvinyl chloride copolymer obtained by copolymerization with another monomer that can be copolymerized with vinyl chloride. Good.
  • the copolymerization monomer component (monomer) of vinyl chloride is not particularly limited.
  • vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, and ethyl acrylate.
  • Examples include acid esters or methacrylate esters, ethylene, propylene and other olefins, maleic anhydride, acrylonitrile, styrene, vinylidene chloride, and the like, even if one of these is combined. You may use together.
  • a homopolymer obtained by polymerizing a vinyl chloride monomer is hard and brittle, and easily deteriorates and yellows when exposed to ultraviolet rays. Therefore, a plasticizer or a stabilizer that prevents photodegradation may be added.
  • a plasticizer or a stabilizer it is optional to add a plasticizer or a stabilizer, but even if it contains no or little plasticizer (concentration of less than about 5% by mass), The effect of the invention can be obtained This is another feature.
  • the epoxy group-containing isocyanurate used in the vinyl chloride resin composition can be represented by the following general formula.
  • R 2 and R 3 each represent a functional group (including H), and at least one of them is a functional group having an epoxy group.
  • the functional group having an epoxy group include epoxy alkyl groups such as 2,3_epoxypropyl group, 3,4_epoxybutyl group, ⁇ -methylepoxypropyl group, S-ethylepoxypropyl group, etc.
  • alkyloxyalkyl glycidyl ester groups such as alkylepoxyalkyl groups such as carboxymethyl glycidyl ester groups, strong methoxymethyl yS-methyl glycidyl ester groups, and carboxyxyl glycidyl ester groups.
  • ⁇ examples include, for example, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a vinyl group, a hydroxyl group, a hydroxyalkyl group, an ester group, a strong loxyl group, and an unsaturated carbonization.
  • a hydrogen atom an alkyl group having 1 to 12 carbon atoms
  • a vinyl group a hydroxyl group
  • a hydroxyalkyl group an ester group
  • a strong loxyl group an unsaturated carbonization.
  • Suitable examples of the epoxy group-containing isocyanurate include mono (2,3_epoxypropyl) isocyanurate, bis (2,3_epoxypropylene), and the like.
  • the epoxy group-containing isocyanurate to be used is preferably an epoxy group-containing isocyanurate having an epoxy equivalent of 90 to 250 g / e q, particularly 95 to 200 g / e q, and particularly preferably 100 to 130 g / e q. If the epoxy equivalent of an epoxy group-containing isocyanurate is less than 90 g / eq, it is difficult to produce commercially. On the other hand, if it exceeds 250 g / eq, the weathering heat resistance effect becomes poor, which is not preferable.
  • Epoxy equivalent is an equivalent per one epoxy group, and is a value determined in accordance with J I S K 7236.
  • the average particle size of the epoxy group-containing isocyanurate used is 1 m to 500 m, especially 1 O rr! ⁇ 300; Um, especially among them! It is preferably ⁇ 200 m.
  • the particle size of the epoxy group-containing isosorbent is smaller than 1 m because the working environment may be deteriorated by the fine powder and the processing may become unstable as the powder fluidity decreases. On the other hand, if it is larger, the dispersibility may be deteriorated and the appearance of the molded product may be deteriorated.
  • Average particle size is the average particle size obtained by the sieving method using standard sieves, etc., and some standard sieves with different mesh sizes (40, 60, 80, 1 1 5, 1 70, 250 mesh) ) Using the sieve passing through that opening The ratio of the excess amount (undersize amount) to the whole is measured, and the value is expressed in terms of the particle size (D 50) at which the total weight percentage is 50%.
  • the amount of the epoxy group-containing isocyanurate is preferably 0.1 to 1 part by weight, preferably 0.1 to 0.5 part by weight, with respect to 100 parts by weight of the vinyl chloride resin. More preferably, it is 0.2 to 0.4 parts by weight.
  • the basic inorganic metal salt can mainly provide a heat stabilizing action to the resin composition.
  • Examples of the metal component of the basic inorganic metal salt include Mg, Ca, Sr, Ba, and the like.
  • examples of the inorganic component include hydroxylation, oxidation, and inorganic acids (phosphoric acid, phosphorous acid, caustic acid, Nitric acid, nitrous acid, sulfuric acid, sulfurous acid, boric acid, carbonic acid, etc.).
  • Mg (H C0 3 ) 2 , B a C0 3 , Mg C0 3 , C a C0 3 , Mg (CO s ) ⁇ C a (CO s ) Species or a combination of two or more may be used.
  • these basic inorganic metal salts one or a combination of two or more selected from the group consisting of a basic inorganic acid magnesium salt, a basic inorganic acid calcium salt, and a basic inorganic acid calcium-magnesium double salt
  • a basic inorganic acid magnesium salt e.g., M g (OH) 2, C a (OH) 2, M g (OH) 2 ⁇ C a (OH) 2, Mg O, C a O, Mg O ⁇ C a 0, M g C0 3 , C a C0 3 , Mg (CO s ) ⁇
  • Mg (CO s ) ⁇
  • the basic inorganic metal salt a surface-treated one can be used.
  • the surface-treated basic inorganic metal salt can further increase the sustained heat stabilization effect as compared with the basic inorganic metal salt that has not been surface-treated.
  • the surface treatment method is not particularly limited.
  • a surface treatment agent is added to a basic inorganic metal salt powder as it is, and a Henschel mixer, a colloid mill, a pole mill, an atomizer, etc.
  • a surface treatment agent and a basic inorganic metal salt in an appropriate solvent such as toluene, xylene, methyl ethyl ketone, acetonitrile, chloroform, jetyl ether, water, ethanol, methanol, and stir. Examples thereof include a method of removing the solvent after mixing.
  • Examples of the surface treatment agent used for the surface treatment of the basic inorganic metal salt include organic acids, organic acid metal salts, and polyhydric alcohol compounds. These compounds may be used alone or as an arbitrary mixture.
  • specific surface treatment agents surface treatment agents composed of these compounds are hereinafter referred to as “specific surface treatment agents”.
  • other surface treatment agents that are usually used industrially are effective for the present invention. As long as it does not inhibit, it may be used together as necessary.
  • Specific examples thereof include silane-based, aluminum-based, and phosphorus-based coupling agents, anionic, cationic, and nonionic surfactants, polymer-based dispersing agents, and the like.
  • the amount of these other surface treatment agents used is that the lead-free vinyl chloride resin composition (for example, a resin composition to which a composite metal stalagmite-based stabilizer is added rather than a lead-based resin) has sufficient sustained heat.
  • the amount used is at least one compound selected from organic acids, organic acid metal salts or polyhydric alcohol compounds (compound as a specific surface treatment agent). It is preferable to make it equal or less.
  • the amount of the specific surface treatment agent used includes the type of basic inorganic metal salt, the specific surface area of the powder particles, the amount of moisture bound to the surface, etc. also it varies depending, in respect basic inorganic metal salt to be surface treated, 0.0 5-4 0 weight 0 / o, preferably from 0.1 to 2 0 weight 0 / o.
  • the amount of the specific surface treatment agent used is less than 0.05% by weight, there is almost no effect of the surface treatment.
  • the surface is saturated with the treatment agent, and the effect of the surface treatment is not further improved.
  • the average particle size of the basic inorganic metal salt is preferably 100 m or less, and more preferably 1 O m or less. If it is larger than 1 OO m, The surface is rough, and physical properties are deteriorated.
  • the blending amount of the basic inorganic metal salt (not including the blending amount of the surface treatment agent) increases the thermal stability more and the weather resistance further increases the weather heat resistance, but too much. Therefore, the amount is preferably from 0.1 to 1 part by weight, more preferably from 0.7 to 0.9 part by weight based on 100 parts by weight of the vinyl chloride resin.
  • a surface-treated basic inorganic metal salt and a non-surface-treated basic inorganic metal salt can be added in combination, and this combined addition stabilizes the vinyl chloride resin composition continuously. The effect can be remarkably improved.
  • titanium oxide used in the vinyl chloride resin composition rutile type titanium dioxide is preferably used, and a commercially available titanium dioxide compound can be used as it is. Surface-treated titanium dioxide can also be used.
  • the average particle diameter of titanium oxide is preferably 0.2 m to 1.0 m.
  • the weathering deterioration can be more effectively suppressed by increasing the blending amount of titanium oxide, and the weather resistance and weathering heat resistance can be further enhanced. Since mold fouling property deteriorates and it is easy to plate out, it is preferably 0.1 to 2 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the vinyl chloride resin. .
  • the composition of the vinyl chloride resin composition is as follows: 0.001 to 1 part by weight of an epoxy group-containing isocyanurate, 0.01 to 1 part by weight of a basic inorganic metal salt with respect to 100 parts by weight of the vinyl chloride resin.
  • the purpose of the present invention excellent thermal stability and good mold contamination resistance, and weather resistance is Lead-free with excellent weathering and heat resistance To obtain a hard vinyl chloride resin composition
  • excellent thermal stability and good mold contamination resistance, and weather resistance is Lead-free with excellent weathering and heat resistance To obtain a hard vinyl chloride resin composition
  • the vinyl chloride resin composition stabilizers, lubricants, impact modifiers, processing aids, fillers, antistatic agents, coloring agents, etc. are added to the vinyl chloride resin composition within an effective and unimpeded range as necessary. It may be added. Furthermore, known resin compounding agents such as ultraviolet absorbers, light stabilizers, perchlorates and the like may be blended according to a known formulation per se.
  • a composite metal stalagmite stabilizer is preferably used.
  • This composite metal stalagmite stabilizer is not particularly limited as long as the metal in the metal stalagmite used in combination is a so-called non-toxic metal stalagmite other than lead and force dome, for example, barium (Ba) / Zinc (Zn), Calcium (Ca) / Zn, Ca / Magnesium (Mg), Ba / Ca / Zn, Ca / Mg / Zn, etc. There is a spider.
  • the acid in the metal sarcophagus is not particularly limited.
  • examples include luranic acid, tyrosinic acid, histidine acid, tryptophan acid, pronic acid, and oxypronic acid.
  • Such a composite metal stalagmite stabilizer is preferably blended in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
  • the composite metal stalagmite stabilizer may be added with a stabilizing aid that exhibits a synergistic action with the composite metal stalagmite stabilizer.
  • the stabilizing aid is not particularly limited as long as it is generally known to be synergistic with the composite metal stalagmite stabilizer.
  • phosphite ester Compounds S_diketone compounds, polyhydric alcohols, hydrotalcite zeolites, antioxidants, and the like. These may be used alone or in combination of two or more.
  • Examples of the lubricant include an internal lubricant and an external lubricant.
  • the internal lubricant is not particularly limited as long as it is used for the purpose of lowering the flow viscosity of the molten resin during molding processing and preventing frictional heat generation.
  • butyl stearate, lauryl alcohol, stearyl alcohol, epoxy Examples include soybean oil, glycerin monostearate, stearic acid, and bisamide. These may be used alone or in combination of two or more.
  • the external lubricant is not particularly limited as long as it is used for the purpose of increasing the sliding effect between the molten resin and the metal surface during molding.
  • paraffin wax, polyolefin wax, ester wax, montanic acid wax And acrylic polymer lubricants may be used alone or in combination of two or more.
  • the impact modifier for example, chlorinated polyethylene containing 30 to 40% of chlorine, acrylic acid ester and / or acrylic acid ester copolymer rubber containing siloxane, methyl methacrylate, styrene, acrylonitrile, etc. And multi-component resins obtained by graft polymerization of these monomers, acrylonitrile butadiene styrene resin, methyl methacrylate butadiene styrene resin, vinyl acetate ethylene copolymer resin, and the like.
  • the processing aid is not particularly limited, and examples thereof include acryl-based processing aids such as alkyl acrylate-alkyl methacrylate copolymers having a weight average molecular weight of 10,000 to 200,000, etc. Specific examples thereof include n-butyl methacrylate-methyl methacrylate copolymer, 2_ethyl hexyl acrylate-methyl methacrylate monobutyl methacrylate copolymer, and the like. These may be used alone or in combination of two or more.
  • acryl-based processing aids such as alkyl acrylate-alkyl methacrylate copolymers having a weight average molecular weight of 10,000 to 200,000, etc. Specific examples thereof include n-butyl methacrylate-methyl methacrylate copolymer, 2_ethyl hexyl acrylate-methyl methacrylate monobutyl methacrylate copolymer, and the like. These may be used alone or in combination of two or more.
  • the filler is not particularly limited, and examples thereof include calcium carbonate and talc. My strength, clay, silica and the like. These may be used alone or in combination of two or more.
  • Power thione compounds such as primary amin salts, tertiary amines, quaternary ammonium compounds, pyridine derivatives,
  • Amphoteric compounds such as carboxylic acid derivatives and imidazoline derivatives are generally usable, but nonionic compounds, especially polyoxyethylene alkylamines or polyoxyethylene alkylamides or fatty acid esters thereof. Fatty acid esters of glycerin and the like are preferable.
  • the colorant is not particularly limited, and examples thereof include organic pigments such as azo-type, phthalocyanine-type, selenium-type, dye lake-type, etc .; Kiichi pump rack, chromic acid molybdenum-type, sulfide ⁇ selenide And inorganic pigments such as phthalocyanine compounds. These may be used alone or in combination of two or more organic pigments such as azo-type, phthalocyanine-type, selenium-type, dye lake-type, etc .; Kiichi pump rack, chromic acid molybdenum-type, sulfide ⁇ selenide And inorganic pigments such as phthalocyanine compounds. These may be used alone or in combination of two or more
  • Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy_4-methoxybenzophenone, and 5,5'-methylenebis (2-hydroxy_4-methoxybenzophene.
  • Non-) 2-hydroxyben Zophenones 2— (2, monohydroxy-5'-methylphenyl) benzotriazol, 2_ (2, monohydroxy-3'- tert-butyl-5'-methylphenyl) 15-clobenzobenzotriazole , 2— (2, monohydroxy 1 5 ′ — tertiary octyl phenyl) benzotriazol, 2_ (2 ′ — hydroxy 3 ′, 5 ′ — dicumyl phenyl) benzotriazol, 2, 2 ′ — methylene bis (4— Tert-octyl-6_benzotriazolyl) 2_ (2′-hydroxyphenyl) benzotriazols such as phenol.
  • Examples of the light stabilizer include 1, 2, 2, 6, 6_pentamethyl _4—piberidyl stearate, 2, 2, 6, 6-tetramethyl _4-piveridyl benzoate, N— (2, 2, 6, 6-tetramethyl _4-piperidyl) dodecylsuccinic acid imide, 1 _ ((3,5-ditertiary butyl 4-hydroxyphenyl) propionyloxychetyl) 1, 2, 2, 6, 6 —Tetramethyl mono 4-piperidyl mono (3,5-ditertiary butyl 4-hydroxyphenyl) propionate, bis (2, 2, 6, 6-tetramethyl _4-piperidyl) Sebacate, tetra (2 , 2, 6, 6-tetramethyl _4-piperidyl) butane tetracarboxylate, tetra (1, 2, 2, 6, 6_pentamethyl _4 —piperidyl) butanetetracarboxylate,
  • hindered amine compounds such as syl) butanetetracarboxylate, bis (1,2,2,6,6_pentamethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate.
  • the perchlorate includes sodium perchlorate, magnesium perchlorate, calcium perchlorate, perchlorate, in addition to perchlorate ion-introduced hydrotalcite and alkali aluminum composite hydroxide salt. Examples include barium acid and zinc perchlorate. In addition, complexes of these perchlorates and polyhydric alcohols can also be used. Preferred polyhydric alcohols include diethylene glycol monomethyl ether, triethylene glycol or propylene glycol monomethyl ether. [0052] The method of mixing the above various additives into the vinyl chloride resin composition is not particularly limited, and examples thereof include a method using hot blending and a method using cold blending.
  • the composite metal stalagmite stabilizer can be used as a one-pack stabilizer in the form of particles (that is, in the form of powder) or in the form of granules.
  • known granulation methods such as extrusion granulation method, spray granulation method, rotary disk granulation method, rolling granulation method, compression granulation method and the like can be used.
  • the particle size of the powder can be arbitrarily adjusted according to the purpose, and it is generally preferable that the particle size is in the range of 50; U m to 5 mm, particularly 70 m to 2 mm.
  • the present vinyl chloride resin composition has good thermal stability, mold contamination resistance, weather resistance, and weathering heat resistance even if it is a hard vinyl chloride resin composition that does not contain plasticity. Therefore, it may be a vinyl chloride resin composition containing a plasticizer. However, the characteristics of the present invention are more effective for a hard vinyl chloride resin composition containing no plasticizer. It is more preferable because it is effective.
  • the use of the present vinyl chloride resin composition is not particularly limited, and is suitable for producing, for example, a molded body, particularly an extrusion molded body. That is, by extruding this vinyl chloride resin composition with an extrusion kneader such as a single screw extruder or a twin screw extruder, an excellent extruded product (hereinafter referred to as “the present extruded product”) is obtained. Can.
  • Such extrusion molding can be carried out using a normal extruder and mold.
  • the molding temperature is preferably 190 to 2100 ° C. If it is less than 90 ° C., various physical properties, particularly impact resistance, of the obtained extruded product are lowered. If it exceeds 2 10 ° C, problems such as the occurrence of decomposition lines in the resulting extruded molded product and inferior long-term moldability may occur.
  • the mold is not particularly limited, and examples thereof include a rod-shaped body, a tubular body, a modified cross-sectional body, a plate-shaped body, a sheet, a film, and the like that can be molded.
  • Weight and heat resistance means the property that the molded body will not discolor when it is heat-processed for a short period of time, such as when it is temporarily stored outdoors. is there.
  • a lead-free hard vinyl chloride resin composition was obtained.
  • Magnesium hydroxide (“Kisuma 5 B” manufactured by Kyowa Chemical Industry Co., Ltd., BET specific surface area 4m2 / g , average particle size (D50) 1m, fatty acid surface treatment),
  • Epoxy group-containing isocyanurate A (“T EP IC—S”, manufactured by Nissan Chemical Industries, Ltd., tris (2,3_epoxypropyl) monoisocyanurate, epoxy equivalent of 100 g / eq, particle size of 160 m, melting point 90 ⁇ (1 25 ° C)
  • Epoxy group-containing isocyanurate B (“T EP IC—G”, manufactured by Nissan Chemical Industries, Ltd., tris-one (2, 3_epoxypropyl) monoisocyanurate, epoxy equivalent 100 g / eq, particle size 360 m, melting point 90-1 (25 ° C)
  • Epoxy group-containing isocyanurate D (manufactured by Nissan Chemical Industries “MT 239", tri (S_methylepoxypropyl) isocyanurate, epoxy equivalent 1 2
  • Epoxy group-containing isocyanurate E (“DA-MG IC” manufactured by Shikoku Kasei Kogyo Co., Ltd., 1,3-diaryl-5_ (2,3_epoxypropane_1_yl) _1,3,5-triazine 4, 6 (1 H, 3 H, 5 H) —trione, epoxy equivalent 270 g / eq)
  • the resulting vinyl chloride resin composition was subjected to a 3 Omm counter-rotating twin screw extruder (Bra Vendor Co., Ltd.) under molding conditions of an extrusion rate of about 20 Kg / h and a mold flow resin temperature of about 205 ° C. "Plasticco 1" made), and the mold was extruded using a slit die having a compressed part with an outlet width of 5 Om m, thickness of 2 mm and gap of 4 mm to 2 mm. Sheet).
  • the kneaded and extruded sheet was heated in an oven at 1 85 ° C for 60 minutes, and the degree of coloring was visually observed and evaluated according to the following criteria.
  • the coloring degree is colorless to light yellow.
  • the coloring degree is yellow to tan.
  • the coloring degree is reddish brown to black.
  • the mold After extruding the vinyl chloride resin composition as described above, the mold was immediately disassembled, and the amount of deposits on the mold surface was visually observed and evaluated according to the following criteria.
  • ⁇ Slightly adhering to a part that tends to adhere, such as part of a corner.
  • the sample was further heated in an oven at 160 ° C for 40 minutes, and the color difference ( ⁇ ) of the heated sample was measured using Minolta's CHRO MA MET ER “CR_200”. did.
  • the degree of color change before and after heating was evaluated according to the following criteria.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 1 0 Example Vinyl chloride resin Vinyl chloride resin 100 100 100 100 100 100 100 100 100 100 100 1 Calcium hydroxide
  • Epoxy group-containing isocyanurate A 0.7 0.1 0.4 0.01 1.0 0.01 1
  • Epoxy group-containing isocyanurate B 0.6
  • Stabilization aid Suaroylpenzomethane 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Trisnonyl phenyl phosphite
  • the epoxy group equivalent of the epoxy group-containing isocyanurate was It is preferably at least less than 2700 g / eq, more preferably 2500 g / eq or less, more preferably 20.0 g / eq or less, and particularly preferably 1300 g / eq or less. It is considered preferable.
  • all of the evaluation items were “O” evaluations. It was found that the smaller the value, the better the effect.
  • the lead-free vinyl chloride resin composition and molded product thereof according to the present invention are subject to thermal degradation (decrease in mechanical properties such as discoloration and elongation, etc.) in hard applications where the use of plasticizer is extremely small or zero. ) And a small amount of deposits on the mold surface during molding. Excellent weather resistance when used outdoors, and excellent resistance to deterioration (weather and heat resistance) during thermal processing after outdoor storage (exposure). Yes.
  • the molded article according to the present invention having such excellent properties is suitable not only for outdoor use but also for secondary processing after outdoor storage, and is preferably used as a pipe, plate, joint, etc. It is something that can be done.

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Abstract

A lead-free vinyl chloride resin composition which combines excellent thermal stability with the property of not fouling molds and has excellent secondary processability after short-term outdoor exposure; and a molded object. The vinyl chloride resin composition is characterized by comprising 100 parts by weight of a vinyl chloride resin and 0.01-1 part by weight of an epoxidized isocyanurate. Due to the introduction of an epoxy group into an isocyanurate, the composition can be satisfactory in the property of not fouling molds (not adhering to molds), weatherability, and heat resistance and can give an extruded object excellent in thermal stability and weatherability.

Description

明 細 書  Specification
非鉛系塩化ビニル系樹脂組成物及び非鉛系塩化ビニル系押出成形体 技術分野  Lead-free vinyl chloride resin composition and lead-free vinyl chloride extrusion molding Technical Field
[0001 ] 本発明は、 熱安定性に優れた押出成形体を作製することができ、 しかも成 形加工時に金型を汚染することのない、 非鉛系塩化ビニル系樹脂組成物、 お よび、 該塩化ビニル系樹脂組成物を押出成形して得られる非鉛系塩化ビニル 系押出成形体に関する。  [0001] The present invention provides a lead-free vinyl chloride resin composition capable of producing an extrusion-molded article having excellent thermal stability and does not contaminate the mold during molding, and The present invention relates to a lead-free vinyl chloride extruded product obtained by extrusion molding of the vinyl chloride resin composition.
背景技術  Background art
[0002] 塩化ビニル系樹脂 （以下、 P V Cと記すこともある） は、 機械的強度、 耐 候性、 耐薬品性に優れているばかりか、 他のプラスチック材料と比較して安 価であることから、 パイプ、 プレート、 継手等の幅広い範囲で利用されてい る。  [0002] Vinyl chloride resin (hereinafter sometimes referred to as PVC) is not only superior in mechanical strength, weather resistance, and chemical resistance, but also is less expensive than other plastic materials. Therefore, it is used in a wide range of pipes, plates, and joints.
[0003] 一般的な塩化ビニル系樹脂は、 熱的に容易に分解するため、 脱塩化水素を 起こして機械強度の低下や着色を起こすという欠点を有している。 そのため 、 従来は鉛化合物などの熱安定化剤を塩化ビニル系樹脂に添加することが行 われていた。 しかし、 近年、 環境問題への関心が高まり、 鉛の毒性が問題に なつており、 無毒性の非鉛系塩化ビニル系樹脂の必要性が高まつている。  [0003] A general vinyl chloride resin is easily decomposed thermally, and thus has a drawback of causing dehydrochlorination to cause a decrease in mechanical strength and coloring. Therefore, conventionally, a heat stabilizer such as a lead compound has been added to the vinyl chloride resin. However, in recent years, interest in environmental issues has increased, lead toxicity has become a problem, and the need for non-toxic non-lead vinyl chloride resins has increased.
[0004] ところが、 鉛系安定剤を添加しない非鉛系塩化ビニル系樹脂組成物は、 鉛 系安定剤を添加した塩化ビニル系樹脂組成物に比べ、 押出成形時に熱劣化し やすい （いわゆる 「熱安定性」 ） ほか、 押出成形品を長期間屋外で使用した 際に劣化しやすい （いわゆる 「耐候性」 ）という課題を抱えていた。  [0004] However, lead-free vinyl chloride resin compositions that do not contain lead-based stabilizers are more susceptible to thermal degradation during extrusion molding than vinyl chloride-based resin compositions that contain lead-based stabilizers (so-called "heat In addition, there was a problem that it was easy to deteriorate when the extruded product was used outdoors for a long time (so-called “weather resistance”).
[0005] そこで、 このような非鉛系塩化ビニル系樹脂組成物の 「熱安定性」 と 「耐 候性」 を改善するため、 次のような提案がなされている。  [0005] Therefore, in order to improve the "thermal stability" and "weather resistance" of such a lead-free vinyl chloride resin composition, the following proposals have been made.
[0006] 例えば、 特許文献 1では、 水酸化カルシウムおよび/または酸化カルシゥ ムと、 ヒドロキシ基含有イソシァヌレートを含む塩化ビニル系樹脂組成物が 提案されている。  [0006] For example, Patent Document 1 proposes a vinyl chloride resin composition containing calcium hydroxide and / or calcium oxide and a hydroxy group-containing isocyanurate.
[0007] また、 特許文献 2では、 有機酸カルシウム塩、 有機酸マグネシウム塩、 有 機亜リン酸エステルとヒドロキシ基含有イソシァヌレートを含む塩化ビニル 系樹脂組成物が提案されている。 [0007] In Patent Document 2, organic acid calcium salt, organic acid magnesium salt, A vinyl chloride resin composition containing an organophosphorous ester and a hydroxy group-containing isocyanurate has been proposed.
[0008] 特許文献 1 ：特表 2 0 0 2 _ 5 1 3 0 6 3公報  [0008] Patent Document 1: Special Table 2 0 0 2 _ 5 1 3 0 6 3
特許文献 2：特開 2 0 0 0 _ 2 7 3 2 5 9公報  Patent Document 2: Japanese Patent Laid-Open No. 2 00 0 _ 2 7 3 2 5 9
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0009] 特許文献 1及び 2に記載された発明はいずれも、 ヒドロキシ基含有イソシ ァヌレートを塩化ビニル系樹脂に添加することを提案するものであり、 これ らの提案によれば、 非鉛系でありながら成形加工時に必要な 「熱安定性」 と 成形後の 「耐候性」 に関して良好な効果が得られることが確かめられている 。 し力、し、 実際に、 ヒドロキシ基含有イソシァヌレートを塩化ビニル系樹脂 に添加した塩化ビニル系樹脂組成物を押出成形してみると、 当該樹脂組成物 が金型に付着して金型を汚したり、 或いは、 得られた押出成形品の耐候耐熱 性が劣るなどの課題があることが明らかになつてきた。  [0009] Both of the inventions described in Patent Documents 1 and 2 propose to add a hydroxy group-containing isocyanurate to a vinyl chloride resin. According to these proposals, Nevertheless, it has been confirmed that good effects can be obtained with regard to “thermal stability” required during molding and “weather resistance” after molding. In fact, when a vinyl chloride resin composition in which a hydroxy group-containing isocyanurate is added to a vinyl chloride resin is extruded, the resin composition adheres to the mold and the mold is soiled. Or, it has become clear that there are problems such as poor weather resistance and heat resistance of the obtained extrusion-molded product.
[0010] そこで本発明の目的は、 以上の諸点を考慮し、 成形加工時における優れた 「熱安定性」 と 「耐金型汚染性」 を兼ね備え、 しかも 「耐候性」 と共に 「耐 候耐熱性」 にも優れた特性を発揮することができる非鉛系の塩化ビニル系樹 脂組成物及び押出成形体を提供することにある。  [0010] In view of the above, the object of the present invention is to combine excellent "thermal stability" and "mold resistance" in molding, and also "weather resistance" together with "weather resistance" It is another object of the present invention to provide a lead-free vinyl chloride resin composition and an extrusion-molded body that can exhibit excellent characteristics.
課題を解決するための手段  Means for solving the problem
[001 1 ] 本発明は、 塩化ビニル系樹脂 1 0 0重量部に対し、 下記一般式で示される 、 エポキシ基を有するイソシァヌレートを 0 . 0 1〜 1重量部含むことを特 徵とする非鉛系塩化ビニル系樹脂組成物を提案する。 [化 1 ] o [001 1] The present invention is a non-lead characterized by containing 0.001 to 1 part by weight of an isocyanurate having an epoxy group represented by the following general formula with respect to 100 parts by weight of a vinyl chloride resin. A vinyl chloride resin composition is proposed. [Chemical 1] o
II  II
3ヽ Nz -Ki 3ヽN z- K i
°丄、 N z ° 丄, N z
R2 R 2
(但し、 式中 F^、 2及び 3は、 それぞれ官能基 （Hを含む） を示し、 且つ 、 少なくともそのうちの一つはエポキシ基を有する官能基である。 ） (In the formula, F ^, 2 and 3 each represent a functional group (including H), and at least one of them is a functional group having an epoxy group.)
[0012] 本発明はまた、 本発明の非鉛系塩化ビニル系樹脂組成物を押出成形して得 られる非鉛系塩化ビニル系押出成形体を提案する。  [0012] The present invention also proposes a lead-free vinyl chloride extruded product obtained by extrusion molding of the lead-free vinyl chloride resin composition of the present invention.
[0013] エポキシ基を有するイソシァヌレートは、 前述の特許文献 1及び 2におい て提案されている 「ヒドロキシ基含有イソシァヌレート」 と比較すると、 ヒ ドロキシ基の代わりにエポキシ基を導入したイソシァヌレートである。 本発 明者は、 イソシァヌレートにエポキシ基を導入することにより、 熱安定性及 び耐候性を維持しつつ、 金型汚染性 （金型付着性） および耐候耐熱性をいず れも良好なものとすることができることを見出し、 かかる知見に基づき、 本 発明を想到したものである。  The isocyanurate having an epoxy group is an isocyanurate in which an epoxy group is introduced in place of a hydroxyl group, as compared with the “hydroxy group-containing isocyanurate” proposed in Patent Documents 1 and 2 described above. By introducing an epoxy group into the isocyanurate, the present inventor maintains both thermal stability and weather resistance, and has good mold contamination (mold adhesion) and weather resistance. The present invention has been conceived based on this finding.
発明の効果  The invention's effect
[0014] 本発明の非鉛系塩化ビニル系樹脂組成物及びその押出成形体は、 鉛化合物 を含まないにもかかわらず、 優れた熱安定性を有し、 金型汚染防止性が良好 であると共に、 耐候性に優れるばかりでなく、 屋外保管 （暴露） 後の熱加工 時における耐劣化 （耐候耐熱性） についても優れている。  [0014] The lead-free vinyl chloride resin composition and the extrusion-molded product thereof according to the present invention have excellent thermal stability and good anti-mold contamination property, despite containing no lead compound. In addition to being excellent in weather resistance, it is also excellent in deterioration resistance (weather and heat resistance) during thermal processing after outdoor storage (exposure).
このような優れた諸特性を有する本発明の樹脂組成物による成形体は、 パ イブ、 プレート、 継手等の素材、 特に屋外使用される素材や屋外保管後に 2 次加工される素材として好適である。  The molded body of the resin composition of the present invention having such excellent characteristics is suitable as a material for pipes, plates, joints, etc., particularly as a material for outdoor use or a material processed secondary after outdoor storage. .
発明を実施するための最良の形態 [0015] 以下に本発明の実施形態について詳細に述べるが、 本発明の範囲が以下に 説明する実施形態に限定されるものではない。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail, but the scope of the present invention is not limited to the embodiments described below.
[0016] 本実施形態の一例として説明する塩化ビニル系樹脂組成物 （以下、 「本塩 化ビニル系樹脂組成物」 という） は、 塩化ビニル系樹脂 1 0 0重量部に対し 、 エポキシ基を有するイソシァヌレート （ 「エポキシ基含有イソシァヌレ一 ト」 とも称する） 0 . 0 1〜 1重量部を含み、 必要に応じて、 塩基性無機金 属塩 0 . 0 1〜 1重量部を、 さらに必要に応じて酸化チタン 0 . 0 1〜2重 量部を含む塩化ビニル系樹脂組成物である。  [0016] The vinyl chloride resin composition (hereinafter referred to as "the present vinyl chloride resin composition") described as an example of this embodiment has an epoxy group with respect to 100 parts by weight of the vinyl chloride resin. Isocyanurate (also referred to as “epoxy group-containing isocyanurate”) 0.1 to 1 part by weight, if necessary, basic inorganic metal salt 0.0 1 to 1 part by weight, further if necessary Titanium oxide A vinyl chloride resin composition containing 0.01 to 2 parts by weight.
[0017] (塩化ビニル系樹脂）  [0017] (vinyl chloride resin)
本塩化ビニル系樹脂組成物に用いる塩化ビニル系樹脂としては、 特に限定 されず、 J I S K 6 7 2 1に準拠した平均重合度が 6 0 0〜2 0 0 0の範 囲のもの、 中でも平均重合度が 7 0 0〜 1 4 5 0の範囲のもの、 その中でも 特に平均重合度が 8 0 0〜 1 3 0 0の範囲のものを好適に用いることができ る。  The vinyl chloride resin used in the present vinyl chloride resin composition is not particularly limited, and the average polymerization degree in accordance with JISK 6 72 1 is in the range of 600 to 200, particularly average polymerization. Those having a degree in the range of 700 to 1450, particularly those having an average degree of polymerization in the range of 80 to 1300 can be suitably used.
[0018] この塩化ビニル系樹脂は、 単独重合体であるポリ塩化ビニル樹脂でもよい し、 また、 塩化ビニルと共重合し得る他のモノマーとを共重合させたポリ塩 化ビニル系共重合体でもよい。 その際、 塩化ビニルの共重合単量体成分 （モ ノマ一） についても、 特に限定されず、 例えば、 酢酸ビニル、 プロピオン酸 ビニル等のビニルエステル、 アクリル酸メチル、 アクリル酸ェチル等のァク リル酸エステルもしくはメタクリル酸エステル、 エチレン、 プロピレン等の ォレフィン、 無水マレイン酸、 アクリロニトリル、 スチレン、 塩化ビニリデ ン等が挙げられ、 これらの 1種であっても、 これらのうちの 2種以上を組み 合わせて併用してもよい。  [0018] This vinyl chloride resin may be a polyvinyl chloride resin that is a homopolymer, or may be a polyvinyl chloride copolymer obtained by copolymerization with another monomer that can be copolymerized with vinyl chloride. Good. At that time, the copolymerization monomer component (monomer) of vinyl chloride is not particularly limited. For example, vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, and ethyl acrylate. Examples include acid esters or methacrylate esters, ethylene, propylene and other olefins, maleic anhydride, acrylonitrile, styrene, vinylidene chloride, and the like, even if one of these is combined. You may use together.
[0019] なお、 塩化ビニルモノマーを重合させただけの単独重合体は、 硬くて脆く 、 紫外線などにあたると劣化黄変しやすいため、 可塑剤や光劣化を防ぐ安定 剤を加えることがある。 本塩化ビニル系樹脂組成物の場合には、 可塑剤や安 定剤を加えることは任意であるが、 可塑剤を全く或いはほとんど含有しない (濃度 5質量％程度未満） 場合であっても、 本発明の効果を得ることができ る点も特徴の一つである。 [0019] A homopolymer obtained by polymerizing a vinyl chloride monomer is hard and brittle, and easily deteriorates and yellows when exposed to ultraviolet rays. Therefore, a plasticizer or a stabilizer that prevents photodegradation may be added. In the case of the present vinyl chloride resin composition, it is optional to add a plasticizer or a stabilizer, but even if it contains no or little plasticizer (concentration of less than about 5% by mass), The effect of the invention can be obtained This is another feature.
(エポキシ基含有ィソシァヌレート）  (Epoxy group-containing isocyanurate)
本塩化ビニル系樹脂組成物に用いるエポキシ基含有イソシァヌレートは、 下記の一般式で表すことができる。  The epoxy group-containing isocyanurate used in the vinyl chloride resin composition can be represented by the following general formula.
[0021 ] [化 1 ]  [0021] [Chemical 1]
Figure imgf000006_0001
Figure imgf000006_0001
R2 R 2
[0022] 式中、 R 2および R 3は、 それぞれ官能基 （Hを含む） を示すものであ り、 少なくともそのうちの一つはエポキシ基を有する官能基である。 In the formula, R 2 and R 3 each represent a functional group (including H), and at least one of them is a functional group having an epoxy group.
エポキシ基を有する官能基の好ましい具体例としては、 例えば 2 , 3 _ェポ キシプロピル基、 3 , 4 _エポキシブチル基などのエポキシアルキル基、 β —メチルエポキシプロピル基、 S—ェチルエポキシプロピル基などのアルキ ルエポキシアルキル基、 カルポキシメチル■グリシジルエステル基、 力ルポ キシメチル■ yS—メチルグリシジルエステル基、 カルポキシェチル■グリシ ジルエステル基などのカルポキシアルキル■アルキルグリシジルエステル基 を挙げることができる。  Preferable specific examples of the functional group having an epoxy group include epoxy alkyl groups such as 2,3_epoxypropyl group, 3,4_epoxybutyl group, β-methylepoxypropyl group, S-ethylepoxypropyl group, etc. And alkyloxyalkyl glycidyl ester groups such as alkylepoxyalkyl groups such as carboxymethyl glycidyl ester groups, strong methoxymethyl yS-methyl glycidyl ester groups, and carboxyxyl glycidyl ester groups.
また、 他の官能基の具体例としては、 例えば水素原子、 炭素数 1〜1 2のァ ルキル基、 フヱ二ル基、 ヒドロキシル基、 ヒドロキシアルキル基、 エステル 基、 力ルポキシル基、 不飽和炭化水素基、 シァノ基、 メルカプト基、 アルコ キシ基、 アミノ基、 ジシクロアルキルアミノ基および N—アルキル—N—ァ リールアミノ基、 その他芳香族炭化水素基やハロゲン原子を構造中に含む基 などを挙げることができる。  Specific examples of other functional groups include, for example, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a vinyl group, a hydroxyl group, a hydroxyalkyl group, an ester group, a strong loxyl group, and an unsaturated carbonization. Hydrogen group, cyano group, mercapto group, alkoxy group, amino group, dicycloalkylamino group and N-alkyl-N-arylamino group, other groups containing aromatic hydrocarbon groups or halogen atoms in the structure, etc. Can be mentioned.
[0023] エポキシ基含有ィソシァヌレ一卜の適当な例としては、 例えばモノ （2 , 3 _エポキシプロピル） イソシァヌレート、 ビス （2 , 3 _エポキシプロピ ル） イソシァヌレート、 トリス （2, 3 _エポキシプロピル） イソシァヌレ —ト、 トリス （3, 4 _エポキシプチル） イソシァヌレート、 トリ （;3—メ チルエポキシプロピル） ィソシァヌレート、 トリ （カルポキシメチル■ィソ シァヌレートトリグリシジルエステル （TCM I CTG) 、 トリ （カルポキ シェチル■イソシァヌレートトリグリシジルエステル （TCE I CTG) 、 トリ （カルポキシメチル■ィソシァヌレートトリ ySメチルグリシジルエステ ル （T CM I C S _M e T G) 等が挙げられる。 中でも、 トリス （2, 3 - エポキシプロピル） ィソシァヌレートが耐候耐熱性や金型汚染性を考慮する うえで好ましい。 [0023] Suitable examples of the epoxy group-containing isocyanurate include mono (2,3_epoxypropyl) isocyanurate, bis (2,3_epoxypropylene), and the like. Isocyanurate, tris (2,3_epoxypropyl) isocyanurate, tris (3,4_epoxyptyl) isocyanurate, tri (; 3-methylepoxypropyl) isocyanurate, tri Triglycidyl ester (TCM I CTG), Tri (Carboxychetyl ■ Isocyanurate triglycidyl ester (TCE I CTG), Tri (Carpoxymethyl ■ Isosianulate tri yS methyl glycidyl ester (T CM ICS _MeTG) Among them, tris (2,3-epoxypropyl) isocynanurate is preferable in view of weather resistance and mold contamination.
[0024] 用いるエポキシ基含有イソシァヌレートは、 エポキシ当量が 90〜250 g/e q、 中でも 95〜200 g/e q、 その中でも特に 1 00〜 1 30 g /e qであるエポキシ基含有ィソシァヌレー卜が好ましい。 エポキシ基含有 ィソシァヌレー卜のエポキシ当量が 90 g/e qより少ないと商業的に生産 することが困難となる。 その一方、 250 g/e qを超えると耐候耐熱効果 が乏しくなるため、 好ましくない。  The epoxy group-containing isocyanurate to be used is preferably an epoxy group-containing isocyanurate having an epoxy equivalent of 90 to 250 g / e q, particularly 95 to 200 g / e q, and particularly preferably 100 to 130 g / e q. If the epoxy equivalent of an epoxy group-containing isocyanurate is less than 90 g / eq, it is difficult to produce commercially. On the other hand, if it exceeds 250 g / eq, the weathering heat resistance effect becomes poor, which is not preferable.
「エポキシ当量」 は、 エポキシ基 1個あたりの当量であり、 J I S K 7236に準拠して求められる値である。  “Epoxy equivalent” is an equivalent per one epoxy group, and is a value determined in accordance with J I S K 7236.
[0025] また、 用いるエポキシ基含有イソシァヌレートの平均粒径は、 1 m〜5 00 m、 中でも 1 O rr！〜 300;Um、 その中でも特に ！〜 200 mであるのが好ましい。 用いるエポキシ基含有イソシァヌレー卜の平均粒 径が小さいほど少量で効果を発揮することができる。 但し、 エポキシ基含有 ィソシァヌレ一卜の粒径が 1 mより小さくなると、 微粉による作業環境の 悪化と共に粉体流動性の低下に伴って加工が安定しなくなる可能性があるの で好ましくない。 また、 より大きくなると、 分散性が悪化して成 形品の外観を低下させる可能性があるので好ましくない。  [0025] The average particle size of the epoxy group-containing isocyanurate used is 1 m to 500 m, especially 1 O rr! ~ 300; Um, especially among them! It is preferably ~ 200 m. The smaller the average particle size of the epoxy group-containing isocyanurate used, the more effective it is. However, it is not preferable that the particle size of the epoxy group-containing isosorbent is smaller than 1 m because the working environment may be deteriorated by the fine powder and the processing may become unstable as the powder fluidity decreases. On the other hand, if it is larger, the dispersibility may be deteriorated and the appearance of the molded product may be deteriorated.
「平均粒径」 は、 標準ふるいなどを用いたふるいわけ法により求められる 平均粒径であり、 目開きの異なるいくつかの標準ふるい （40, 60, 80, 1 1 5, 1 70, 250メッシュ） を用いて 、 その目開きを通過したふるい下通 過量 （アンダーサイズ量） の全体に対する比率を測定し、 積算■重量百分率 が 50%となる粒度 （D 50) で表した値である。 “Average particle size” is the average particle size obtained by the sieving method using standard sieves, etc., and some standard sieves with different mesh sizes (40, 60, 80, 1 1 5, 1 70, 250 mesh) ) Using the sieve passing through that opening The ratio of the excess amount (undersize amount) to the whole is measured, and the value is expressed in terms of the particle size (D 50) at which the total weight percentage is 50%.
[0026] 本塩化ビニル系樹脂組成物では、 エポキシ基含有ィソシァヌレー卜の配合 量が少なすぎると耐候耐熱性が低下する傾向があり、 多すぎると押出安定性 や金型汚染性が悪化するため、 エポキシ基含有ィソシァヌレー卜の配合量は 、 塩化ビニル系樹脂 1 00重量部に対し、 0. 0 1〜 1重量部とするのが重 要であり、 好ましくは 0. 1〜0. 5重量部、 さらに好ましくは 0. 2〜0 . 4重量部である。  [0026] In the present vinyl chloride resin composition, if the amount of the epoxy group-containing isocyanurate is too small, the weathering heat resistance tends to decrease, and if it is too large, the extrusion stability and mold contamination are deteriorated. The amount of the epoxy group-containing isocyanurate is preferably 0.1 to 1 part by weight, preferably 0.1 to 0.5 part by weight, with respect to 100 parts by weight of the vinyl chloride resin. More preferably, it is 0.2 to 0.4 parts by weight.
[0027] (塩基性無機金属塩）  [0027] (Basic inorganic metal salt)
本塩化ビニル系樹脂組成物において、 塩基性無機金属塩は、 樹脂組成物に 主に熱安定化作用をもたらすことができる。  In the present vinyl chloride resin composition, the basic inorganic metal salt can mainly provide a heat stabilizing action to the resin composition.
この塩基性無機金属塩の金属成分としては、 Mg、 C a、 S r、 B a等が 挙げられ、 無機成分としては、 水酸化、 酸化、 無機酸 （リン酸、 亜リン酸、 ケィ酸、 硝酸、 亜硝酸、 硫酸、 亜硫酸、 ホウ酸、 炭酸など） の塩が挙げられ る。  Examples of the metal component of the basic inorganic metal salt include Mg, Ca, Sr, Ba, and the like. Examples of the inorganic component include hydroxylation, oxidation, and inorganic acids (phosphoric acid, phosphorous acid, caustic acid, Nitric acid, nitrous acid, sulfuric acid, sulfurous acid, boric acid, carbonic acid, etc.).
[0028] 具体的には、  [0028] Specifically,
1 ) 金属水酸化物として、 Mg (OH)2、 C a (OH)2、 B a (OH)2、 M g (O H)2■ C a (O H)2など 1) As metal hydroxide, Mg (OH) 2 , C a (OH) 2 , B a (OH) 2 , Mg (OH) 2 ■ C a (OH) 2 etc.
2) 金属酸化物として、 Mg O、 C a O、 B a O、 Mg O ' C a Oなど 2) As metal oxides, MgO, CaO, BaO, MgO'CaO, etc.
3) 無機酸の塩として、 Mg O ■ Mg3(P04)2、 3 C a O ■ C a3(P04)2、 C a (O H)2■ C a3(P 04)2、 B a (O H ) 2■ C a 3 ( P 04) 2■ 3 H20、 S r (O H)2 ■ S r3(P04)2、 B a O ■ B a3(P 04)2、 3 B a (OH) - B a3(P04)2など のリン酸塩、 3) Mg O ■ Mg 3 (P0 4 ) 2 , 3 C a O ■ C a 3 (P0 4 ) 2 , C a (OH) 2 ■ C a 3 (P 0 4 ) 2 , B a (OH) 2 ■ C a 3 (P 0 4 ) 2 ■ 3 H 2 0, S r (OH) 2 ■ S r 3 (P0 4 ) 2 , B a O ■ B a 3 (P 0 4 ) 2 , 3 B a (OH)-B a 3 (P0 4 ) 2 and other phosphates,
Mg O - Mg P H03、 5M g (O H)2■ (2) M g P H 03、 C a O ■ C a P H 03、 3 C a O (O H)2C a P H 03、 B a (O H ) 2■ C a P H 03、 5 C a O ■ C a P H03、 B a O ' B a P H03、 2 B a (O H ) 2■ B a P H 03、 3 B a (O H )2■ B a P H 03■ 3 H20などの亜リン酸塩、 Mg O-Mg P H0 3 , 5M g (OH) 2 ∎ (2) Mg PH 0 3 , C a O ■ C a PH 0 3 , 3 C a O (OH) 2 C a PH 0 3 , B a (OH) 2 ■ C a PH 0 3 , 5 C a O ■ C a P H0 3 , B a O 'B a P H0 3 , 2 B a (OH) 2 ■ B a PH 0 3 , 3 B a ( OH) 2 ■ B a PH 0 3 ■ 3 H 2 0 and other phosphites
M g (O H)2■ M g2S i 04、 3 M g O ■ M g S i 03、 C a O ■ C a2S i 04 、 3 C a O ■ L i 2S i 03 3 C a O ■ C a S i 205、 2 C a (O H)2■ C a2S i 308、 S r O ■ S r S i 03、 5 B a O ■ B a 2 S i 04、 B a (O H)2■ B a2 S i 04■ 6 H20、 B a (O H)2■ B a S i 03、 3 B a (OH) ■ B a S i 205 、 3 B a O . B a2S i 04、 B a (O H)2■ C a S i Oなどのケィ酸塩、 M g (OH) 2 ■ M g 2 S i 0 4 , 3 M g O ■ M g S i 0 3 , C a O ■ C a 2 S i 0 4 , 3 C a O ■ L i 2 S i 0 3 3 C a O ■ C a S i 2 0 5 , 2 C a (OH) 2 ■ C a 2 S i 3 0 8 , S r O ■ S r S i 0 3 , 5 B a O ■ B a 2 S i 0 4 , B a (OH) 2 ■ B a 2 S i 0 4 ■ 6 H 2 0, B a (OH) 2 ■ B a S i 0 3 , 3 B a (OH) ■ B a S i 20 5 , 3 B a O. B a 2 S i 0 4 , B a (OH) 2 ■ C a S i O
M g (OH) ■ M g (N 03)2 (3) 、 3 C a O ■ C a (N 03)2、 2 C a (O H )2■ C a (N 02)2■ 5 H20、 3 B a O ■ B a ( N 03) 2、 B a (O H)2■ N a N 03 などの硝酸塩及び亜硝酸塩、 M g (OH) ■ M g (N 0 3 ) 2 (3), 3 C a O ■ C a (N 0 3 ) 2 , 2 C a (OH) 2 ■ C a (N 0 2 ) 2 ■ 5 H 2 0, 3 B a O ∎ B a (N 0 3 ) 2 , B a (OH) 2 ∎ Nitrate and nitrite such as N a N 0 3 ,
3 C a O ■ K2S 03、 M g (O H)2■ M g S 04、 5 M g O ■ M g S 03、 2 M g O ■ M g S 03、 M g O ■ C a S 03、 5 C a O ■ C a S 04、 C a (O H)2■ C a S04、 3 C a O - C a S 03 3 B a O ■ B a S 04 3 B a O - C a SO 3、 B a (O H)2■ B a S 04などの硫酸塩及び亜硫酸塩、 3 C a O ■ K 2 S 0 3 , Mg (OH) 2 ■ Mg S 0 4 , 5 Mg O ■ Mg S 0 3 , 2 Mg O ■ Mg S 0 3 , Mg O ■ C a S 0 3 , 5 C a O ■ C a S 0 4 , C a (OH) 2 ■ C a S0 4 , 3 C a O-C a S 0 3 3 B a O ■ B a S 0 4 3 B a O-C a SO 3, B a (OH) 2 ■ Sulfates and sulfites such as B a S 0 4 ,
M g O ■ M g3 (B04)2、 C a O ■ (B04)2、 5 C a (O H ) 2■ C a 3 ( B 04) 2 、 3 C a O ■ C a (B02)2、 3 B a (O H)2■ B a3 ( B 04)2 3 B a O ■ B a B4 H7、 5 B a (O H)2■ B a ( B 02) 2などのホウ酸塩、 Mg (H C03)2、 B a C03、 Mg C03、 C a C03、 Mg (COs) ■ C a (COs) などの炭酸 塩が挙げられ、 これらは 1種又は 2種以上を組み合わせて用いても良い。 M g O ■ M g 3 (B0 4 ) 2 , C a O ■ (B0 4 ) 2 , 5 Ca (OH) 2 ■ C a 3 (B 0 4 ) 2, 3 C a O ■ C a (B0 2 ) 2 , 3 B a (OH) 2 ■ B a 3 (B 0 4 ) 2 3 B a O ■ B a B 4 H 7 , 5 B a (OH) 2 ■ B a (B 0 2 ) 2 etc. Borate, Mg (H C0 3 ) 2 , B a C0 3 , Mg C0 3 , C a C0 3 , Mg (CO s ) ■ C a (CO s ) Species or a combination of two or more may be used.
[0029] これら塩基性無機金属塩の中でも、 塩基性無機酸マグネシウム塩、 塩基性 無機酸カルシウム塩、 塩基性無機酸カルシウム—マグネシウム複塩からなる 群から選ばれる 1種又は 2種以上の組み合わせであり、 より好ましくは、 M g (OH)2、 C a (OH)2、 M g (O H)2■ C a (O H)2、 Mg O、 C a O、 Mg O ■ C a 0、 M g C03、 C a C03、 M g (COs) ■ C a (COs) から選ば れる 1種又は 2種以上の組み合わせである。 [0029] Among these basic inorganic metal salts, one or a combination of two or more selected from the group consisting of a basic inorganic acid magnesium salt, a basic inorganic acid calcium salt, and a basic inorganic acid calcium-magnesium double salt There, more preferably, M g (OH) 2, C a (OH) 2, M g (OH) 2 ■ C a (OH) 2, Mg O, C a O, Mg O ■ C a 0, M g C0 3 , C a C0 3 , Mg (CO s ) ■ One or a combination of two or more selected from C a (CO s ).
[0030] 塩基性無機金属塩は、 表面処理されたものを用いることもできる。 表面処 理された塩基性無機金属塩は、 表面処理をしていない塩基性無機金属塩と比 較して、 その持続熱安定化効果を更に増大することができる。  [0030] As the basic inorganic metal salt, a surface-treated one can be used. The surface-treated basic inorganic metal salt can further increase the sustained heat stabilization effect as compared with the basic inorganic metal salt that has not been surface-treated.
[0031] かかる表面処理の方法としては特別な制限はなく、 例えば、 （1 ) 塩基性 の無機金属塩の粉体に表面処理剤をそのまま添加してヘンシェルミキサー、 コロイ ドミル、 ポールミル、 アトマイザ一等の粉砕機を用いて共粉砕する方 法、 （2 ) トルエン、 キシレン、 メチルェチルケトン、 ァセトニトリル、 ク ロロホルム、 ジェチルェ一テル、 水、 エタノール、 メタノール等の適当な溶 媒中に表面処理剤と塩基性無機金属塩とを加え、 撹拌混合後、 溶媒を除去す る方法、 等を挙げることができる。 [0031] The surface treatment method is not particularly limited. For example, (1) a surface treatment agent is added to a basic inorganic metal salt powder as it is, and a Henschel mixer, a colloid mill, a pole mill, an atomizer, etc. To co-grind using other crushers (2) Add a surface treatment agent and a basic inorganic metal salt in an appropriate solvent such as toluene, xylene, methyl ethyl ketone, acetonitrile, chloroform, jetyl ether, water, ethanol, methanol, and stir. Examples thereof include a method of removing the solvent after mixing.
[0032] 塩基性無機金属塩の表面処理に用いる表面処理剤としては、 有機酸、 有機 酸金属塩、 多価アルコール化合物が挙げられる。 これらの化合物は各々単独 で用いてもよく、 任意の混合物として用いてもよい。  [0032] Examples of the surface treatment agent used for the surface treatment of the basic inorganic metal salt include organic acids, organic acid metal salts, and polyhydric alcohol compounds. These compounds may be used alone or as an arbitrary mixture.
また、 上記化合物 （これらの化合物からなる表面処理剤を、 以下、 「特定の 表面処理剤」 と記す） 以外に、 工業的に通常使用されている他の表面処理剤 を、 本発明の効果を阻害しない範囲で、 必要に応じ適宜に併用してもよい。 その具体例としては、 シラン系、 アルミニウム系、 リン系等のカップリング 剤や、 ァニオン系、 カチオン系、 ノニオン系等の界面活性剤、 高分子系の分 散剤等を挙げることができる。 但し、 これら他の表面処理剤の使用量は、 非 鉛系塩化ビニル系樹脂組成物 （例えば、 鉛系ではなく複合金属石鹼系の安定 剤が添加された樹脂組成物） が十分な持続熱安定化効果を得るためには、 有 機酸、 有機酸金属塩または多価アルコール化合物から選ばれる少なくとも一 種の化合物 （特定の表面処理剤としての化合物） の使用量に対して、 多くと も同量以下にすることが好ましい。  In addition to the above-mentioned compounds (surface treatment agents composed of these compounds are hereinafter referred to as “specific surface treatment agents”), other surface treatment agents that are usually used industrially are effective for the present invention. As long as it does not inhibit, it may be used together as necessary. Specific examples thereof include silane-based, aluminum-based, and phosphorus-based coupling agents, anionic, cationic, and nonionic surfactants, polymer-based dispersing agents, and the like. However, the amount of these other surface treatment agents used is that the lead-free vinyl chloride resin composition (for example, a resin composition to which a composite metal stalagmite-based stabilizer is added rather than a lead-based resin) has sufficient sustained heat. In order to obtain a stabilizing effect, at most, the amount used is at least one compound selected from organic acids, organic acid metal salts or polyhydric alcohol compounds (compound as a specific surface treatment agent). It is preferable to make it equal or less.
[0033] 特定の表面処理剤の使用量は、 適宜併用される他の表面処理剤も含めて、 塩基性無機金属塩の種類、 その粉体粒子の比表面積及びその表面に結合した 水分量等によっても異なるが、 表面処理されるべき塩基性無機金属塩に対し て、 0 . 0 5〜4 0重量0 /o、 好ましくは、 0 . 1〜2 0重量0 /oである。 [0033] The amount of the specific surface treatment agent used, including other surface treatment agents used as appropriate, includes the type of basic inorganic metal salt, the specific surface area of the powder particles, the amount of moisture bound to the surface, etc. also it varies depending, in respect basic inorganic metal salt to be surface treated, 0.0 5-4 0 weight 0 / o, preferably from 0.1 to 2 0 weight 0 / o.
特定の表面処理剤の使用量が 0 . 0 5重量％未満では表面処理の効果がほ とんどなく、 一方、 4 0重量％より多く使用しても、 塩基性無機金属塩の粉 体粒子の表面が処理剤で飽和してしまい、 表面処理の効果はそれ以上向上し ない。  When the amount of the specific surface treatment agent used is less than 0.05% by weight, there is almost no effect of the surface treatment. The surface is saturated with the treatment agent, and the effect of the surface treatment is not further improved.
[0034] 塩基性無機金属塩の平均粒径は、 1 0 0 m以下が好ましく、 更に好まし くは 1 O m以下である。 1 O O mより大きいと、 成形加工後の加工品の 表面がざらつき、 物理的特性の低下が起こり好ましくない。 [0034] The average particle size of the basic inorganic metal salt is preferably 100 m or less, and more preferably 1 O m or less. If it is larger than 1 OO m, The surface is rough, and physical properties are deteriorated.
[0035] 塩基性無機金属塩の配合量 （表面処理剤の配合量を含めない） は、 多くす れば熱安定性がより一層高まり、 耐候性ゃ耐候耐熱性がより一層高まる反面 、 多過ぎると金型汚染性が悪化するため、 塩化ビニル系樹脂 1 0 0重量部に 対し 0 . 0 1〜 1重量部が好ましく、 より好ましくは 0 . 7〜0 . 9重量部 である。  [0035] The blending amount of the basic inorganic metal salt (not including the blending amount of the surface treatment agent) increases the thermal stability more and the weather resistance further increases the weather heat resistance, but too much. Therefore, the amount is preferably from 0.1 to 1 part by weight, more preferably from 0.7 to 0.9 part by weight based on 100 parts by weight of the vinyl chloride resin.
また、 表面処理された塩基性無機金属塩と表面処理されていない塩基性無 機金属塩とを併用添加することもでき、 この併用添加によって当該塩化ビ二 ル系樹脂組成物の持続熱安定化効果を著しく向上させることができる。  In addition, a surface-treated basic inorganic metal salt and a non-surface-treated basic inorganic metal salt can be added in combination, and this combined addition stabilizes the vinyl chloride resin composition continuously. The effect can be remarkably improved.
[0036] (酸化チタン） [0036] (Titanium oxide)
本塩化ビニル系樹脂組成物に用いる酸化チタンとしては、 ルチル型二酸化 チタンを使用するのが好ましく、 通常市販されている二酸化チタン化合物を そのまま使用することができる。 また、 表面処理された二酸化チタンも使用 できる。  As the titanium oxide used in the vinyl chloride resin composition, rutile type titanium dioxide is preferably used, and a commercially available titanium dioxide compound can be used as it is. Surface-treated titanium dioxide can also be used.
酸化チタンの平均粒径は 0 . 2 m〜 1 . 0 mであるのが好ましい。  The average particle diameter of titanium oxide is preferably 0.2 m to 1.0 m.
[0037] 酸化チタンの配合量は、 酸化チタンの配合量を多くすれば、 耐候劣化をよ り有効に抑えることができ、 耐候性及び耐候耐熱性をより一層高めることが できる反面、 多過ぎると金型汚染性が悪化しプレートァゥトし易くなるので 、 塩化ビニル系樹脂 1 0 0重量部に対し 0 . 0 1〜 2重量部が好ましく、 よ り好ましくは 0 . 0 1〜 1重量部である。 [0037] If the blending amount of titanium oxide is increased, the weathering deterioration can be more effectively suppressed by increasing the blending amount of titanium oxide, and the weather resistance and weathering heat resistance can be further enhanced. Since mold fouling property deteriorates and it is easy to plate out, it is preferably 0.1 to 2 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the vinyl chloride resin. .
[0038] (組成） [0038] (Composition)
本塩化ビニル系樹脂組成物の組成としては、 塩化ビニル系樹脂 1 0 0重量 部に対し、 エポキシ基含有イソシァヌレート 0 . 0 1〜 1重量部、 塩基性無 機金属塩 0 . 0 1〜 1重量部、 酸化チタン 0 . 0 1〜2重量部を含んでなる ことが特に好ましい。  The composition of the vinyl chloride resin composition is as follows: 0.001 to 1 part by weight of an epoxy group-containing isocyanurate, 0.01 to 1 part by weight of a basic inorganic metal salt with respect to 100 parts by weight of the vinyl chloride resin. In particular, it is particularly preferable to contain 0.01 to 2 parts by weight of titanium oxide.
これら各化合物を、 このような特定の配合比率 （特に酸化チタン添加量が 少ない系） で組み合わせる場合において、 本発明の目的 （熱安定性が優れる と共に耐金型汚染性が良好で、 耐候性はもとより耐候耐熱性が優れた非鉛系 硬質塩化ビニル系樹脂組成物を得ること） をより良好に達成することができ る。 In the case where these compounds are combined at such a specific mixing ratio (particularly a system with a small amount of added titanium oxide), the purpose of the present invention (excellent thermal stability and good mold contamination resistance, and weather resistance is Lead-free with excellent weathering and heat resistance To obtain a hard vinyl chloride resin composition) can be achieved more satisfactorily.
[0039] (その他の含有可能な成分）  [0039] (Other components that can be contained)
本塩化ビニル系樹脂組成物には、 必要に応じて、 安定剤、 滑剤、 衝撃改良 剤、 加工助剤、 充填剤、 帯電防止剤、 着色剤等を、 効果的かつ支障とならな い範囲で添加してもよい。 さらに、 紫外線吸収剤、 光安定剤、 過塩素酸塩等 の公知の樹脂配合剤を、 それ自体公知の処方に従って配合してもよい。  In this vinyl chloride resin composition, stabilizers, lubricants, impact modifiers, processing aids, fillers, antistatic agents, coloring agents, etc. are added to the vinyl chloride resin composition within an effective and unimpeded range as necessary. It may be added. Furthermore, known resin compounding agents such as ultraviolet absorbers, light stabilizers, perchlorates and the like may be blended according to a known formulation per se.
[0040] 安定剤としては、 複合金属石鹼系安定剤を用いることが好ましい。  [0040] As the stabilizer, a composite metal stalagmite stabilizer is preferably used.
この複合金属石鹼系安定剤は、 複合して用いられる金属石鹼の中の金属が 、 鉛及び力 ドミゥム以外の、 いわゆる無毒性の金属石鹼であれば、 特に限定 されず、 例えば、 バリウム （Ba) /亜鉛 （Z n) 系、 カルシウム （Ca) /Z n系、 C a /マグネシウム （Mg) 系、 Ba/Ca/Z n系、 Ca/M g/Z n系等の複合金属石鹼が挙げられる。  This composite metal stalagmite stabilizer is not particularly limited as long as the metal in the metal stalagmite used in combination is a so-called non-toxic metal stalagmite other than lead and force dome, for example, barium (Ba) / Zinc (Zn), Calcium (Ca) / Zn, Ca / Magnesium (Mg), Ba / Ca / Zn, Ca / Mg / Zn, etc. There is a spider.
また、 上記金属石鹼の中の酸についても、 特に限定されない。 例えば、 脂 肪酸系では、 2 _ェチルへキソイン酸、 ラウリン酸、 ミリスチン酸、 パルミ チン酸、 ステアリン酸、 イソステアリン酸、 ヒドロキシステアリン酸、 ォレ イン酸、 リシノール酸、 リノール酸、 ベヘン酸等が挙げられる。 また、 アミ ノ酸系では、 グリシン酸、 ァラニン酸、 ロイシン酸、 イソロイシン酸、 セリ ン酸、 トレォニン酸、 システィン酸、 シスチン酸、 メチォニン酸、 ァスパラ ギン酸、 グルタミン酸、 リシン酸、 アルギン酸、 フヱ二ルァラニン酸、 チロ シン酸、 ヒスチジン酸、 トリプトファン酸、 プロニン酸、 ォキシプロニン酸 等が挙げられる。  Further, the acid in the metal sarcophagus is not particularly limited. For example, in fatty acid systems, 2_ethylhexoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid, etc. Can be mentioned. In the amino acid system, glycine acid, alanic acid, leucine acid, isoleucine acid, seric acid, threonic acid, cysteic acid, cystic acid, methionic acid, aspartic acid, glutamic acid, ricinic acid, alginic acid, and fusin. Examples include luranic acid, tyrosinic acid, histidine acid, tryptophan acid, pronic acid, and oxypronic acid.
[0041] このような複合金属石鹼系安定剤は、 上記塩化ビニル系樹脂 1 00重量部 に対して、 0. 5〜3. 0重量部の範囲で配合するのが好ましい。  [0041] Such a composite metal stalagmite stabilizer is preferably blended in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
[0042] また、 上記複合金属石鹼系安定剤には、 該複合金属石鹼系安定剤と相乗作 用を示す安定化助剤が添加されていてもよい。  [0042] The composite metal stalagmite stabilizer may be added with a stabilizing aid that exhibits a synergistic action with the composite metal stalagmite stabilizer.
この安定化助剤としては、 一般的に複合金属石鹼系安定剤と相乗作用が知 られている安定化助剤であれば、 特に限定されず、 例えば、 亜リン酸エステ ル化合物、 ；S _ジケトン化合物、 多価アルコール類、 ハイ ドロタルサイ トゃ ゼォライ ト類、 酸化防止剤等が挙げられる。 これらは単独で使用してもよく 、 2種以上を併用してもよい。 The stabilizing aid is not particularly limited as long as it is generally known to be synergistic with the composite metal stalagmite stabilizer. For example, phosphite ester Compounds, S_diketone compounds, polyhydric alcohols, hydrotalcite zeolites, antioxidants, and the like. These may be used alone or in combination of two or more.
[0043] 滑剤としては、 内部滑剤、 及び外部滑剤が挙げられる。 [0043] Examples of the lubricant include an internal lubricant and an external lubricant.
上記内部滑剤は、 成形加工時の溶融樹脂の流動粘度を下げ、 摩擦発熱を防 止する目的で使用されるものであれば、 特に限定されず、 例えば、 プチルス テアレート、 ラウリルアルコール、 ステアリルアルコール、 エポキシ大豆油 、 グリセリンモノステアレート、 ステアリン酸、 ビスアミ ド等が挙げられる これらは単独で使用してもよく、 2種以上を併用してもよい。 上記外部滑剤は、 成形加工時の溶融樹脂と金属面との滑り効果を上げる目 的で使用されるものであれば、 特に限定されず、 例えば、 パラフィンヮック ス、 ポリオレフインワックス、 エステルワックス、 モンタン酸ワックス、 ァ クリル系高分子滑剤等が挙げられる。 これらは単独で使用してもよく、 2種 以上を併用してもよい。  The internal lubricant is not particularly limited as long as it is used for the purpose of lowering the flow viscosity of the molten resin during molding processing and preventing frictional heat generation. For example, butyl stearate, lauryl alcohol, stearyl alcohol, epoxy Examples include soybean oil, glycerin monostearate, stearic acid, and bisamide. These may be used alone or in combination of two or more. The external lubricant is not particularly limited as long as it is used for the purpose of increasing the sliding effect between the molten resin and the metal surface during molding. For example, paraffin wax, polyolefin wax, ester wax, montanic acid wax And acrylic polymer lubricants. These may be used alone or in combination of two or more.
[0044] 衝撃改良剤としては、 例えば 3 0〜4 0 %の塩素を含有する塩素化ポリエ チレン、 ァクリル酸エステル及び/またはシロキサンを含有するァクリル酸 エステル共重合ゴムにメチルメタクリレート、 スチレン、 アクリロニトリル 等の単量体をグラフト重合した多成分系樹脂、 アクリロニトリル■ ブタジェ ン■スチレン樹脂、 メチルメタクリレ一ト ■ ブタジエン■スチレン樹脂、 酢 酸ビニル■エチレン共重合体樹脂などが挙げられる。  [0044] As the impact modifier, for example, chlorinated polyethylene containing 30 to 40% of chlorine, acrylic acid ester and / or acrylic acid ester copolymer rubber containing siloxane, methyl methacrylate, styrene, acrylonitrile, etc. And multi-component resins obtained by graft polymerization of these monomers, acrylonitrile butadiene styrene resin, methyl methacrylate butadiene styrene resin, vinyl acetate ethylene copolymer resin, and the like.
[0045] 上記加工助剤としては、 特に限定されず、 例えば、 重量平均分子量 1 0万 〜2 0 0万のアルキルァクリレート一アルキルメタクリレ一ト共重合体等の ァクリル系加工助剤等が挙げられ、 その具体例としては、 n—プチルァクリ レ一トーメチルメタクリレ一ト共重合体、 2 _ェチルへキシルァクリレ一ト —メチルメタクリレート一ブチルメタクリレ一ト共重合体等が挙げられる。 これらは単独で使用してもよく、 2種以上を併用してもよい。  [0045] The processing aid is not particularly limited, and examples thereof include acryl-based processing aids such as alkyl acrylate-alkyl methacrylate copolymers having a weight average molecular weight of 10,000 to 200,000, etc. Specific examples thereof include n-butyl methacrylate-methyl methacrylate copolymer, 2_ethyl hexyl acrylate-methyl methacrylate monobutyl methacrylate copolymer, and the like. These may be used alone or in combination of two or more.
[0046] 上記充填剤としては、 特に限定されず、 例えば、 炭酸カルシウム、 タルク 、 マイ力、 クレー、 シリカ等が挙げられる。 これらは単独で使用してもよく 、 2種以上を併用してもよい。 [0046] The filler is not particularly limited, and examples thereof include calcium carbonate and talc. My strength, clay, silica and the like. These may be used alone or in combination of two or more.
[0047] 上記帯電防止剤としては、 [0047] As the antistatic agent,
(ィ） 第一級ァミン塩、 第三級ァミン、 第四級アンモニゥム化合物、 ピリジ ン誘導体等の力チオン系のもの、  (I) Power thione compounds such as primary amin salts, tertiary amines, quaternary ammonium compounds, pyridine derivatives,
(口） 硫酸化油、 石ケン、 硫酸化エステル油、 硫酸化アミ ド油、 ォレフィン の硫酸エステル塩類、 脂肪アルコール硫酸エステル塩、 アルキル硫酸エルテ ル塩、 脂肪酸ェチルスルホン酸塩、 アルキルナフタレンスルホン酸塩、 アル キルベンゼンスルホン酸塩、 コハク酸エステルスルホン酸塩、 リン酸エステ ル塩等のァニオン系のもの、  (Mouth) Sulfated oil, soap, sulfated ester oil, sulfated amide oil, sulfate salt of olefin, fatty alcohol sulfate ester, alkyl sulfate ester salt, fatty acid ethyl sulfonate, alkyl naphthalene sulfonate, Any anion series such as alkyl benzene sulfonate, succinate ester sulfonate, ester phosphate,
(ハ） 多価アルコールの部分的脂肪酸エステル、 脂肪アルコールのエチレン ォキサイ ド付加物、 脂肪酸のエチレンォキサイ ド付加物、 脂肪アミノまたは 脂肪酸アミ ドのエチレンォキサイ ド付加物、 アルキルフエノールのエチレン ォキサイ ド付加物、 アルキルナフトールのエチレンォキサイ ド付加物、 多価 アルコールの部分的脂肪酸エステルのエチレンォキサイ ド付加物、 ポリェチ レングリコール等の非イオン系のもの、  (C) Partial fatty acid ester of polyhydric alcohol, ethylene oxide adduct of fatty alcohol, ethylene oxide adduct of fatty acid, ethylene oxide adduct of fatty amino or fatty acid amide, ethylene oxide of alkylphenol Adducts, ethylene oxide adducts of alkyl naphthols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, non-ionic ones such as polyethylene glycol,
(二） カルボン酸誘導体、 イミダゾリン誘導体等の両性系のもの、 等が一般的に使用可能であるが、 特に非イオン系、 中でもポリオキシェチレ ンアルキルアミンゃポリオキシエチレンアルキルアミ ドないしそれらの脂肪 酸エステル、 グリセリンの脂肪酸エステル等が好ましい。  (2) Amphoteric compounds such as carboxylic acid derivatives and imidazoline derivatives are generally usable, but nonionic compounds, especially polyoxyethylene alkylamines or polyoxyethylene alkylamides or fatty acid esters thereof. Fatty acid esters of glycerin and the like are preferable.
[0048] 上記着色剤としては、 特に限定されず、 例えば、 ァゾ系、 フタロシアニン 系、 スレン系、 染料レーキ系等の有機顔料； 力一ポンプラック、 クロム酸モ リブデン系、 硫化物■セレン化物系、 フヱロシアニン化物系等の無機顔料等 が挙げられる。 これらは単独で使用してもよく、 2種以上を併用してもよい [0048] The colorant is not particularly limited, and examples thereof include organic pigments such as azo-type, phthalocyanine-type, selenium-type, dye lake-type, etc .; Kiichi pump rack, chromic acid molybdenum-type, sulfide ■ selenide And inorganic pigments such as phthalocyanine compounds. These may be used alone or in combination of two or more
[0049] 上記紫外線吸収剤としては、 例えば、 2 , 4—ジヒドロキシベンゾフエノン 、 2—ヒドロキシ _ 4—メ トキシベンゾフエノン、 5 , 5 ' —メチレンビス ( 2—ヒドロキシ _ 4—メ トキシベンゾフエノン） 等の 2—ヒドロキシベン ゾフエノン類； 2— (2， 一ヒドロキシ一 5' —メチルフエニル） ベンゾト リアゾ一ル、 2_ (2， 一ヒドロキシ一3' —第三ブチル一5' —メチルフ ェニル） 一5—クロ口べンゾトリァゾ一ル、 2— (2， 一ヒドロキシ一 5' —第三ォクチルフエ二ル） ベンゾトリアゾ一ル、 2_ (2' —ヒドロキシ 3 ' , 5' —ジクミルフエニル） ベンゾトリァゾ一ル、 2, 2' —メチレンビ ス （4—第三ォクチル一 6 _ベンゾトリアゾリル） フエノール等の 2 _ (2 ' —ヒドロキシフエニル） ベンゾトリアゾ一ル類が挙げられる。 [0049] Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy_4-methoxybenzophenone, and 5,5'-methylenebis (2-hydroxy_4-methoxybenzophene. Non-) 2-hydroxyben Zophenones; 2— (2, monohydroxy-5'-methylphenyl) benzotriazol, 2_ (2, monohydroxy-3'- tert-butyl-5'-methylphenyl) 15-clobenzobenzotriazole , 2— (2, monohydroxy 1 5 ′ — tertiary octyl phenyl) benzotriazol, 2_ (2 ′ — hydroxy 3 ′, 5 ′ — dicumyl phenyl) benzotriazol, 2, 2 ′ — methylene bis (4— Tert-octyl-6_benzotriazolyl) 2_ (2′-hydroxyphenyl) benzotriazols such as phenol.
[0050] 上記光安定剤としては、 例えば、 1 , 2, 2, 6, 6_ペンタメチル _4 —ピベリジルステアレート、 2, 2, 6, 6—テトラメチル _4—ピベリジ ルベンゾェ一ト、 N— (2, 2, 6, 6—テトラメチル _4—ピペリジル） ドデシルコハク酸イミ ド、 1 _ 〔 （3, 5—ジ第三ブチル _4—ヒドロキシ フエニル） プロピオ二ルォキシェチル〕 一 2, 2, 6, 6—テトラメチル一 4—ピペリジル一 （3, 5—ジ第三ブチル _4—ヒドロキシフエニル） プロ ピオネート、 ビス （2, 2, 6, 6—テトラメチル _4—ピペリジル） セバ ケ一ト、 テトラ （2, 2, 6, 6—テトラメチル _4—ピペリジル） ブタン テトラカルポキシレート、 テトラ （ 1 , 2, 2, 6, 6_ペンタメチル _4 —ピペリジル） ブタンテトラカルポキシレート、 ビス （2, 2, 6, 6—テ トラメチル _ 4—ピぺリジル） ■ジ （トリデ [0050] Examples of the light stabilizer include 1, 2, 2, 6, 6_pentamethyl _4—piberidyl stearate, 2, 2, 6, 6-tetramethyl _4-piveridyl benzoate, N— (2, 2, 6, 6-tetramethyl _4-piperidyl) dodecylsuccinic acid imide, 1 _ ((3,5-ditertiary butyl 4-hydroxyphenyl) propionyloxychetyl) 1, 2, 2, 6, 6 —Tetramethyl mono 4-piperidyl mono (3,5-ditertiary butyl 4-hydroxyphenyl) propionate, bis (2, 2, 6, 6-tetramethyl _4-piperidyl) Sebacate, tetra (2 , 2, 6, 6-tetramethyl _4-piperidyl) butane tetracarboxylate, tetra (1, 2, 2, 6, 6_pentamethyl _4 —piperidyl) butanetetracarboxylate, bis (2, 2, 6, 6—Tetramethyl _ 4—Piperidyl) ■ Di (Torde
シル） ブタンテトラカルポキシレート、 ビス （1 , 2, 2, 6, 6_ペンタ メチル _4—ピペリジル） .ジ （トリデシル） ブタンテトラカルポキシレ一 ト等のヒンダ一ドアミン系化合物が挙げられる。  And hindered amine compounds such as syl) butanetetracarboxylate, bis (1,2,2,6,6_pentamethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate.
[0051] 上記過塩素酸塩としては、 過塩素酸イオン導入ハイ ドロタルサイ ト及びァ ルカリアルミニウム複合水酸化物塩の他には、 過塩素酸ナトリウム、 過塩素 酸マグネシウム、 過塩素酸カルシウム、 過塩素酸バリウム、 過塩素酸亜鉛が 挙げられる。 また、 それら過塩素酸塩と多価アルコールとの錯体も使用でき 、 好ましい多価アルコールとしては、 ジエチレングリコールモノメチルェ一 テル、 トリエチレングリコールもしくはプロピレングリコールモノメチルェ 一テルが挙げられる。 [0052] 以上のような各種添加剤を、 本塩化ビニル系樹脂組成物に混合する方法と しては、 特に限定されず、 例えば、 ホットブレンドによる方法、 コールドブ レンドによる方法等が挙げられる。 [0051] The perchlorate includes sodium perchlorate, magnesium perchlorate, calcium perchlorate, perchlorate, in addition to perchlorate ion-introduced hydrotalcite and alkali aluminum composite hydroxide salt. Examples include barium acid and zinc perchlorate. In addition, complexes of these perchlorates and polyhydric alcohols can also be used. Preferred polyhydric alcohols include diethylene glycol monomethyl ether, triethylene glycol or propylene glycol monomethyl ether. [0052] The method of mixing the above various additives into the vinyl chloride resin composition is not particularly limited, and examples thereof include a method using hot blending and a method using cold blending.
[0053] 複合金属石鹼系安定剤は、 粉粒体の形 （即ち粉末の形） 、 或いは粒状物の 形で、 ワンパックの安定剤として使用することができる。 粒状物の製造には 、 押出成形造粒法、 噴霧造粒法、 回転円盤造粒法、 転動造粒法、 圧縮造粒法 等のそれ自体公知の造粒法を用いることができる。 粉粒体の粒度は、 目的に 応じて任意に調節することができ、 一般に粒径が 5 0 ;U m〜5 m m、 特に 7 0 m〜 2 m mの範囲にあるのが好適である。  [0053] The composite metal stalagmite stabilizer can be used as a one-pack stabilizer in the form of particles (that is, in the form of powder) or in the form of granules. For the production of granules, known granulation methods such as extrusion granulation method, spray granulation method, rotary disk granulation method, rolling granulation method, compression granulation method and the like can be used. The particle size of the powder can be arbitrarily adjusted according to the purpose, and it is generally preferable that the particle size is in the range of 50; U m to 5 mm, particularly 70 m to 2 mm.
[0054] なお、 本塩化ビニル系樹脂組成物は、 可塑在を含まない硬質塩化ビニル樹 脂組成物であっても、 熱安定性、 耐金型汚染性、 耐候性及び耐候耐熱性を良 好に維持することができる特徴を有しているため、 可塑剤を含む塩化ビニル 樹脂組成物であってもよいが、 可塑剤を含まない硬質塩化ビニル樹脂組成物 の方が本発明の特徴が効果的に発揮されるため、 より好ましい。  [0054] It should be noted that the present vinyl chloride resin composition has good thermal stability, mold contamination resistance, weather resistance, and weathering heat resistance even if it is a hard vinyl chloride resin composition that does not contain plasticity. Therefore, it may be a vinyl chloride resin composition containing a plasticizer. However, the characteristics of the present invention are more effective for a hard vinyl chloride resin composition containing no plasticizer. It is more preferable because it is effective.
[0055] (用途）  [0055] (Application)
本塩化ビニル系樹脂組成物の用途は特に限定されるものではなく、 例えば 成形体、 特に押出成形体を製造するのに適している。 すなわち、 本塩化ビニ ル系樹脂組成物を単軸押出機、 二軸押出機等の押出混練装置によって押出成 形することにより、 優れた押出成形体 （以下 「本押出成形体」 という） を得 ることができる。  The use of the present vinyl chloride resin composition is not particularly limited, and is suitable for producing, for example, a molded body, particularly an extrusion molded body. That is, by extruding this vinyl chloride resin composition with an extrusion kneader such as a single screw extruder or a twin screw extruder, an excellent extruded product (hereinafter referred to as “the present extruded product”) is obtained. Can.
[0056] このような押出成形は、 通常の押出成形機及び金型を用いて実施すること ができる。 この場合の成形温度は、 1 9 0〜2 1 0 °Cが好ましい。 1 9 0 °C 未満であると、 得られる押出成形体の諸物性、 特に耐衝撃性が低下する。 2 1 0 °Cを超えると、 得られる押出成形体に分解線が生じたり、 長期成形性に 劣るようになったりする等の問題が発生する。 上記金型については、 特に限 定されず、 例えば、 棒状体、 管状体、 異型断面体、 板状体、 シート、 フィル ム等を成形できるもの等が挙げられる。  [0056] Such extrusion molding can be carried out using a normal extruder and mold. In this case, the molding temperature is preferably 190 to 2100 ° C. If it is less than 90 ° C., various physical properties, particularly impact resistance, of the obtained extruded product are lowered. If it exceeds 2 10 ° C, problems such as the occurrence of decomposition lines in the resulting extruded molded product and inferior long-term moldability may occur. The mold is not particularly limited, and examples thereof include a rod-shaped body, a tubular body, a modified cross-sectional body, a plate-shaped body, a sheet, a film, and the like that can be molded.
[0057] (用語の説明） 本明細書において 「Χ〜Υ」 （Χ、 Υは任意の数字） と記載した場合、 特 にことわらない限り 「X以上 Υ以下」 の意と共に、 「好ましくは Xより大き し、」 或いは 「好ましくは Υより小さい」 の意も包含する。 [0057] (Explanation of terms) In this specification, when “Χ to Υ” (Υ and 任意 are arbitrary numbers) is described, it means “preferably larger than X”, with the meaning of “X or more and Υ or less” unless otherwise specified. The term “preferably smaller than Υ” is also included.
また、 「耐候耐熱性」 とは、 一時的に屋外に保管される場合など、 屋外に 短期間暴露された成型体を熱加工する際に、 成形体が変色することのない性 質の意味である。  “Weather and heat resistance” means the property that the molded body will not discolor when it is heat-processed for a short period of time, such as when it is temporarily stored outdoors. is there.
実施例  Example
[0058] 以下、 本発明の実施例について説明するが、 以下に説明する実施例はあく まで例であって、 本発明の範囲がこれらに制限されるものではない。  [0058] Hereinafter, examples of the present invention will be described. However, the examples described below are merely examples, and the scope of the present invention is not limited thereto.
[0059] くサンプル 1〜26> [0059] Sample 1 to 26>
下記の原料を、 表 1に示す割合で、 3 O Lスーパ一ミキサー （力ヮタ社製 3 OL Super Mixer (Rikita Co., Ltd.) at the ratio shown in Table 1
) 中に投入し、 低速回転で 5分間になつた時点で、 混合を完了して抜き出し) Add to the inside, mix at 5 minutes at low speed and finish mixing
、 非鉛系硬質塩化ビニル系樹脂組成物を得た。 A lead-free hard vinyl chloride resin composition was obtained.
[0060] (使用原料） [0060] (Raw materials used)
[塩化ビニル系樹脂]  [Vinyl chloride resin]
■平均重合度 1 030の塩化ビニル単独重合体 （ヴィテック社製 "ΜΤ— 1 1 00" 、 かさ比重 0. 52 g/m I、 平均粒径 （D 50) 1 00 U m) [0061] [塩基性無機金属塩]  ■ Vinyl chloride homopolymer with an average degree of polymerization of 1 030 (“ΜΤ— 1 1 00” manufactured by Vitec, bulk specific gravity 0.52 g / m I, average particle size (D 50) 1 00 U m) [0061] [ Basic inorganic metal salt]
■水酸化カルシウム （協和化学工業社製 "アル力マイザ一 CA" 、 B E T比 表面積 1 3m2/g、 平均粒径 （D 50) 2 U m アルミ—シリカ表面処理） ■ Calcium hydroxide ("Al force Mizer CA" manufactured by Kyowa Chemical Industry Co., Ltd., BET specific surface area 13 m 2 / g, average particle size (D 50) 2 U m aluminum-silica surface treatment)
■水酸化マグネシウム （協和化学工業社製 "キスマ 5 B" 、 B E T比表面積 4m2/g、 平均粒径 （D 50) 1 m、 脂肪酸表面処理） 、 ■ Magnesium hydroxide ("Kisuma 5 B" manufactured by Kyowa Chemical Industry Co., Ltd., BET specific surface area 4m2 / g , average particle size (D50) 1m, fatty acid surface treatment),
■酸化マグネシウム （協和化学工業社製 "マグサラット 30" 、 B E T比表 面積 38m2/g、 平均粒径 （D 50) 2 m、 脂肪酸表面処理） 、 ■軽焼ドロマイ ト （味の素ファインテクノ社製 "H C 1 03 S" 、 平均粒径 (D 50) 2 m、 有機酸塩多価アルコール表面処理）  ■ Magnesium oxide (“Masarat 30” manufactured by Kyowa Chemical Industry Co., Ltd., BET ratio table area 38 m2 / g, average particle size (D 50) 2 m, fatty acid surface treatment), ■ Light baked dolomite (“Ajinomoto Fine Techno Co. 1 03 S ", average particle size (D 50) 2 m, organic acid salt polyhydric alcohol surface treatment)
[0062] [イソシァヌレート化合物] ■エポキシ基含有イソシァヌレート A (日産化学工業社製 "T EP I C— S " 、 トリス一 （2, 3 _エポキシプロピル） 一イソシァヌレート、 エポキシ 当量 1 00 g/e q、 粒径 1 60 m、 融点 90〜 1 25 °C) [0062] [Isocyanurate compound] ■ Epoxy group-containing isocyanurate A (“T EP IC—S”, manufactured by Nissan Chemical Industries, Ltd., tris (2,3_epoxypropyl) monoisocyanurate, epoxy equivalent of 100 g / eq, particle size of 160 m, melting point 90 ~ (1 25 ° C)
■エポキシ基含有イソシァヌレート B (日産化学工業社製 "T EP I C— G " 、 トリス一 （2, 3 _エポキシプロピル） 一イソシァヌレート、 エポキシ 当量 1 00 g/e q、 粒径 360 m、 融点 90〜 1 25 °C)  ■ Epoxy group-containing isocyanurate B (“T EP IC—G”, manufactured by Nissan Chemical Industries, Ltd., tris-one (2, 3_epoxypropyl) monoisocyanurate, epoxy equivalent 100 g / eq, particle size 360 m, melting point 90-1 (25 ° C)
■エポキシ基含有イソシァヌレート C (日産化学工業社製 "T EP I C— S ■ Epoxy group-containing isocyanurate C (manufactured by Nissan Chemical Industries, Ltd. “T EP I C— S
P" 、 トリス一 （2, 3 _エポキシプロピル） 一イソシァヌレート、 ェポキ シ当量 1 O O g/e q、 粒径 1 0 m、 融点 90〜 1 25 °C) P ", tris (2,3_epoxypropyl) monoisocyanurate, epoxy equivalent 1 O O g / e q, particle size 10 m, melting point 90 ~ 125 ° C)
■エポキシ基含有イソシァヌレート D (日産化学工業社製 "MT 239" 、 トリ （S _メチルエポキシプロピル） イソシァヌレート、 エポキシ当量 1 2 ■ Epoxy group-containing isocyanurate D (manufactured by Nissan Chemical Industries "MT 239", tri (S_methylepoxypropyl) isocyanurate, epoxy equivalent 1 2
2 g / e q、 液体） 2 g / e q, liquid)
■エポキシ基含有イソシァヌレート E (四国化成工業社製 "DA— MG I C " 、 1 , 3—ジァリル— 5 _ (2, 3 _エポキシプロパン _ 1 _ィル） _ 1 3, 5—トリアジン一 2, 4, 6 ( 1 H, 3 H, 5 H) —トリオン、 ェポ キシ当量 270 g/e q)  ■ Epoxy group-containing isocyanurate E ("DA-MG IC" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1,3-diaryl-5_ (2,3_epoxypropane_1_yl) _1,3,5-triazine 4, 6 (1 H, 3 H, 5 H) —trione, epoxy equivalent 270 g / eq)
■ ヒドロキシ基含有イソシァヌレート （日産化学工業社製 "タナック P" ) [0063] [酸化チタン]  ■ Hydroxyl group-containing isocyanurate (Nissan Chemical Industries "Tanac P") [0063] [Titanium oxide]
■ルチル型酸化チタン （堺化学工業社製 "R—3 L" 、 平均粒径 （D50) ■ Rutile type titanium oxide ("R-3 L", Sakai Chemical Industry Co., Ltd., average particle size (D50)
0. 26 m、 アルミ—シリカ表面処理） 0.26 m, aluminum-silica surface treatment)
[0064] [Ca/Z n系安定剤] [0064] [Ca / Zn stabilizer]
-ステアリン酸カルシウム （日本油脂社製 "カルシウムステアレート G F 2 -Calcium stearate (Nippon Yushi Co., Ltd. "Calcium stearate G F 2
00" ) 00 ")
-ステアリン酸亜鉛 （日本油脂社製 "ジンクステアレート G F 200" ) [安定化助剤]  -Zinc stearate ("Zinc stearate G F 200" manufactured by NOF Corporation) [Stabilization aid]
■ハイ ドロタルサイ ト （協和化学工業社製 "アル力マイザ一 P 93" ) ■ Hydro Site (Kyowa Chemical Industry Co., Ltd. “Al Power Mizer 1 P 93”)
■ステアロイルペンゾメタン （口一デァ社製 "RHOD I AS TAB55"■ Stearoyl Penzomethane ("RHOD I AS TAB55" manufactured by Kuchiichi Dea)
) ■ トリスノニルフエニルホスファイ ト （城北化学工業社製 J P 35 1 ) ) ■ Trisnonyl phenyl phosphite (Johoku Chemical Industry JP 35 1)
[滑剤]  [Lubricant]
■パラフィン系滑剤 （サゾ一ル社製 "H 1 —N 4" )  ■ Paraffinic lubricant ("H 1 —N 4" manufactured by SazoIru)
■エステル系滑剤 （理研ビタミン社製 " S L _ 02 " )  ■ Ester lubricant ("S L _ 02" manufactured by Riken Vitamin)
[充填剤]  [filler]
■炭酸カルシウム （日東粉化社製 "N S— 400" )  ■ Calcium carbonate ("N S-400" manufactured by Nitto Flour Chemical Co., Ltd.)
[0065] (押出成形体の製造） [0065] (Manufacture of extruded product)
得られた塩化ビニル系樹脂組成物を、 押出量約 20 K g/h、 金型流動樹脂 温度約 205°Cとなる成形条件下で、 3 Omm異方向回転二軸押出機 （ブラ ベンダ一社製 "プラスチコ一ダ一" ） を用い、 金型については出口幅 5 Om m、 厚み 2 mmでギャップ 4 mmから 2 mmの圧縮部を有するスリットダイ を用いてそれぞれ押出成形を行い、 成形体 （シート） を得た。  The resulting vinyl chloride resin composition was subjected to a 3 Omm counter-rotating twin screw extruder (Bra Vendor Co., Ltd.) under molding conditions of an extrusion rate of about 20 Kg / h and a mold flow resin temperature of about 205 ° C. "Plasticco 1" made), and the mold was extruded using a slit die having a compressed part with an outlet width of 5 Om m, thickness of 2 mm and gap of 4 mm to 2 mm. Sheet).
[0066] <評価方法 > [0066] <Evaluation method>
各塩化ビニル系樹脂組成物及びその成形体につき、 物性を下記の評価方法 で評価し、 この結果を表 1及び表 2に合わせて示す。  The physical properties of each vinyl chloride resin composition and its molded product were evaluated by the following evaluation methods, and the results are shown in Tables 1 and 2.
[0067] ( 1 ) 熱安定性 [0067] (1) Thermal stability
混練押出成形したシートを、 オーブン中にて 1 85°CX 60分間加熱し、 目視にて着色度合いを観察し、 次の基準で評価した。  The kneaded and extruded sheet was heated in an oven at 1 85 ° C for 60 minutes, and the degree of coloring was visually observed and evaluated according to the following criteria.
〇：着色度合いが無色〜淡黄色であるもの。  ◯: The coloring degree is colorless to light yellow.
△：着色度合いが黄色〜黄褐色であるもの。  Δ: The coloring degree is yellow to tan.
X ：着色度合いが赤褐色〜黒色であるもの。  X: The coloring degree is reddish brown to black.
[0068] (2) 金型汚染性 [0068] (2) Mold contamination
前記のように塩化ビニル系樹脂組成物を押出した後、 すぐに金型を解体し て、 金型表面の付着物量を目視観察し、 次の基準で評価した。  After extruding the vinyl chloride resin composition as described above, the mold was immediately disassembled, and the amount of deposits on the mold surface was visually observed and evaluated according to the following criteria.
〇：金型付着物が全くないもの。  ○: No deposit on the mold.
△： コーナ一部等の付着しやすい部分に若干付着しているもの。  Δ: Slightly adhering to a part that tends to adhere, such as part of a corner.
X ：付着物量が多いもの。  X: A large amount of deposits.
[0069] (3) 耐候性 混練押出成形したシートについて、 サンシャインウエザーメータ一 （スガ 試験機株式会社製、 形式 S 80 D、 光源：サンシャインカーボンアーク、 試 料面放射照度： 255 W/m2) を使用し、 J I S A 1 41 5に準拠し て、 ブラックパネル温度 63°C、 相対湿度 50%RHにて、 1 02分照射 - 1 8分噴射のサイクルで 50時間照射した。 照射前後のサンプルについて、 ミノルタ社製 CHROMA MET ER 「CR_200」 を使用して色差 （ ΔΕ) を測定し、 次の基準で評価した。 [0069] (3) Weather resistance For the kneaded extruded sheet, use a sunshine weather meter (Suga Test Instruments Co., Ltd., Model S 80 D, light source: sunshine carbon arc, sample surface irradiance: 255 W / m 2 ). In accordance with the above, irradiation was performed for 50 hours with a cycle of 102 minutes irradiation-18 minutes injection at a black panel temperature of 63 ° C and a relative humidity of 50% RH. For samples before and after irradiation, the color difference (ΔΕ) was measured using a CHROMA MET ER “CR_200” manufactured by Minolta Co., Ltd., and evaluated according to the following criteria.
〇：色差 （△ E) が〇≤△ E≤3 ○: Color difference (△ E) is ○ ≤ △ E≤3
△：色差 （△ E) が 3<Δ E≤5 Δ: Color difference (Δ E) is 3 <Δ E≤5
x ：色差 （△ E) が 5<Δ E x: Color difference (△ E) is 5 <Δ E
(4) 耐候性試験後の耐熱性 （耐候耐熱性）  (4) Heat resistance after weather resistance test (Weather resistance)
混練押出成形したシートについて、 サンシャインウエザーメータ一 （スガ 試験機株式会社製、 形式 S 80 D、 光源：サンシャインカーボンアーク、 試 料面放射照度： 255 W/m2) を使用し、 J I S A 1 41 5に準拠し て、 ブラックパネル温度 63°C、 相対湿度 50%RHにて、 1 02分照射 - 1 8分噴射のサイクルで 50時間照射し、 照射後のサンプルについて、 ミノ ルタ社製 CHROMA MET ER 「CR_200」 を使用して色差 （ΔΕ ) を測定した。 For the kneaded extruded sheet, use a sunshine weather meter (Suga Test Instruments Co., Ltd., Model S 80 D, light source: sunshine carbon arc, sample surface irradiance: 255 W / m 2 ). In accordance with the following conditions, a black panel temperature of 63 ° C and a relative humidity of 50% RH, irradiation of 102 minutes-18 minutes of injection for 50 hours, and samples after irradiation were processed by Minolta CHROMA MET ER The color difference (ΔΕ) was measured using “CR_200”.
また、 サンシャインウエザーメータ一照射後、 さらにオーブン中にて 1 6 0°CX 40分間加熱し、 加熱後のサンプルについて、 ミノルタ社製 CHRO MA MET ER 「CR_200」 を使用して色差 （ΔΕ) を測定した。 そして、 加熱前後の着色変化度合いを次の基準で評価した。  In addition, after irradiating with a sunshine weather meter, the sample was further heated in an oven at 160 ° C for 40 minutes, and the color difference (ΔΕ) of the heated sample was measured using Minolta's CHRO MA MET ER “CR_200”. did. The degree of color change before and after heating was evaluated according to the following criteria.
〇：色差 （△ E) が〇≤△ E≤3 ○: Color difference (△ E) is ○ ≤ △ E≤3
△：色差 （△ E) が 3<Δ E≤5 Δ: Color difference (Δ E) is 3 <Δ E≤5
x ：色差 （△ E) が 5<Δ E サンプル No x: Color difference (△ E) is 5 <Δ E Sample No
例 1 例 2 例 3 例 4 例 5 例 6 例 7 例 8 例 9 例 1 0 例 塩化ビニル樹脂 塩化ビニル樹脂 100 100 100 100 100 100 100 100 100 100 1 水酸化カルシウム  Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 1 0 Example Vinyl chloride resin Vinyl chloride resin 100 100 100 100 100 100 100 100 100 100 1 Calcium hydroxide
水酸化マグネシウム 0.5 0.5 0.8 0.8 0.05 0.8 0.8 0.8 0.8 1 0 塩基性無機金属  Magnesium hydroxide 0.5 0.5 0.8 0.8 0.05 0.8 0.8 0.8 0.8 1 0 Basic inorganic metal
酸化マグネシウム  Magnesium oxide
軽焼ドロマイト (酸化マグネシウム-酸  Lightly burned dolomite (magnesium oxide-acid
化カルシウム *t塩）  Calcium chloride * t salt)
エポキシ基含有イソシァヌレート A 0.7 0.1 0.4 0.01 1.0 0.01 1 エポキシ基含有イソシァヌレート B 0.6  Epoxy group-containing isocyanurate A 0.7 0.1 0.4 0.01 1.0 0.01 1 Epoxy group-containing isocyanurate B 0.6
イソシァヌレー H匕エポキシ基含有イソシァヌレート C 0.3 Isocyanurate H 匕 Epoxy group-containing isocyanurate C 0.3
合物 エポキシ基含有イソシァヌレ一ト D 0.4 Compound Epoxy group-containing isocyanurate D 0.4
エポキシ基含有イソシァヌレート E 0.4 ヒドロキジ基含有イソシァヌレ一ト  Epoxy group-containing isocyanurate E 0.4 Hydroxy group-containing isocyanurate
酸化チタン 酸化チタン 0.1 1.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 ステアリン酸カルシウム 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4Titanium oxide Titanium oxide 0.1 1.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Calcium stearate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
Ca/Zn系安定剤 Ca / Zn stabilizer
ステアリン酸亜鉛 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 ハイド口タルサイト  Zinc stearate 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Hyde mouth talcite
安定化助剤 ス亍ァロイルペンゾメタン 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 トリスノニルフエニルホスファイト Stabilization aid Suaroylpenzomethane 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Trisnonyl phenyl phosphite
ノ ラフィン Wax 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 滑剤  Norafin Wax 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Lubricant
エステ ·ίΙ Λ 3χ  Esthetic · ίΙ Λ 3χ
充填剤 炭酸カルシウム 4 4 4 4 4 4 4 4 4 4 評価 Filler Calcium carbonate 4 4 4 4 4 4 4 4 4 4 Evaluation
熱安定性 O 〇 Δ Δ o o 厶 Δ 厶 成形加工時 △  Thermal stability O ○ Δ Δ o o 厶 Δ 時 During molding △
金型汚染性 〇 △ 〇 O △ o o o △ Δ 耐候性 厶 O 〇 〇 〇 o o o Δ O 成形品  Mold contamination ○ △ ○ O △ o o o △ Δ Weather resistance 厶 O ○ ○ ○ o o o Δ O Molded product
耐候試験後の耐熱性 (耐候耐熱性） O Δ O Δ 〇 o o 厶 Δ 厶 Heat resistance after weathering test (weathering heat resistance) O Δ O Δ ○ oo 厶 Δ 厶
ほ 2] 2
Figure imgf000022_0001
Figure imgf000022_0001
(考察)  (Discussion)
ヒドロキシ基含有イソシァヌレートを添加したサンプル例 2 1及び 2 4— 2 6に比べて- エポキシ基含有ィソシァヌレ一トを添加したサンプル例 1― 1 6はいずれも、 金型汚染性 （金型付着性） が顕著に優れることが分かった また、 エポキシ基当量 2 7 0 g / e qのエポキシ基含有イソシァヌレ一ト を添加したサンプル例 9と比較して、 エポキシ基当量がより小さなエポキシ 基含有イソシァヌレートを添加したサンプルは、 金型汚染性 （金型付着性） がより良好であった点を考慮すると、 エポキシ基含有イソシァヌレートのェ ポキシ基当量は少なくとも 2 7 0 g / e q未満であるのが好ましく、 より好 ましくは 2 5 0 g / e q以下、 中でもより好ましくは 2 0 0 g / e q以下、 その中でも特に 1 3 0 g / e q以下であるのが好ましいと考えられる。 また、 エポキシ基当量が同じで粒径が異なるエポキシ基含有ィソシァヌレ —トを添加したサンプル例 3、 6及び 7を比較すると、 いずれも全ての評価 項目が 「〇」 評価であつたが、 粒径が小さい程少量で効果を発揮することが 分かった。 The hydroxy group-containing Isoshianureto samples Example 2 1 and 2 4 2 6 compared to the addition of - Sample Example 1 with the addition of an epoxy group-containing Isoshianure Ichito - 1 6 was found to be remarkably superior in mold fouling (mold adhesion). Compared to sample 9 with an epoxy group-containing isocyanurate having an epoxy group equivalent of 2700 g / eq. In view of the fact that the sample with the epoxy group-containing isocyanurate having a lower epoxy group equivalent had better mold contamination (mold adhesion), the epoxy group equivalent of the epoxy group-containing isocyanurate was It is preferably at least less than 2700 g / eq, more preferably 2500 g / eq or less, more preferably 20.0 g / eq or less, and particularly preferably 1300 g / eq or less. It is considered preferable. In addition, comparing sample examples 3, 6 and 7 to which epoxy group-containing isocyanates with the same epoxy group equivalent but different particle sizes were compared, all of the evaluation items were “O” evaluations. It was found that the smaller the value, the better the effect.
産業上の利用可能性 Industrial applicability
本発明による鉛を含まない塩化ビニル系樹脂組成物及びその成形体は、 可 塑剤の使用が極少量かゼロである硬質用途において、 熱劣化 （変色、 伸びな どの機械的性質の低下、 等） が少ないうえ、 成形加工時の金型表面上の付着 物量も少なく、 屋外使用における耐候性に優れると共に、 屋外保管 （暴露） 後の熱加工時における耐劣化 （耐候耐熱性） についても優れている。  The lead-free vinyl chloride resin composition and molded product thereof according to the present invention are subject to thermal degradation (decrease in mechanical properties such as discoloration and elongation, etc.) in hard applications where the use of plasticizer is extremely small or zero. ) And a small amount of deposits on the mold surface during molding. Excellent weather resistance when used outdoors, and excellent resistance to deterioration (weather and heat resistance) during thermal processing after outdoor storage (exposure). Yes.
このような優れた諸特性を有する本発明による成形体は、 屋外使用はもと より、 屋外保管後の 2次加工にも適しており、 パイプ、 プレート、 継手等と して好適に使用することができるものである。  The molded article according to the present invention having such excellent properties is suitable not only for outdoor use but also for secondary processing after outdoor storage, and is preferably used as a pipe, plate, joint, etc. It is something that can be done.

Claims

請求の範囲 塩化ビニル系樹脂 1 0 0重量部に対し、 下記一般式で示される、 エポキシ 基を有するイソシァヌレートを 0 . 0 1〜 1重量部含むことを特徴とする非 鉛系塩化ビニル系樹脂組成物。 A lead-free vinyl chloride resin composition comprising 0.01 to 1 part by weight of an isocyanurate having an epoxy group represented by the following general formula with respect to 100 parts by weight of a vinyl chloride resin: object.
[化 1 ]  [Chemical 1]
R I
Figure imgf000024_0001
RI
Figure imgf000024_0001
(但し、 式中 2及び 3は、 それぞれ官能基 （Hを含む） を示し、 且つ 、 少なくともそのうちの一つはエポキシ基を有する官能基である。 ） (However, 2 and 3 in the formula each represent a functional group (including H), and at least one of them is a functional group having an epoxy group.)
[2] エポキシ基を有するイソシァヌレ一卜のエポキシ当量が 9 0〜 2 5 0 g / e qであることを特徴とする請求項 1記載の非鉛系塩化ビニル系樹脂組成物 [2] The lead-free vinyl chloride resin composition according to claim 1, wherein the epoxy equivalent of the epoxy group-containing isocyanurate is 90 to 2500 g / eq
[3] さらに塩化ビニル系樹脂 1 0 0重量部に対し、 0 . 0 1〜1重量部の塩基 性無機金属塩を含むことを特徴とする請求項 1又は 2に記載の非鉛系塩化ビ ニル系樹脂組成物。 [3] The lead-free vinyl chloride according to claim 1 or 2, further comprising 0.01 to 1 part by weight of a basic inorganic metal salt with respect to 100 parts by weight of the vinyl chloride resin. Nyl resin composition.
[4] 塩基性無機金属塩が、 塩基性無機酸マグネシウム塩、 塩基性無機酸カルシ ゥム塩、 及び、 塩基性無機酸カルシウム—マグネシウム複塩からなる群から 選ばれる 1種又は 2種以上の組み合わせである請求項 3に記載の非鉛系塩化 ビニル系樹脂組成物。  [4] The basic inorganic metal salt is one or more selected from the group consisting of a basic inorganic acid magnesium salt, a basic inorganic acid calcium salt, and a basic inorganic acid calcium-magnesium double salt. The lead-free vinyl chloride resin composition according to claim 3, which is a combination.
[5] さらに塩化ビニル系樹脂 1 0 0重量部に対し、 0 . 0 1〜2重量部の酸化 チタンを含むことを特徴とする請求項 1〜 4の何れかに記載の非鉛系塩化ビ ニル系樹脂組成物。  [5] The lead-free polyvinyl chloride according to any one of claims 1 to 4, further comprising 0.01 to 2 parts by weight of titanium oxide with respect to 100 parts by weight of the vinyl chloride resin. Nyl resin composition.
[6] 請求項 1〜 5の何れかに記載の塩化ビニル系樹脂組成物を押出成形してな る非鉛系塩化ビニル系押出成形体。 [6] An extrusion molding of the vinyl chloride resin composition according to any one of claims 1 to 5. Lead-free vinyl chloride extruded product.
サンシャインゥヱザ一メータ一を使用して、 J I S A 1 41 5に準拠 し、 ブラックパネル温度 63 °C、 相対湿度 50%RHにて 50時間照射した 際の色差 （ΔΕ) と、 さらにオーブンにて 1 60°Cx 40分間加熱した後の 色差 （ΔΕ) との差が、 0≤ΔΕ≤5であることを特徴とする請求項 6に記 載の非鉛系塩化ビニル系押出成形体。  Using a sunshine meter, color difference (Δ 1) when irradiated for 50 hours at a black panel temperature of 63 ° C and a relative humidity of 50% RH in accordance with JISA 1 41 5 1 The lead-free vinyl chloride-based extrudate according to claim 6, wherein the difference from the color difference (ΔΕ) after heating at 60 ° C x 40 minutes is 0≤ΔΕ≤5.
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WO2018180393A1 (en) * 2017-03-27 2018-10-04 株式会社カネカ Vinyl chloride-vinyl acetate copolymer resin composition
JP2020197242A (en) * 2019-06-03 2020-12-10 積水化学工業株式会社 Method of manufacturing pipe connector and pipe connector
CN112442242A (en) * 2019-08-28 2021-03-05 旭化成株式会社 Fresh-keeping film

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