WO2019045014A1 - Clarifying agent composition, olefinic resin composition using same, and molded article thereof - Google Patents

Clarifying agent composition, olefinic resin composition using same, and molded article thereof Download PDF

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WO2019045014A1
WO2019045014A1 PCT/JP2018/032254 JP2018032254W WO2019045014A1 WO 2019045014 A1 WO2019045014 A1 WO 2019045014A1 JP 2018032254 W JP2018032254 W JP 2018032254W WO 2019045014 A1 WO2019045014 A1 WO 2019045014A1
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tert
mass
butyl
bis
parts
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PCT/JP2018/032254
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French (fr)
Japanese (ja)
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潤二 上山
隆裕 堀越
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株式会社Adeka
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1575—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a clarifying agent composition, an olefin resin composition using the same, and a molded article thereof, and more specifically, there is no problem such as irritation, harmfulness and odor, and the melting point of the dibenzylidene sorbitol compound is jumped
  • the present invention relates to a clarifying agent composition capable of exerting excellent transparency by reducing it, an olefin resin composition using the same, and a molded article thereof.
  • the dibenzylidene sorbitol compound obtained by condensing aromatic aldehyde and sorbitol with an acetal in the presence of an acid catalyst is utilized as a clarifier which improves the transparency of olefin resin.
  • a dibenzylidene sorbitol compound for example, 1,3: 2,4: -bis (O-benzylidene) sorbitol, 1,3: 2,4-bis (p-chlorobenzylidene) sorbitol, 1,3: Known are 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-dimethylbenzylidenesorbitol) and the like.
  • the mechanism of action of these dibenzylidene sorbitol compounds as a clarifying agent is as follows: the crystal structure of the dibenzylidene sorbitol compound is once collapsed (gel-sol transition) by heating accompanying the molding of the olefin resin composition (olefin) After dissolution of the dibenzylidene sorbitol compound in the resin, in the cooling step, the network structure of the dibenzylidene sorbitol compound is newly reformed in the olefin resin (re-transfer from sol to gel), which is used as a nucleating agent By functioning, it is believed that a clearing effect can be expressed.
  • 1,3: 2,4-bis (p-methylbenzylidene) sorbitol 1,3: 2,4-bis (3,4-dimethylbenzylidenesorbitol) has a high melting point of 270 to 275 ° C.
  • 1,3: 2,4-bis (3,4-dimethylbenzylidenesorbitol) has a high melting point of 270 to 275 ° C.
  • Patent Document 2 discloses that a dibenzylidene sorbitol compound is mixed with an aliphatic carboxylic acid amide and / or an aromatic carboxylic acid amide, or the surface of the dibenzylidene sorbitol compound is an aliphatic carboxylic acid amide and / or, Compositions coated with aromatic carboxylic acid amides have been proposed.
  • Patent Document 3 proposes a composition in which a sulfate ester salt and an aliphatic carboxylic acid are dispersed in a dibenzylidene sorbitol compound.
  • Patent Document 4 proposes using a clarifier having a gel-sol transition temperature of 180 ° C. or less.
  • Patent Documents 1 to 3 are directed to 1,3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-dimethylbenzylidenesorbitol).
  • 1,3: 2,4-bis 1,4-dimethylbenzylidenesorbitol
  • the use of aliphatic carboxylic acids and anionic surfactants has problems in terms of irritation, harm and odor.
  • the clarifying agent composition described in Patent Document 4 although the trade name “Mirado NX 8000” manufactured by Milliken & Co. has been proposed, it is still insufficient, and further improvement has been desired.
  • an object of the present invention is a transparentizing agent composition which can exhibit excellent transparency without problems such as irritation, harmfulness and odor, an olefin resin composition using the same, and molding thereof To provide goods.
  • the clarifying agent composition of the present invention has (A) general formula (1),
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom
  • B relative to 100 parts by mass of a clarifying agent represented by the alkoxycarbonyl group of to 4 or a halogen atom, and s, t and u each independently represent an integer of 1 to 5)
  • the component (A) is preferably 1,3: 2,4-bis (3,4-dimethylbenzylidene sorbitol).
  • the component (B) is at least one selected from the group consisting of tert-butylphenyl salicylate, nicotinamide and 3-phenoxy-1,2-propanediol. It is preferable to contain the compound of
  • the olefin resin composition of the present invention is characterized by containing the transparentizing agent composition of the present invention such that the component (A) is 0.001 to 10 parts by mass with respect to 100 parts by mass of the olefin resin. It is said that.
  • the molded article of the present invention is characterized by using the olefin resin composition of the present invention.
  • a transparentizing agent composition which can exhibit excellent transparency without problems such as irritation, harmfulness and odor, an olefin resin composition using the same, and a molded article thereof
  • the dibenzylidene sorbitol compound can exert its effect as a clarifying agent even at low temperature molding, so that problems of odor and color tone are not caused, and transparency is achieved.
  • An excellent molded article can be provided.
  • the clarifier according to the present invention has the general formula (1), It is a dibenzylidene sorbitol compound represented by
  • each of R 1 , R 2 and R 3 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carbon atom And an alkoxycarbonyl group of 1 to 4 or a halogen atom is represented, and s, t and u each independently represent an integer of 1 to 5.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R 1 , R 2 and R 3 in the general formula (1) include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl Etc.
  • Examples of the alkoxy group having 1 to 4 carbon atoms represented by R 1 , R 2 and R 3 in the general formula (1) include methoxy, ethoxy, propoxy, isopropoxy, butoxy and the like.
  • the alkoxycarbonyl group having 1 to 4 carbon atoms represented by R 1 , R 2 and R 3 in the general formula (1) is, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group Etc.
  • halogen atom represented by R ⁇ 1 >, R ⁇ 2 > and R ⁇ 3 > in General formula (1), a fluorine atom, a chlorine atom, a bromine atom etc. are mentioned.
  • s, t and u each independently represent an integer of 1 to 5, but s and t are preferably 1, 2 or 3 and u is more preferably 1 It is.
  • the following compounds may be mentioned as specific examples of the clarifying agent represented by (A) the general formula (1).
  • the dibenzylidene sorbitol compound according to the present invention is not limited to these compounds.
  • MDBS 1,3: 2,4-bis (p-methylbenzylidene) sorbitol melting point 255-262 ° C.
  • D4MoBS 1,3: 2,4-bis (p-methoxybenzylidene) sorbitol
  • D4ClBS 1,3: 2,4-bis (p-chlorobenzylidene) sorbitol
  • EDBS 1,3: 2,4-bis (p-ethylbenzylidene) sorbitol
  • DMDBS 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol
  • DOPMN 1,2,3-Toridesoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] nonitol
  • the (B) dispersion aid in the clarifying agent composition of the present invention is a compound having an SP value of 11.0 or more and a melting point of 200 ° C. or less calculated by the Fedors method. More preferably, the sp value is 11.5 to 13.8.
  • the melting point of the (B) dispersion aid is 200 ° C. or less, more preferably 145 ° C. or less. If it is a dispersion assistant having a melting point of 200 ° C. or less, it is sufficiently melted during processing of the olefin resin, and the effects of the present invention can be obtained well.
  • (B) dispersion aid is 30 to 100 parts by mass with respect to 100 parts by mass of the clarifying agent represented by the general formula (1)
  • the transparentizing agent composition of the present invention may have a transparentizing agent or nucleating agent other than the transparentizing agent represented by (A) the general formula (1), and is used for the olefin resin You may contain the additive.
  • the olefin resin composition of the present invention is transparent so that the transparentizing agent represented by the general formula (A) is contained in an amount of 0.001 to 10 parts by mass with respect to 100 parts by mass of the olefin resin.
  • the composition contains the agent composition, preferably 0.005 to 5 parts by mass, and more preferably 0.01 to 0.5 parts by mass. If the amount is less than 0.001 part by mass, the effect of adding the clarifying agent may be insufficient. If the amount is more than 10 parts by mass, the components of the clarifying agent composition may bleed out from the molded article.
  • olefin resin used for the olefin resin composition of the present invention for example, low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), high density polyethylene (HDPE), isotactic polypropylene, syndi ⁇ such as tactic polypropylene, hemiisotactic polypropylene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene -Olefin polymer, ethylene / propylene block or random copolymer, impact copolymer polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, air Len - butyl acrylate copolymer, ethylene - vinyl acetate copolymer, ethylene - alpha-olefin copolymer such
  • these may be an elastomer.
  • these two or more kinds may be blended and used, a block copolymer may be formed and used as a block polymer type, and the resin may be alloyed.
  • chlorinated products of these olefin resins may be used.
  • Examples of the hard segment include at least one selected from polypropylene homopolymers, polypropylene block copolymers, polypropylene random copolymers, and the like.
  • soft segment examples include ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), vinyl acetate homopolymer and the like. You may blend and use these 2 or more types.
  • the above olefin resin production methods include Ziegler catalysts, Ziegler-Natta catalysts, metallocene catalysts and other various polymerization catalysts including cocatalysts, catalyst carriers, chain transfer agents, and also gas phase polymerization, solution polymerization, emulsion polymerization,
  • resins having physical properties suitable for the target product such as temperature, pressure, concentration, flow rate and various polymerization conditions such as removal of catalyst residue can be obtained, and molding of the target product It selects suitably what can obtain resin of a physical property suitable for processing.
  • any known resin additive for example, a phenolic antioxidant, a phosphorus antioxidant, etc.
  • any known resin additive for example, a phenolic antioxidant, a phosphorus antioxidant, etc.
  • Thioether-based antioxidants, UV absorbers, hindered amine compounds, nucleating agents different from the clarifying agents represented by the above-mentioned (A) general formula (1), flame retardants, flame retardant aids, lubricants, fillers, hydrotal Sites, antistatic agents, pigments, fluorescent whitening agents, dyes, etc. may be contained.
  • phenolic antioxidant for example, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis (4 -Ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis 3- (3,5-Di-tert-butyl-4-hydroxyphenyl) pro
  • the blending amount of the phenolic antioxidant is preferably 0.001 to 5 parts by mass, and more preferably 0.03 to 3 parts by mass, with respect to 100 parts by mass of the olefin resin.
  • phosphorus-based antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, diphenyl Tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (Tridecyl) phosphite, tris (isodecyl) phosphite
  • the blending amount of the phosphorus-based antioxidant is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
  • thioether-based antioxidants include tetrakis [methylene-3- (laurylthio) propionate] methane and bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl ) Sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropioate , Lauryl / stearylthiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-thiobis (6-tert-butyl-p-cresol), distearyl-di Sulfide is mentioned.
  • the blending amount of the thioether antioxidant is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
  • UV absorbers examples include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) ) Benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 -Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert- Octyl-6-benzotriazolylphenol), 2- (2-hydroxy) Polyethylene glycol ester of -3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy
  • the blending amount of the ultraviolet absorber is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
  • hindered amine compound for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6- Tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 2,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6- Tetramethyl-4-piperidyl), di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-pipe) Jyl) -di (tridecyl) -1,2,3,4--
  • the blending amount of the hindered amine compound is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
  • nucleating agents different from the clarifying agent represented by the above general formula (A) include sodium benzoate, aluminum salt of 4-tert-butylbenzoic acid, sodium adipate and disodium bicyclo [2.2. .1]
  • Metal carboxylates such as heptane-2,3-dicarboxylate, N, N ', N "-tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N', Amide compounds such as N ′ ′-tricyclohexyl-1,3,5-benzenetricarboxamide, N, N′-dicyclohexyl naphthalene dicarboxamide, 1,3,5-tri (dimethylisopropoylamino) benzene etc.
  • the blending amount of the nucleating agent different from the clarifying agent represented by the general formula (1) (A) is represented by the general formula (1) with respect to 100 parts by mass of the olefin resin.
  • the total amount with the clarifying agent is preferably 0.001 to 10 parts by mass, more preferably in the range of 0.005 to 5 parts by mass.
  • a flame retardant for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methyl ethylidene) -4,1-phenylene tetraphenyl diphosphate, 1,3-phenylene tetrakis (2,6-dimethylphenyl) phosphate, manufactured by ADEKA CORPORATION under the trade name "Adecastab FP-500", “Adecastab FP-600", “Adecastab FP” Phosphonates such as aromatic phosphoric acid ester of "-800", divinyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, diphenyl
  • flame retardants are preferably used in combination with anti-drip agents such as fluorocarbon resins and the like, and flame retardant aids such as polyhydric alcohols and hydrotalcites.
  • the blending amount in the case of blending the flame retardant is preferably 1 to 100 parts by mass, and more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the olefin resin.
  • a lubricant is added for the purpose of imparting lubricity to the surface of the molded body to enhance the scratch resistance.
  • unsaturated fatty acid amides such as oleic acid amide and erucic acid amide
  • saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, monoglyceride stearate, sorbitan monopalmitate tartrate, Sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylenebisstearic acid amide and the like can be mentioned.
  • the blending amount in the case of blending the lubricant is preferably 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
  • the filler for example, talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium hydroxide, magnesium hydroxide, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite Silica, alumina, potassium titanate whiskers, wallastonite, fibrous magnesium oxysulfate, etc., and the particle diameter (fiber diameter, fiber length and aspect ratio in fibrous form) can be appropriately selected and used. . One of these may be used alone, or two or more may be used in combination. Moreover, the filler can use what was surface-treated as needed.
  • the blending amount in the case of blending the filler is preferably 1 to 80 parts by mass, more preferably 3 to 50 parts by mass, still more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the olefin resin .
  • the hydrotalcites are complex salt compounds consisting of magnesium, aluminum, hydroxyl group, carbonate group and any crystal water known as natural products or synthetic compounds, and some of magnesium or aluminum are alkali metal, zinc and others. What substituted by metal, and what substituted the hydroxyl group and the carbonic acid group by the other anion group is mentioned, For example, the metal of the hydrotalcite represented by following General formula (2) is substituted by the alkali metal Are listed. Further, as the Al—Li-based hydrotalcites, compounds represented by the following general formula (3) can also be used.
  • x1 and x2 each represent a number satisfying the condition represented by the following formula, 0 ⁇ x2 / x1 ⁇ 10, 2 ⁇ x1 + x2 ⁇ 20, and p is 0 or a positive number. Represent.
  • a q- represents a q-valent anion
  • p represents 0 or a positive number
  • the carbonate anion in these hydrotalcites may be partially substituted by another anion.
  • the hydrotalcites may be those obtained by dehydrating water of crystallization, and higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and organic sulfonic acid metals such as alkali metal dodecylbenzene sulfonate It may be coated with a salt, a higher fatty acid amide, a higher fatty acid ester or a wax.
  • the hydrotalcites may be natural products or may be synthetic products.
  • a method for synthesizing hydrotalcites JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, JP-A-61-174270. Examples thereof include known methods described in JP-A-5-179052.
  • hydrotalcites can be used without being limited to the crystal structure, crystal particles and the like. One of these may be used alone, or two or more may be used in combination.
  • the blending amount of the hydrotalcites is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the olefin resin.
  • antistatic agents include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, alkyl of anionic type Anionic antistatic agents such as sulfonates, higher alcohol sulfuric acid ester salts, higher alcohol ethylene oxide adduct sulfuric acid ester salts, higher alcohol ethylene oxide adduct phosphoric acid ester salts; polyhydric alcohol fatty acid esters, polyglycol phosphoric acid esters, polyoxy acids
  • Nonionic antistatic agent such as ethylene alkyl allyl ether
  • amphoteric alkyl betaine such as alkyl dimethylamino acetic acid betaine
  • amphoteric antistatic agent such as imidazoline type amphoteric surfactant, and high molecular weight such as polyether ester polyamide Type antistatic agents.
  • the blending amount of the antistatic agent is preferably 0.03 to 2 parts by mass, and more preferably 0.1 to 0.8 parts by mass with respect to 100 parts by mass of the olefin resin.
  • pigments commercially available pigments can also be used.
  • the fluorescent whitening agent is a compound that absorbs the ultraviolet rays of sunlight or artificial light, converts the light into a violet to blue visible light and emits the visible light, thereby promoting the whiteness and bluishness of the molded product.
  • As the brightening agents benzoxazole compounds C.I. I. Fluorescent Brightner 184; coumarin compound C.I. I. Fluorescent Brightner 52; diaminostilbenedisulfonic acid compound C.I. I. Fluorescent Brightner 24, 85, 71 etc. are mentioned.
  • the blending amount in the case of using the fluorescent whitening agent is preferably 0.00001 to 0.1 part by mass, and more preferably 0.00005 to 0.05 part by mass with respect to 100 parts by mass of the olefin resin.
  • dyes As dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazolyl dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And cyanine dyes and the like, and these may be used alone or in combination of two or more.
  • a molded article can be obtained using an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calendar molding method, a slush molding method, a dip molding method, a foam molding method or the like.
  • olefin resin composition of the present invention includes automotive materials for bumpers, dashboards, instrument panels, etc., housing applications such as refrigerators, washing machines, vacuum cleaners, household goods such as dishes, buckets, bathing articles, etc.
  • articles, storage of articles such as tanks, molded articles such as containers for preservation, films, fibers and the like can be mentioned.
  • the melting points and the sp values of the test compounds shown in Table 1 below were measured by the following procedures.
  • the melting point and the sp value of the test compound used for the evaluation are shown together in Table 1 respectively.
  • ⁇ Sp value> Calculated by the Fedors method.
  • the evaporation energy at 25 ° C. of each atom or group was calculated using the data described in “RF Fedors; Polym. Eng. Sci., 14 [2], 147-154 (1974)” to calculate the sp value. .
  • DMDBS 1,3: 2,4-bis (3,4-dimethylbenzylidene sorbitol)
  • EBSA N. N'-ethylenebisstearic acid amide BA: behenic acid amide SA: stearic acid amide OA: oleic acid amide
  • GMS stearic acid monoglyceride PV100: manufactured by Riken Vitamin Co., Ltd. trade name "POEM PV-100" (glyceride stearate and palmitic acid Mixture with glycerol (mass ratio: 1: 1))
  • LA-12 Made by ADEKA Co., Ltd. Brand name "ADK Stab LA-12" tBPS: tert-Butyl phenyl salicylate
  • a random-polypropylene of MFR 12 g / min
  • an antioxidant and a neutralizing agent were prepared in the amounts described in Table 3, and dry-blended using a Henschel mixer. After blending, the mixture was granulated using an extruder under conditions of a resin temperature of 200 ° C. to obtain pellets. The obtained pellet was dried in a 60 ° C. incubator for 8 hours. After
  • the transparency performance was evaluated by the following procedure.
  • the sheet was heated to 200 ° C. under the conditions of 100 ° C./min, held at 200 ° C. for 1 min, and then cooled to room temperature at a rate of 10 ° C./min.
  • When cooling it was confirmed by a polarization microscope, and when polarization of the olefin resin was confirmed at the boundary of the clarifying agent composition, it was evaluated as having transparency performance, and when polarization could not be confirmed, no transparency performance .
  • the results are shown in Table 3 respectively.
  • AO-60 tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxymethyl] methane 2112: tris (2,4-di-tert-butylphenyl) phosphite
  • Ca-St stea Calcium phosphate
  • each of the resin compositions of Examples 2-1 to 2-3 adjusted to 0.16 parts by mass of the clarifying agent is dry-blended using a Henschel mixer, and after blending, an extruder is used. And pelletize the obtained pellet in a thermostat at 60 ° C. for 8 hours, and then use an injection molding machine to make a 1 mm thick sheet at an injection temperature of 200 ° C. When molded, transparency was good even at low temperature processing at 200 ° C., and no odor was generated.
  • the clarifying agent composition of the present invention can significantly lower the melting point of the dibenzylidene sorbitol compound. Then, it was confirmed that low temperature molding was possible, odor was suppressed, and molded articles having excellent transparency could be provided.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided are: a clarifying agent composition capable of exhibiting excellent transparency without problems involving irritation, toxicity, odor, etc.; an olefinic resin composition in which said composition is used; and a molded article thereof. A clarifying agent composition containing 30-100 mass parts of a dispersion aid (B) per 100 mass parts of a clarifying agent (A) represented by general formula (1) (in general formula (1), R1, R2, and R3 each independently represent a hydrogen atom, a C1-4 alkyl group, a C1-4 alkoxy group, a C1-4 alkoxycarbonyl group, or a halogen atom; and s, t, and u each independently represent an integer of 1-5), wherein the dispersion aid (B) has an SP value, as calculated by Fedor's method, of 11.0 or higher, and a melting point of 200°C or lower.

Description

透明化剤組成物、これを用いたオレフィン系樹脂組成物、およびその成形品Transparency agent composition, olefin resin composition using the same, and molded article thereof
　本発明は、透明化剤組成物、これを用いたオレフィン系樹脂組成物、およびその成形品に関し、詳しくは、刺激性、有害性、臭気等の問題がなく、ジベンジリデンソルビトール化合物の融点を飛躍的に低下させることにより、優れた透明性を発揮することができる透明化剤組成物、これを用いたオレフィン系樹脂組成物、およびその成形品に関する。 The present invention relates to a clarifying agent composition, an olefin resin composition using the same, and a molded article thereof, and more specifically, there is no problem such as irritation, harmfulness and odor, and the melting point of the dibenzylidene sorbitol compound is jumped The present invention relates to a clarifying agent composition capable of exerting excellent transparency by reducing it, an olefin resin composition using the same, and a molded article thereof.
　芳香族アルデヒドとソルビトールとを酸触媒の存在下、アセタールと縮合させることによって得られるジベンジリデンソルビトール化合物は、オレフィン系樹脂の透明性を改善する透明化剤として利用されている。このようなジベンジリデンソルビトール化合物としては、例えば、１，３：２，４：－ビス（Ｏ－ベンジリデン）ソルビトール、１，３：２，４－ビス（ｐ－クロロベンジリデン）ソルビトール、１，３：２，４－ビス（ｐ－メチルベンジリデン）ソルビトール、１，３：２，４－ビス（３，４－ジメチルベンジリデンソルビトール）等が知られている。 The dibenzylidene sorbitol compound obtained by condensing aromatic aldehyde and sorbitol with an acetal in the presence of an acid catalyst is utilized as a clarifier which improves the transparency of olefin resin. As such a dibenzylidene sorbitol compound, for example, 1,3: 2,4: -bis (O-benzylidene) sorbitol, 1,3: 2,4-bis (p-chlorobenzylidene) sorbitol, 1,3: Known are 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-dimethylbenzylidenesorbitol) and the like.
　これらジベンジリデンソルビトール化合物の透明化剤としての作用機構は、オレフィン系樹脂組成物の成形に伴う加熱によって、ジベンジリデンソルビトール化合物の結晶構造が一旦崩壊する過程（ゲル－ゾル転移）を経て、オレフィン系樹脂中でジベンジリデンソルビトール化合物が溶解した後、冷却工程において、オレフィン系樹脂中に新たにジベンジリデンソルビトール化合物のネットワーク構造が再形成されて（ゾルからゲルへの再転移）、それが核剤として機能することにより、透明化効果を発現することができると考えられている。 The mechanism of action of these dibenzylidene sorbitol compounds as a clarifying agent is as follows: the crystal structure of the dibenzylidene sorbitol compound is once collapsed (gel-sol transition) by heating accompanying the molding of the olefin resin composition (olefin) After dissolution of the dibenzylidene sorbitol compound in the resin, in the cooling step, the network structure of the dibenzylidene sorbitol compound is newly reformed in the olefin resin (re-transfer from sol to gel), which is used as a nucleating agent By functioning, it is believed that a clearing effect can be expressed.
　このような透明化剤を使用してオレフィン系樹脂の透明化を改善するためには、成形工程において、ジベンジリデンソルビトール化合物が溶解する温度以上に加熱することが不可欠である。しかしながら、１，３：２，４－ビス（ｐ－メチルベンジリデン）ソルビトール、１，３：２，４－ビス（３，４－ジメチルベンジリデンソルビトール）は、２７０～２７５℃の高い融点を持っており、高温で加工すると、ジベンジリデンソルビトール化合物に熱分解が生じ、臭気が強いベンズアルデヒドが発生する問題がある。作業環境の保護や省エネの観点から低温（２００℃以下）で加工することが求められている。 In order to improve the transparency of the olefin resin by using such a clarifying agent, it is essential to heat at a temperature at which the dibenzylidene sorbitol compound dissolves in the molding step. However, 1,3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-dimethylbenzylidenesorbitol) has a high melting point of 270 to 275 ° C. When processed at high temperatures, there is a problem that the dibenzylidene sorbitol compound is thermally decomposed to generate strong odorous benzaldehyde. Processing at low temperature (200 ° C. or less) is required from the viewpoint of protection of work environment and energy saving.
　ジベンジリデンソルビトール化合物を用いて低温加工するために、ジベンジリデンソルビトール化合物の融点を低下させる検討が行われている。例えば、特許文献１には、融点が、２７５～２８０℃である１，３－Ｏ－３，４－ジメチルベンジリデン－２，４－Ｏ－ベンジリデンソルビトールおよび／または１，３－Ｏ－ベンジリデン－２，４－Ｏ－３，４－ジメチルベンジリデンソルビトールに対し、融点が、２１５～２２０℃であるビス（Ｏ－３，４－ジメチルベンジリデンソルビトール）をブレンドした組成物が提案されている。 Studies have been made to reduce the melting point of dibenzylidene sorbitol compounds for low temperature processing with dibenzylidene sorbitol compounds. For example, U.S. Pat. No. 4,959,959 describes 1,3-O-3,4-dimethylbenzylidene-2,4-O-benzylidene sorbitol and / or 1,3-O-benzylidene-2 having a melting point of 275-280.degree. A composition is proposed in which bis (O-3,4-dimethylbenzylidene sorbitol) having a melting point of 215 to 220 ° C. is blended with 4, 4-O-3,4-dimethylbenzylidene sorbitol.
　特許文献２には、ジベンジリデンソルビトール化合物に対し、脂肪族カルボン酸アミドおよび／または、芳香族カルボン酸アミドを混和されているか、ジベンジリデンソルビトール化合物の表面を、脂肪族カルボン酸アミドおよび／または、芳香族カルボン酸アミドで被覆した組成物が提案されている。 Patent Document 2 discloses that a dibenzylidene sorbitol compound is mixed with an aliphatic carboxylic acid amide and / or an aromatic carboxylic acid amide, or the surface of the dibenzylidene sorbitol compound is an aliphatic carboxylic acid amide and / or, Compositions coated with aromatic carboxylic acid amides have been proposed.
　特許文献３には、ジベンジリデンソルビトール化合物に対し、硫酸エステル塩および脂肪族者カルボン酸を分散させた組成物が提案されている。特許文献４には、ゲル－ゾル転移温度が１８０℃以下である透明化剤を用いることが提案されている。 Patent Document 3 proposes a composition in which a sulfate ester salt and an aliphatic carboxylic acid are dispersed in a dibenzylidene sorbitol compound. Patent Document 4 proposes using a clarifier having a gel-sol transition temperature of 180 ° C. or less.
特開平７－２７８３６２号公報Unexamined-Japanese-Patent No. 7-278362 特許３３４３７５４号Patent No. 3343754 特許３３５８６５９号Patent 3358659 特開２０１０－２５４８８２号公報Unexamined-Japanese-Patent No. 2010-254882
　しかしながら、特許文献１～３に記載の方法は、１，３：２，４－ビス（ｐ－メチルベンジリデン）ソルビトール、１，３：２，４－ビス（３，４－ジメチルベンジリデンソルビトール）に対しては充分なものではなく、さらなる改善が求められていた。特に、脂肪族カルボン酸や、アニオン系界面活性剤の使用は、刺激性、有害性、臭気の点で問題があった。また、特許文献４に記載の透明化剤組成物は、ミリケン・アンド・カンパニー社製商品名「ミラッドＮＸ８０００」が提案されているが、未だ不十分であり、さらなる改善が求められていた。 However, the methods described in Patent Documents 1 to 3 are directed to 1,3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-dimethylbenzylidenesorbitol). Was not enough, and further improvement was required. In particular, the use of aliphatic carboxylic acids and anionic surfactants has problems in terms of irritation, harm and odor. Further, as for the clarifying agent composition described in Patent Document 4, although the trade name “Mirado NX 8000” manufactured by Milliken & Co. has been proposed, it is still insufficient, and further improvement has been desired.
　そこで、本発明の目的は、刺激性、有害性、臭気等の問題がなく、優れた透明性を発揮することができる透明化剤組成物、これを用いたオレフィン系樹脂組成物、およびその成形品を提供することにある。 Therefore, an object of the present invention is a transparentizing agent composition which can exhibit excellent transparency without problems such as irritation, harmfulness and odor, an olefin resin composition using the same, and molding thereof To provide goods.
　本発明者等は、上記課題を解決すべく鋭意検討した結果、ジベンジリデンソルビトール化合物に対し、特定の分散助剤を混合した透明化剤組成物を用いることで、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a clarifying agent composition in which a specific dispersing aid is mixed with the dibenzylidene sorbitol compound. The present invention has been completed.
　すなわち、本発明の透明化剤組成物は、（Ａ）一般式（１）、
（一般式（１）中、Ｒ１、Ｒ２およびＲ３は、各々独立して、水素原子、炭素原子数１～４のアルキル基、炭素原子数１～４のアルコキシ基、炭素原子数１～４のアルコキシカルボニル基、または、ハロゲン原子を表し、ｓ、ｔおよびｕは、各々独立して、１～５の整数を表す）で表される透明化剤１００質量部に対し、（Ｂ）分散助剤を、３０～１００質量部含有する透明化剤組成物であって、（Ｂ）分散助剤が、Ｆｅｄｏｒｓ法で算出したＳＰ値が、１１．０以上であり、かつ、融点が２００℃以下であることを特徴とするものである。 That is, the clarifying agent composition of the present invention has (A) general formula (1),
In the general formula (1), R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom (B) relative to 100 parts by mass of a clarifying agent represented by the alkoxycarbonyl group of to 4 or a halogen atom, and s, t and u each independently represent an integer of 1 to 5) A clarifying agent composition containing 30 to 100 parts by mass of a dispersion aid, wherein (B) the dispersion aid has an SP value calculated by Fedors method of 11.0 or more, and a melting point of 200 C. or less.
　本発明の透明化剤組成物においては、（Ａ）成分は、１，３：２，４－ビス（３，４－ジメチルベンジリデンソルビトール）であることが好ましい。また、本発明の透明化剤組成物においては、（Ｂ）成分は、ｔｅｒｔ－ブチルフェニルサリチレート、ニコチンアミド、３－フェノキシ－１，２－プロパンジオールからなる群から選択される少なくとも１種の化合物を含有することが好ましい。 In the clarifying agent composition of the present invention, the component (A) is preferably 1,3: 2,4-bis (3,4-dimethylbenzylidene sorbitol). Further, in the clarifying agent composition of the present invention, the component (B) is at least one selected from the group consisting of tert-butylphenyl salicylate, nicotinamide and 3-phenoxy-1,2-propanediol. It is preferable to contain the compound of
　本発明のオレフィン系樹脂組成物は、オレフィン系樹脂１００質量部に対し、（Ａ）成分が、０．００１～１０質量部となるように本発明の透明化剤組成物を含有することを特徴とするものである。 The olefin resin composition of the present invention is characterized by containing the transparentizing agent composition of the present invention such that the component (A) is 0.001 to 10 parts by mass with respect to 100 parts by mass of the olefin resin. It is said that.
　本発明の成形品は、本発明のオレフィン系樹脂組成物を用いてなることを特徴とするものである。 The molded article of the present invention is characterized by using the olefin resin composition of the present invention.
　本発明によれば、刺激性、有害性、臭気等の問題がなく、優れた透明性を発揮することができる透明化剤組成物、これを用いたオレフィン系樹脂組成物、およびその成形品を提供することができる。本発明のオレフィン系樹脂であれば、低温成形時においても、ジベンジリデンソルビトール化合物が透明化剤としての効果を発揮することが可能となるため、臭気や色調の問題を生じさせず、透明性に優れる成形品を提供することができる。 According to the present invention, a transparentizing agent composition which can exhibit excellent transparency without problems such as irritation, harmfulness and odor, an olefin resin composition using the same, and a molded article thereof Can be provided. In the case of the olefin resin of the present invention, the dibenzylidene sorbitol compound can exert its effect as a clarifying agent even at low temperature molding, so that problems of odor and color tone are not caused, and transparency is achieved. An excellent molded article can be provided.
　以下、本発明の実施の形態について詳細に説明する。
　まず、本発明に係る（Ａ）一般式（１）で表される透明化剤について説明する。本発明に係る透明化剤は、一般式（１）、
Figure JPOXMLDOC01-appb-I000003
で表されるジベンジリデンソルビトール化合物である。ここで、一般式（１）中、Ｒ１、Ｒ２およびＲ３は、各々独立して、水素原子、炭素原子数１～４のアルキル基、炭素原子数１～４のアルコキシ基、炭素原子数１～４のアルコキシカルボニル基、または、ハロゲン原子を表し、ｓ、ｔおよびｕは、各々独立して、１～５の整数を表す。 Hereinafter, embodiments of the present invention will be described in detail.
First, the clarifying agent represented by (A) General formula (1) which concerns on this invention is demonstrated. The clarifier according to the present invention has the general formula (1),
Figure JPOXMLDOC01-appb-I000003
It is a dibenzylidene sorbitol compound represented by Here, in the general formula (1), each of R 1 , R 2 and R 3 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carbon atom And an alkoxycarbonyl group of 1 to 4 or a halogen atom is represented, and s, t and u each independently represent an integer of 1 to 5.
　一般式（１）において、Ｒ１、Ｒ２およびＲ３で表される炭素原子数１～４のアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル等が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms represented by R 1 , R 2 and R 3 in the general formula (1) include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl Etc.
　一般式（１）において、Ｒ１、Ｒ２およびＲ３で表される炭素原子数１～４のアルコキシ基としては、例えば、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ等が挙げられる。 Examples of the alkoxy group having 1 to 4 carbon atoms represented by R 1 , R 2 and R 3 in the general formula (1) include methoxy, ethoxy, propoxy, isopropoxy, butoxy and the like.
　一般式（１）において、Ｒ１、Ｒ２およびＲ３で表される炭素原子数１～４のアルコキシカルボニル基としては、例えば、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、イソプロポキシカルボニル基等が挙げられる。 The alkoxycarbonyl group having 1 to 4 carbon atoms represented by R 1 , R 2 and R 3 in the general formula (1) is, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group Etc.
　一般式（１）において、Ｒ１、Ｒ２およびＲ３で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子等が挙げられる。 As a halogen atom represented by R < 1 >, R < 2 > and R < 3 > in General formula (1), a fluorine atom, a chlorine atom, a bromine atom etc. are mentioned.
　一般式（１）において、ｓ、ｔおよびｕは、各々独立して１～５の整数を表すが、ｓおよびｔは、好ましくは１，２または３であり、ｕは、より好ましくは、１である。 In the general formula (1), s, t and u each independently represent an integer of 1 to 5, but s and t are preferably 1, 2 or 3 and u is more preferably 1 It is.
　（Ａ）一般式（１）で表される透明化剤の具体例として、下記の化合物が挙げられる。ただし、本発明に係るジベンジリデンソルビトール化合物は、これらの化合物に限定されるものではない。 The following compounds may be mentioned as specific examples of the clarifying agent represented by (A) the general formula (1). However, the dibenzylidene sorbitol compound according to the present invention is not limited to these compounds.
Figure JPOXMLDOC01-appb-I000004
ＤＢＳ： 1,3:2,4-bis(O-benzylidene)sorbitol　融点２１８℃
Figure JPOXMLDOC01-appb-I000004
DBS: 1,3: 2,4-bis (O-benzylidene) sorbitol mp 218 ° C
Figure JPOXMLDOC01-appb-I000005
ＭＤＢＳ：1,3:2,4-bis(p-methylbenzylidene)sorbitol　　融点２５５－２６２℃
Figure JPOXMLDOC01-appb-I000005
MDBS: 1,3: 2,4-bis (p-methylbenzylidene) sorbitol melting point 255-262 ° C.
Figure JPOXMLDOC01-appb-I000006
1,3-O-benzylidene-2,4-O-3,4-dimethylbenzylidenesorbitol
Figure JPOXMLDOC01-appb-I000006
1,3-O-benzylidene-2,4-O-3,4-dimethylbenzylidenesorbitol
Figure JPOXMLDOC01-appb-I000007
Ｄ４ＭｏＢＳ: 1,3:2,4-bis(p-methoxybenzylidene)sorbitol
Figure JPOXMLDOC01-appb-I000007
D4MoBS: 1,3: 2,4-bis (p-methoxybenzylidene) sorbitol
Figure JPOXMLDOC01-appb-I000008
Ｄ４ＣｌＢＳ：1,3:2,4-bis(p-chlorobenzylidene)sorbitol
Figure JPOXMLDOC01-appb-I000008
D4ClBS: 1,3: 2,4-bis (p-chlorobenzylidene) sorbitol
Figure JPOXMLDOC01-appb-I000009
ＥＤＢＳ： 1,3:2,4-bis(p-ethylbenzylidene)sorbitol
Figure JPOXMLDOC01-appb-I000009
EDBS: 1,3: 2,4-bis (p-ethylbenzylidene) sorbitol
Figure JPOXMLDOC01-appb-I000010
ＤＭＤＢＳ：1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol
Figure JPOXMLDOC01-appb-I000010
DMDBS: 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol
Figure JPOXMLDOC01-appb-I000011
ＤＯＰＭＮ：1,2,3-toridesoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonitol
Figure JPOXMLDOC01-appb-I000011
DOPMN: 1,2,3-Toridesoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] nonitol
　本発明の透明化剤組成物における（Ｂ）分散助剤は、Ｆｅｄｏｒｓ法にて算出したＳＰ値が、１１．０以上でかつ、融点が２００℃以下の化合物である。より好ましくは、ｓｐ値が、１１．５～１３．８である。（Ｂ）分散助剤として、上記要件を満足する化合物を用いることで、（Ａ）一般式（１）で表されるジベンジリデンソルビトール化合物のオレフィン系樹脂に対する相溶性を改善することができる。これにより、オレフィン系樹脂に対して優れた透明化効果を付与することができる。 The (B) dispersion aid in the clarifying agent composition of the present invention is a compound having an SP value of 11.0 or more and a melting point of 200 ° C. or less calculated by the Fedors method. More preferably, the sp value is 11.5 to 13.8. By using a compound satisfying the above requirements as the (B) dispersion aid, the compatibility of the dibenzylidene sorbitol compound represented by the general formula (1) with the olefin resin can be improved. As a result, an excellent transparency effect can be provided to the olefin resin.
　本発明の透明化剤組成物において、ｓｐ値は、Ｆｅｄｏｒｓの方法により算出する。具体的には、ＳＰ値は、化合物の各原子または原子団の２５℃における蒸発エネルギーΔｅ（ｃａｌ）と、化合物を形成する各原子または原子団の２５℃におけるモル容積ΔＶ（ｃｍ３）とから、下記の式により算出する。
ｓｐ値＝（ΣΔｅ／ΣΔｖ）１／２
　なお、化合物が混合物である場合は、個々の成分のｓｐ値を算出し、これらのｓｐ値のそれぞれに対して各構成成分のモル分率を乗じたものを合算して算出する。 In the clarifying agent composition of the present invention, the sp value is calculated by the method of Fedors. Specifically, the SP value is calculated from the evaporation energy Δe (cal) at 25 ° C. of each atom or atomic group of the compound and the molar volume ΔV (cm 3 ) at 25 ° C. of each atom or atomic group forming the compound. , Calculated by the following equation.
sp value = (ΣΔe / ΣΔv) 1/2
In addition, when a compound is a mixture, the sp value of each component is calculated, and what multiplied the mole fraction of each component with respect to each of these sp values is added and calculated.
　本発明の透明化剤組成物は、（Ｂ）分散助剤の融点が、２００℃以下であるが、より好ましくは、１４５℃以下である。融点が２００℃以下の分散助剤であれば、オレフィン系樹脂の加工の際に十分溶融しており、本発明の効果を良好に得ることができる。 In the clarifying agent composition of the present invention, the melting point of the (B) dispersion aid is 200 ° C. or less, more preferably 145 ° C. or less. If it is a dispersion assistant having a melting point of 200 ° C. or less, it is sufficiently melted during processing of the olefin resin, and the effects of the present invention can be obtained well.
　本発明の透明化剤組成物は、（Ａ）一般式（１）で表される透明化剤１００質量部に対し、（Ｂ）分散助剤が、３０～１００質量部であり、（Ａ）一般式（１）で表される透明化剤を少なくとも５０質量％以上含むことが好ましく、６０質量％以上であることがより好ましい。また、本発明の透明化剤組成物は、（Ａ）一般式（１）で表される透明化剤以外の透明化剤や核剤を有していてもよく、オレフィン系樹脂に使用される添加剤を含有していてもよい。（Ａ）一般式（１）で表される透明化剤以外の透明化剤や核剤や添加剤としては、後述するオレフィン系樹脂組成物に配合され得る樹脂添加剤が挙げられる。 In the clarifying agent composition of the present invention, (B) dispersion aid is 30 to 100 parts by mass with respect to 100 parts by mass of the clarifying agent represented by the general formula (1), (A) It is preferable to include at least 50% by mass or more of the clarifying agent represented by General Formula (1), and more preferable to be 60% by mass or more. The transparentizing agent composition of the present invention may have a transparentizing agent or nucleating agent other than the transparentizing agent represented by (A) the general formula (1), and is used for the olefin resin You may contain the additive. (A) As a clarifier other than a clarifier represented by General formula (1), a nucleating agent, and an additive, the resin additive which may be mix | blended with the olefin resin composition mentioned later is mentioned.
　次に、本発明のオレフィン系樹脂組成物について説明する。
　本発明のオレフィン系樹脂組成物は、オレフィン系樹脂１００質量部に対して、（Ａ）一般式（１）で表される透明化剤が、０．００１～１０質量部含有するように、透明化剤組成物を含有するものであり、０．００５～５質量部が好ましく、０．０１～０．５質量部の範囲がより好ましい。０．００１質量部より少ないと透明化剤の添加効果が不十分になる場合があり、１０質量部より多いと、成形品から透明化剤組成物の成分が、ブリードアウトする場合がある。 Next, the olefin resin composition of the present invention will be described.
The olefin resin composition of the present invention is transparent so that the transparentizing agent represented by the general formula (A) is contained in an amount of 0.001 to 10 parts by mass with respect to 100 parts by mass of the olefin resin. The composition contains the agent composition, preferably 0.005 to 5 parts by mass, and more preferably 0.01 to 0.5 parts by mass. If the amount is less than 0.001 part by mass, the effect of adding the clarifying agent may be insufficient. If the amount is more than 10 parts by mass, the components of the clarifying agent composition may bleed out from the molded article.
　本発明のオレフィン系樹脂組成物に用いられるオレフィン樹脂としては、例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（Ｌ－ＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、ヘミアイソタクチックポリプロピレン、シクロオレフィンポリマー、ステレオブロックポリプロピレン、ポリ－３－メチル－１－ブテン、ポリ－３－メチル－１－ペンテン、ポリ－４－メチル－１－ペンテン等のα－オレフィン重合体、エチレン／プロピレンブロックまたはランダム共重合体、インパクトコポリマーポリプロピレン、エチレン－メチルメタクリレート共重合体、エチレン－メチルアクリレート共重合体、エチレン－エチルアクリレート共重合体、エチレン－ブチルアクリレート共重合体、エチレン－酢酸ビニル共重合体、エチレン－ビニルアルコール樹脂（ＥＶＯＨ）等のα－オレフィン共重合体等が挙げられ、エラストマーであってもよい。本発明においては、これら２種以上をブレンドして使用してもよく、ブロック共重合体を形成してブロックポリマー型として使用してもよく、樹脂がアロイ化されていてもよい。また、これらのオレフィン系樹脂の塩素化物であってもよい。 As an olefin resin used for the olefin resin composition of the present invention, for example, low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), high density polyethylene (HDPE), isotactic polypropylene, syndi Α such as tactic polypropylene, hemiisotactic polypropylene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene -Olefin polymer, ethylene / propylene block or random copolymer, impact copolymer polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, air Len - butyl acrylate copolymer, ethylene - vinyl acetate copolymer, ethylene - alpha-olefin copolymer such as polyvinyl alcohol resin (EVOH). These may be an elastomer. In the present invention, these two or more kinds may be blended and used, a block copolymer may be formed and used as a block polymer type, and the resin may be alloyed. In addition, chlorinated products of these olefin resins may be used.
　オレフィン系樹脂のエラストマーとしては、ハードセグメントとしてポリプロピレンやポリエチレン等のポリオレフィン、ソフトセグメントとしてエチレン－プロピレンゴム等のゴムを用いて、これらをブレンドすることにより得られるエラストマー、或いは動的架橋により得られるエラストマーが挙げられる。 Elastomers obtained by blending polyolefins such as polypropylene and polyethylene as hard segments and rubbers such as ethylene-propylene rubber as soft segments as elastomers of olefin resins, or elastomers obtained by dynamic crosslinking Can be mentioned.
　ハードセグメントとしては、例えば、ポリプロピレンホモポリマー、ポリプロピレンブロックコポリマー、ポリプロピレンランダムコポリマー等から選ばれる少なくとも１種があげられる。 Examples of the hard segment include at least one selected from polypropylene homopolymers, polypropylene block copolymers, polypropylene random copolymers, and the like.
　ソフトセグメントとしては、エチレンープロピレン共重合体（ＥＰＭ）、エチレン－プロピレン－ジエン共重合体（ＥＰＤＭ）、エチレン－酢酸ビニル共重合体（ＥＶＡ）、酢酸ビニルホモポリマー等が挙げられる。これら２種以上をブレンドして使用してもよい。 Examples of the soft segment include ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), vinyl acetate homopolymer and the like. You may blend and use these 2 or more types.
　上記オレフィン系樹脂の製造方法は、チーグラー触媒、チーグラー・ナッタ触媒、メタロセン触媒その他の各種重合触媒を助触媒、触媒の担体、連鎖移動剤を含め、また、気相重合、溶液重合、乳化重合、塊状重合等の各種重合方法において、温度、圧力、濃度、流速や触媒残渣の除去等の各種重合条件等、目的とする製品に適した物性の樹脂が得られるものや、目的とする製品の成形加工に適した物性の樹脂が得られるものを適宜選択して製造される。オレフィン系樹脂の数平均分子量、重量平均分子量、分子量分布、メルトフローレート（ＭＦＲ）、融点、融解ピーク温度、アイソタクチック、シンジオタクチック等の立体規則性、分岐の有無や程度、比重、各種溶媒への溶解成分の比率、Ｈａｚｅ、グロス、衝撃強度、曲げ弾性率、オルゼン剛性、その他の特性および各特性値が特定の式を満足するか否か等は所望する特性に応じて適宜選択することができる。 The above olefin resin production methods include Ziegler catalysts, Ziegler-Natta catalysts, metallocene catalysts and other various polymerization catalysts including cocatalysts, catalyst carriers, chain transfer agents, and also gas phase polymerization, solution polymerization, emulsion polymerization, In various polymerization methods such as bulk polymerization, resins having physical properties suitable for the target product such as temperature, pressure, concentration, flow rate and various polymerization conditions such as removal of catalyst residue can be obtained, and molding of the target product It selects suitably what can obtain resin of a physical property suitable for processing. Number average molecular weight, weight average molecular weight, molecular weight distribution, melt flow rate (MFR), melting point, melting peak temperature, stereoregularity such as isotactic and syndiotactic, presence or absence of branching, specific gravity, various types of olefin resins The ratio of components dissolved in solvent, Haze, gloss, impact strength, flexural modulus, Olsen stiffness, other characteristics, and whether each characteristic value satisfies a specific equation, etc. are appropriately selected according to the desired characteristics. be able to.
　本発明の透明化剤組成物、またはオレフィン系樹脂組成物においては、本発明の効果を著しく損なわない範囲で、任意で公知の樹脂添加剤（例えば、フェノール系酸化防止剤、リン系酸化防止剤、チオエーテル系酸化防止剤、紫外線吸収剤、ヒンダードアミン化合物、上記（Ａ）一般式（１）で表される透明化剤と異なる核剤、難燃剤、難燃助剤、滑剤、充填剤、ハイドロタルサイト類、帯電防止剤、顔料、蛍光増白剤、染料等）を含有させてもよい。 In the clarifying agent composition or the olefin resin composition of the present invention, any known resin additive (for example, a phenolic antioxidant, a phosphorus antioxidant, etc.) can be used as long as the effects of the present invention are not significantly impaired. Thioether-based antioxidants, UV absorbers, hindered amine compounds, nucleating agents different from the clarifying agents represented by the above-mentioned (A) general formula (1), flame retardants, flame retardant aids, lubricants, fillers, hydrotal Sites, antistatic agents, pigments, fluorescent whitening agents, dyes, etc.) may be contained.
　フェノール系酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－エチルフェノール、２－ｔｅｒｔ－ブチル－４，６－ジメチルフェノール、スチレン化フェノール、２，２’－メチレンビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－チオビス－（６－ｔｅｒｔ－ブチル－４－メチルフェノール）、２，２’－チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２－メチル－４，６－ビス（オクチルスルファニルメチル）フェノール、２，２’－イソブチリデンビス（４，６－ジメチルフェノール）、イソオクチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ’－ヘキサン－１，６－ジイルビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオンアミド、２，２’－オキサミド－ビス［エチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２－エチルヘキシル－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート、２，２’－エチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェノール）、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ－ベンゼンプロパン酸およびＣ１３－１５アルキルのエステル、２，５－ジ－ｔｅｒｔ－アミルヒドロキノン、ヒンダードフェノールの重合物（ＡＤＥＫＡ　ＰＯＬＹＭＥＲ　ＡＤＤＩＴＩＶＥＳ　ＥＵＲＯＰＥ　ＳＡＳ社製商品名「ＡＯ．ＯＨ．９８」）、２，２’－メチレンビス［６－（１－メチルシクロヘキシル）－ｐ－クレゾール］、２－ｔｅｒｔ－ブチル－６－（３－ｔｅｒｔ－ブチル－２－ヒドロキシ－５－メチルベンジル）－４－メチルフェニルアクリレート、２－［１－（２－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ペンチルフェニル）エチル］－４，６－ジ－ｔｅｒｔ－ペンチルフェニルアクリレート、６－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチル）プロポキシ］－２，４，８，１０－テトラ－ｔｅｒｔ－ブチルベンズ［ｄ，ｆ］［１，３，２］－ジオキサホスフォビン、ヘキサメチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、ビス［モノエチル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）ホスホネート］カルシウム塩、５，７－ビス（１，１－ジメチルエチル）－３－ヒドロキシ－２（３Ｈ）－ベンゾフラノンとｏ－キシレンとの反応生成物、２，６－ジ－ｔｅｒｔ－ブチル－４－（４，６－ビス（オクチルチオ）－１，３，５－トリアジン－２－イルアミノ）フェノール、ＤＬ－ａ－トコフェノール（ビタミンＥ）、２，６－ビス（α－メチルベンジル）－４－メチルフェノール、ビス［３，３－ビス－（４’－ヒドロキシ－３’－ｔｅｒｔ－ブチル－フェニル）ブタン酸］グリコールエステル、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、２，６－ジフェニル－４－オクタデシロキシフェノール、ステアリル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、ジステアリル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）ホスホネート、トリデシル－３，５－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルチオアセテート、チオジエチレンビス［（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、４，４’－チオビス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）、２－オクチルチオ－４，６－ジ（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェノキシ）－ｓ－トリアジン、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、ビス［３，３－ビス（４－ヒドロキシ－３－ｔｅｒｔ－ブチルフェニル）ブチリックアシッド］グリコールエステル、４，４’－ブチリデンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）、４，４’－ブチリデンビス（６－ｔｅｒｔ－ブチル－３－メチルフェノール）、２，２’－エチリデンビス（４，６－ジ－ｔｅｒｔ－ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、ビス［２－ｔｅｒｔ－ブチル－４－メチル－６－（２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－メチルベンジル）フェニル］テレフタレート、１，３，５－トリス（２，６－ジメチル－３－ヒドロキシ－４－ｔｅｒｔ－ブチルベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－２，４，６－トリメチルベンゼン、１，３，５－トリス［（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシエチル］イソシアヌレート、テトラキス［メチレン－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン、２－ｔｅｒｔ－ブチル－４－メチル－６－（２－アクリロイルオキシ－３－ｔｅｒｔ－ブチル－５－メチルベンジル）フェノール、３，９－ビス［２－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルヒドロシンナモイルオキシ）－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、トリエチレングリコールビス［β－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート］、ステアリル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド、パルミチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド、ミリスチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド、ラウリル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド等の３－（３，５－ジアルキル－４－ヒドロキシフェニル）プロピオン酸誘導体等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。フェノール系酸化防止剤を配合する場合の配合量は、オレフィン系樹脂１００質量部に対し、０．００１～５質量部が好ましく、より好ましくは、０．０３～３質量部である。 As a phenolic antioxidant, for example, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis (4 -Ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis 3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionamide, 2,2′-oxamido-bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], 2-ethylhexyl 3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2,2′-ethylenebis (4,6-di-tert-butylphenol), 3 , 5-Di-tert-butyl-4-hydroxy-benzenepropanoic acid and esters of C13-15 alkyl, 2,5-di-tert-amyl hydroquinone, polymers of hindered phenols (ADEKA POLYMER ADDITIVES EUROPE SAS products Name "AO. OH. 98"), 2,2'-Methylene bis [6- 1-Methylcyclohexyl) -p-cresol], 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-) Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-Tetra-tert-butylbenz [d, f] [1,3,2] -dioxaphosphobin, hexamethylene bis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate, bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] calcium salt, 5 Product of the reaction of 2,7-bis (1,1-dimethylethyl) -3-hydroxy-2 (3H) -benzofuranone with o-xylene, 2,6-di-tert-butyl-4- (4,6- Bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, DL-a-tocopherol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3 , 3-Bis- (4'-hydroxy-3'-tert-butyl-phenyl) butanoic acid] glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octade Siloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxyl) Benzyl) phosphonate, tridecyl-3,5-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4 -Methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidene bis (2,6-di-tert -Butylphenol), 4,4'-Butylidenebis (6-tert-butyl-3-methylpheno) ), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [ 2-tert-Butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy- 4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-) tert-Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyl oxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- ( 2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1- Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl- 3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionic acid amide, palmitic acid 3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionic acid amide, myristyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl- Examples thereof include 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide. One of these may be used alone, or two or more may be used in combination. The blending amount of the phenolic antioxidant is preferably 0.001 to 5 parts by mass, and more preferably 0.03 to 3 parts by mass, with respect to 100 parts by mass of the olefin resin.
　リン系酸化防止剤としては、例えば、トリフェニルホスファイト、ジイソオクチルホスファイト、ヘプタキス（ジプロピレングリコール）トリホスファイト、トリイソデシルホスファイト、ジフェニルイソオクチルホスファイト、ジイソオクチルフェニルホスファイト、ジフェニルトリデシルホスファイト、トリイソオクチルホスファイト、トリラウリルホスファイト、ジフェニルホスファイト、トリス（ジプロピレングリコール）ホスファイト、ジイソデシルペンタエリスリトールジホスファイト、ジオレイルヒドロゲンホスファイト、トリラウリルトリチオホスファイト、ビス（トリデシル）ホスファイト、トリス（イソデシル）ホスファイト、トリス（トリデシル）ホスファイト、ジフェニルデシルホスファイト、ジノニルフェニルビス（ノニルフェニル）ホスファイト、ポリ（ジプロピレングリコール）フェニルホスファイト、テトラフェニルジプロピルグリコールジホスファイト、トリスノニルフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチル－５－メチルフェニル）ホスファイト、トリス〔２－ｔｅｒｔ－ブチル－４－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニルチオ）－５－メチルフェニル〕ホスファイト、トリ（デシル）ホスファイト、オクチルジフェニルホスファイト、ジ（デシル）モノフェニルホスファイト、ジステアリルペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールとステアリン酸カルシウム塩との混合物、アルキル（Ｃ１０）ビスフェノールＡホスファイト、ジ（トリデシル）ペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４，６－トリ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト、テトラフェニル－テトラ（トリデシル）ペンタエリスリトールテトラホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）エチルホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）－４，４’－ｎ－ブチリデンビス（２―ｔｅｒｔ－ブチル－５－メチルフェノール）ジホスファイト、ヘキサ（トリデシル）－１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタントリホスファイト、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ビフェニレンジホスホナイト、９，１０－ジハイドロ－９－オキサ－１０－ホスファフェナンスレン－１０－オキサイド、（１－メチル－１―プロペニル－３－イリデン）トリス（１，１－ジメチルエチル）－５－メチル－４，１－フェニレン）ヘキサトリデシルホスファイト、２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）－２－エチルヘキシルホスファイト、２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）－オクタデシルホスファイト、２，２’－エチリデンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）フルオロホスファイト、４，４’－ブチリデンビス（３－メチル－６－ｔｅｒｔ－ブチルフェニルジトリデシル）ホスファイト、トリス（２－〔（２，４，８，１０－テトラキス－ｔｅｒｔ－ブチルジベンゾ〔ｄ，ｆ〕〔１，３，２〕ジオキサホスフェピン－６－イル）オキシ〕エチル）アミン、３，９－ビス（４－ノニルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスフェススピロ［５，５］ウンデカン、２，４，６－トリ－ｔｅｒｔ－ブチルフェニル－２－ブチル－２－エチル－１，３－プロパンジオールホスファイト、ポリ４，４’－イソプロピリデンジフェノールＣ１２－１５アルコールホスファイト等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。リン系酸化防止剤を配合する場合の配合量は、オレフィン系樹脂１００質量部に対して、０．００１～１０質量部が好ましく、より好ましくは、０．０１～０．５質量部である。 Examples of phosphorus-based antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, diphenyl Tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (Tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyl decyl phosphite, dinonylphenyl (Nonylphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyl dipropyl glycol diphosphite, tris nonyl phenyl phosphite, tris (2,4- di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methyl Phenyl] phosphite, tri (decyl) phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl (C 0) Bisphenol A phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2) , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) ) Pentaerythritol diphosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidene diphenol- Ludiphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-) Hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, (1-methyl-1-propenyl-3-ylidene) tris (1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecyl phosphite, 2,2′-methylene bis (4 , 6-Di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methyle Bis (4,6-di-tert-butylphenyl) -octadecyl phosphite, 2,2'-ethylidene bis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4'-butylidene bis (3- Methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphe) Pin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphes spiro [5,5] undecane, 2 , 4,6-Tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4'-isopropylidene dipheno Le C12-15 alcohols phosphite, and the like. One of these may be used alone, or two or more may be used in combination. The blending amount of the phosphorus-based antioxidant is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
　チオエーテル系酸化防止剤としては、例えば、テトラキス［メチレン－３－（ラウリルチオ）プロピオネート］メタン、ビス（メチル－４－［３－ｎ－アルキル（Ｃ１２／Ｃ１４）チオプロピオニルオキシ］５－ｔｅｒｔ－ブチルフェニル）スルファイド、ジトリデシル－３，３’－チオジプロピオネート、ジラウリル－３，３’－チオジプロピオネート、ジミリスチル－３，３’－チオジプロピオネート、ジステアリル－３，３’－チオジプロピオネート、ラウリル／ステアリルチオジプロピオネート、４，４’－チオビス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）、２，２’－チオビス（６－ｔｅｒｔ－ブチル－ｐ－クレゾール）、ジステアリル－ジサルファイドが挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。チオエーテル系酸化防止剤を配合する場合の配合量は、オレフィン系樹脂１００質量部に対して、０．００１～１０質量部が好ましく、より好ましくは、０．０１～０．５質量部である。 Examples of thioether-based antioxidants include tetrakis [methylene-3- (laurylthio) propionate] methane and bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl ) Sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropioate , Lauryl / stearylthiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-thiobis (6-tert-butyl-p-cresol), distearyl-di Sulfide is mentioned. One of these may be used alone, or two or more may be used in combination. The blending amount of the thioether antioxidant is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
　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ェノン、５，５’－メチレンビス（２－ヒドロキシ－４－メトキシベンゾフェノン）等の２－ヒドロキシベンゾフェノン類；２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ｔｅｒｔ－オクチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２－ヒドロキシ－３，５－ジクミルフェニル）ベンゾトリアゾール、２，２’－メチレンビス（４－ｔｅｒｔ－オクチル－６－ベンゾトリアゾリルフェノール）、２－（２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－カルボキシフェニル）ベンゾトリアゾールのポリエチレングリコールエステル、２－〔２－ヒドロキシ－３－（２－アクリロイルオキシエチル）－５－メチルフェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－（２－メタクリロイルオキシエチル）－５－ｔｅｒｔ－ブチルフェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－（２－メタクリロイルオキシエチル）－５－ｔｅｒｔ－オクチルフェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－（２－メタクリロイルオキシエチル）－５－ｔｅｒｔ－ブチルフェニル〕－５－クロロベンゾトリアゾール、２－〔２－ヒドロキシ－５－（２－メタクリロイルオキシエチル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－（２－メタクリロイルオキシエチル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－ｔｅｒｔ－アミル－５－（２－メタクリロイルオキシエチル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－（３－メタクリロイルオキシプロピル）フェニル〕－５－クロロベンゾトリアゾール、２－〔２－ヒドロキシ－４－（２－メタクリロイルオキシメチル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－４－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－４－（３－メタクリロイルオキシプロピル）フェニル〕ベンゾトリアゾール等の２－（２－ヒドロキシフェニル）ベンゾトリアゾール類；フェニルサリシレート、レゾルシノールモノベンゾエート、２，４－ジ－ｔｅｒｔ－ブチルフェニル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンゾエート、オクチル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、ドデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、テトラデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、ヘキサデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、オクタデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、ベヘニル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート等のベンゾエート類；２－エチル－２’－エトキシオキザニリド、２－エトキシ－４’－ドデシルオキザニリド等の置換オキザニリド類；エチル－α－シアノ－β，β－ジフェニルアクリレート、メチル－２－シアノ－３－メチル－３－（ｐ－メトキシフェニル）アクリレート等のシアノアクリレート類；各種の金属塩、または金属キレート、特にニッケル、クロムの塩、またはキレート類等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。紫外線吸収剤を配合する場合の配合量は、オレフィン系樹脂１００質量部に対して、０．００１～１０質量部が好ましく、より好ましくは、０．０１～０．５質量部である。 Examples of UV absorbers include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) ) Benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 -Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert- Octyl-6-benzotriazolylphenol), 2- (2-hydroxy) Polyethylene glycol ester of -3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy -3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3 tert-Butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2- Hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [ 2- (2-hydroxy) such as 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole Phenyl) benzotriazoles Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) Benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl- Benzoates such as 4-hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl- 2'-Ethoxy oxanilide, 2-ethoxy-4'-dode Substituted oxanilides such as luoxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts, Or metal chelates, particularly salts of nickel, chromium, or chelates. One of these may be used alone, or two or more may be used in combination. The blending amount of the ultraviolet absorber is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
　ヒンダードアミン化合物としては、例えば、２，２，６，６－テトラメチル－４－ピペリジルステアレート、１，２，２，６，６－ペンタメチル－４－ピペリジルステアレート、２，２，６，６－テトラメチル－４－ピペリジルベンゾエート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、テトラキス（２，２，６，６－テトラメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）・ジ（トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、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）－１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，４，４－ペンタメチル－４－ピペリジル）－２－ブチル－２－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）マロネート、１－（２－ヒドロキシエチル）－２，２，６，６－テトラメチル－４－ピペリジノ－ル／コハク酸ジエチル重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－モルホリノ－ｓ－トリアジン重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－ｔｅｒｔ－オクチルアミノ－ｓ－トリアジン重縮合物、１，５，８，１２－テトラキス〔２，４－ビス（Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕－１，５，８，１２－テトラアザドデカン、１，５，８，１２－テトラキス〔２，４－ビス（Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕－１，５，８－１２－テトラアザドデカン、１，６，１１－トリス〔２，４－ビス（Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕アミノウンデカン、１，６，１１－トリス〔２，４－ビス（Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕アミノウンデカン、ビス｛４－（１－オクチルオキシ－２，２，６，６－テトラメチル）ピペリジル｝デカンジオナート、ビス｛４－（２，２，６，６－テトラメチル－１－ウンデシルオキシ）ピペリジル）カーボナート等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。ヒンダードアミン化合物を配合する場合の配合量は、オレフィン系樹脂１００質量部に対して、０．００１～１０質量部が好ましく、より好ましくは０．０１～０．５質量部である。 As the hindered amine compound, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6- Tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 2,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6- Tetramethyl-4-piperidyl), di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-pipe) Jyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5) -Di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6 -Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6, 6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-) Butyl-N- ( 2,2,6,6-Tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2, 2, 4-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane 1,1,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane 1,1,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] amino Undecane, bis {4- (1-octyloxy-2,2,6,6 -Tetramethyl) piperidyl} decantionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate and the like. One of these may be used alone, or two or more may be used in combination. The blending amount of the hindered amine compound is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
　上記（Ａ）一般式（１）で表される透明化剤と異なる核剤としては、例えば、安息香酸ナトリウム、４－ｔｅｒｔ－ブチル安息香酸アルミニウム塩、アジピン酸ナトリウムおよび２ナトリウムビシクロ［２．２．１］ヘプタン－２，３－ジカルボキシレート等のカルボン酸金属塩、Ｎ，Ｎ’，Ｎ”－トリス［２－メチルシクロヘキシル］－１，２，３－プロパントリカルボキサミド、Ｎ，Ｎ’，Ｎ”－トリシクロヘキシル－１，３，５－ベンゼントリカルボキサミド、Ｎ，Ｎ’－ジシクロヘキシルナフタレンジカルボキサミド、１，３，５－トリ（ジメチルイソプロポイルアミノ）ベンゼン等のアミド化合物等を挙げることができる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。（Ａ）一般式（１）で表される透明化剤と異なる核剤を配合する場合の配合量は、オレフィン系樹脂１００質量部に対して、（Ａ）一般式（１）で表される透明化剤との合計量が０．００１～１０質量部が好ましく、より好ましくは、０．００５～５質量部の範囲内である。 Examples of nucleating agents different from the clarifying agent represented by the above general formula (A) include sodium benzoate, aluminum salt of 4-tert-butylbenzoic acid, sodium adipate and disodium bicyclo [2.2. .1] Metal carboxylates such as heptane-2,3-dicarboxylate, N, N ', N "-tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N', Amide compounds such as N ′ ′-tricyclohexyl-1,3,5-benzenetricarboxamide, N, N′-dicyclohexyl naphthalene dicarboxamide, 1,3,5-tri (dimethylisopropoylamino) benzene etc. may be mentioned it can. One of these may be used alone, or two or more may be used in combination. The blending amount of the nucleating agent different from the clarifying agent represented by the general formula (1) (A) is represented by the general formula (1) with respect to 100 parts by mass of the olefin resin. The total amount with the clarifying agent is preferably 0.001 to 10 parts by mass, more preferably in the range of 0.005 to 5 parts by mass.
　難燃剤としては、例えば、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、クレジル－２，６－ジキシレニルホスフェート、レゾルシノールビス（ジフェニルホスフェート）、（１－メチルエチリデン）－４，１－フェニレンテトラフェニルジホスフェート、１，３－フェニレンテトラキス（２，６－ジメチルフェニル）ホスフェート、株式会社ＡＤＥＫＡ製商品名「アデカスタブＦＰ－５００」、「アデカスタブＦＰ－６００」、「アデカスタブＦＰ－８００」の芳香族リン酸エステル、フェニルホスホン酸ジビニル、フェニルホスホン酸ジアリル、フェニルホスホン酸（１－ブテニル）等のホスホン酸エステル、ジフェニルホスフィン酸フェニル、ジフェニルホスフィン酸メチル、９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド誘導体等のホスフィン酸エステル、ビス（２－アリルフェノキシ）ホスファゼン、ジクレジルホスファゼン等のホスファゼン化合物、リン酸メラミン、ピロリン酸メラミン、ポリリン酸メラミン、ポリリン酸メラム、ポリリン酸アンモニウム、リン酸ピペラジン、ピロリン酸ピペラジン、ポリリン酸ピペラジン、リン含有ビニルベンジル化合物および赤リン等のリン系難燃剤、水酸化マグネシウム、水酸化アルミニウム等の金属水酸化物、臭素化ビスフェノールＡ型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂、ヘキサブロモベンゼン、ペンタブロモトルエン、エチレンビス（ペンタブロモフェニル）、エチレンビステトラブロモフタルイミド、１，２－ジブロモ－４－（１，２－ジブロモエチル）シクロヘキサン、テトラブロモシクロオクタン、ヘキサブロモシクロドデカン、ビス（トリブロモフェノキシ）エタン、臭素化ポリフェニレンエーテル、臭素化ポリスチレンおよび２，４，６－トリス（トリブロモフェノキシ）－１，３，５－トリアジン、トリブロモフェニルマレイミド、トリブロモフェニルアクリレート、トリブロモフェニルメタクリレート、テトラブロモビスフェノールＡ型ジメタクリレート、ペンタブロモベンジルアクリレート、および、臭素化スチレン等の臭素系難燃剤等を挙げることができる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。これら難燃剤はフッ素樹脂等のドリップ防止剤や多価アルコール、ハイドロタルサイト等の難燃助剤と併用することが好ましい。難燃剤を配合する場合の配合量は、オレフィン系樹脂１００質量部に対して、１～１００質量部が好ましく、より好ましくは、１０～７０質量部である。 As a flame retardant, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methyl ethylidene) -4,1-phenylene tetraphenyl diphosphate, 1,3-phenylene tetrakis (2,6-dimethylphenyl) phosphate, manufactured by ADEKA CORPORATION under the trade name "Adecastab FP-500", "Adecastab FP-600", "Adecastab FP" Phosphonates such as aromatic phosphoric acid ester of "-800", divinyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, diphenyl Phosphinic acid esters such as methyl sphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, melamine phosphate Phosphorus flame retardants such as melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinyl benzyl compound and red phosphorus, magnesium hydroxide, hydroxide Metal hydroxides such as aluminum, brominated bisphenol A epoxy resin, brominated phenol novolak epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis (pentabromophenyl), ethylene biste Labromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2 , 4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate, and Brominated flame retardants, such as brominated styrene etc. can be mentioned. One of these may be used alone, or two or more may be used in combination. These flame retardants are preferably used in combination with anti-drip agents such as fluorocarbon resins and the like, and flame retardant aids such as polyhydric alcohols and hydrotalcites. The blending amount in the case of blending the flame retardant is preferably 1 to 100 parts by mass, and more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the olefin resin.
　滑剤は、成形体表面に滑性を付与し傷つき防止効果を高める目的で加えられる。滑剤としては、例えば、オレイン酸アミド、エルカ酸アミド等の不飽和脂肪酸アミド；ベヘン酸アミド、ステアリン酸アミド等の飽和脂肪酸アミド、ブチルステアレート、ステアリルアルコール、ステアリン酸モノグリセライド、ソルビタンモノパルミチテート、ソルビタンモノステアレート、マンニトール、ステアリン酸、硬化ひまし油、ステアリン酸アマイド、オレイン酸アマイド、エチレンビスステアリン酸アマイド等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。滑剤を配合する場合の配合量は、オレフィン系樹脂１００質量部に対して、０．０１～２質量部が好ましく、より好ましくは、０．０３～０．５質量部である。 A lubricant is added for the purpose of imparting lubricity to the surface of the molded body to enhance the scratch resistance. As the lubricant, for example, unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, monoglyceride stearate, sorbitan monopalmitate tartrate, Sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylenebisstearic acid amide and the like can be mentioned. One of these may be used alone, or two or more may be used in combination. The blending amount in the case of blending the lubricant is preferably 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.
　充填剤としては、例えば、タルク、マイカ、炭酸カルシウム、酸化カルシウム、水酸化カルシウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、硫酸マグネシウム、水酸化アルミニウム、硫酸バリウム、ガラス粉末、ガラス繊維、クレー、ドロマイト、シリカ、アルミナ、チタン酸カリウムウィスカー、ワラステナイト、繊維状マグネシウムオキシサルフェート等を挙げることができ、粒子径（繊維状においては繊維径や繊維長およびアスペクト比）を適宜選択して用いることができる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。また、充填剤は、必要に応じて表面処理したものを用いることができる。充填剤を配合する場合の配合量は、オレフィン系樹脂１００質量部に対して、１～８０質量部が好ましく、より好ましくは、３～５０質量部、さらに好ましくは、５～４０質量部である。 As the filler, for example, talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium hydroxide, magnesium hydroxide, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite Silica, alumina, potassium titanate whiskers, wallastonite, fibrous magnesium oxysulfate, etc., and the particle diameter (fiber diameter, fiber length and aspect ratio in fibrous form) can be appropriately selected and used. . One of these may be used alone, or two or more may be used in combination. Moreover, the filler can use what was surface-treated as needed. The blending amount in the case of blending the filler is preferably 1 to 80 parts by mass, more preferably 3 to 50 parts by mass, still more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the olefin resin .
　ハイドロタルサイト類としては、天然物や合成物として知られるマグネシウム、アルミニウム、水酸基、炭酸基および任意の結晶水からなる複合塩化合物であり、マグネシウムまたはアルミニウムの一部をアルカリ金属や亜鉛等他の金属で置換したものや水酸基、炭酸基を他のアニオン基で置換したものが挙げられ、具体的には、例えば、下記一般式（２）で表されるハイドロタルサイトの金属をアルカリ金属に置換したものが挙げられる。また、Ａｌ－Ｌｉ系のハイドロタルサイト類としては、下記一般式（３）で表される化合物も用いることができる。 The hydrotalcites are complex salt compounds consisting of magnesium, aluminum, hydroxyl group, carbonate group and any crystal water known as natural products or synthetic compounds, and some of magnesium or aluminum are alkali metal, zinc and others. What substituted by metal, and what substituted the hydroxyl group and the carbonic acid group by the other anion group is mentioned, For example, the metal of the hydrotalcite represented by following General formula (2) is substituted by the alkali metal Are listed. Further, as the Al—Li-based hydrotalcites, compounds represented by the following general formula (3) can also be used.
Figure JPOXMLDOC01-appb-I000012
　ここで、一般式（２）中、ｘ１およびｘ２はそれぞれ下記式、０≦ｘ２／ｘ１＜１０，２≦ｘ１＋ｘ２≦２０で表される条件を満たす数を表し、ｐは０または正の数を表す。
Figure JPOXMLDOC01-appb-I000012
Here, in the general formula (2), x1 and x2 each represent a number satisfying the condition represented by the following formula, 0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 ≦ 20, and p is 0 or a positive number. Represent.
Figure JPOXMLDOC01-appb-I000013
　ここで、一般式（３）中、Ａｑ－は、ｑ価のアニオンを表し、ｐは０または正の数を表す。また、これらハイドロタルサイト類における炭酸アニオンは、一部を他のアニオンで置換したものでもよい。
Figure JPOXMLDOC01-appb-I000013
Here, in the general formula (3), A q- represents a q-valent anion, and p represents 0 or a positive number. In addition, the carbonate anion in these hydrotalcites may be partially substituted by another anion.
　ハイドロタルサイト類は、結晶水を脱水したものであってもよく、ステアリン酸等の高級脂肪酸、オレイン酸アルカリ金属塩等の高級脂肪酸金属塩、ドデシルベンゼンスルホン酸アルカリ金属塩等の有機スルホン酸金属塩、高級脂肪酸アミド、高級脂肪酸エステルまたはワックス等で被覆されたものであってもよい。 The hydrotalcites may be those obtained by dehydrating water of crystallization, and higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and organic sulfonic acid metals such as alkali metal dodecylbenzene sulfonate It may be coated with a salt, a higher fatty acid amide, a higher fatty acid ester or a wax.
　ハイドロタルサイト類は、天然物であってもよく、また合成品であってもよい。ハイドロタルサイト類の合成方法としては、特公昭４６－２２８０号公報、特公昭５０－３００３９号公報、特公昭５１－２９１２９号公報、特公平３－３６８３９号公報、特開昭６１－１７４２７０号公報、特開平５－１７９０５２号公報等に記載されている公知の方法が挙げられる。また、ハイドロタルサイト類は、その結晶構造、結晶粒子等に制限されることなく使用することができる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。ハイドロタルサイト類を配合する場合の配合量は、オレフィン系樹脂１００質量部に対し、０．００１～５質量部が好ましく、より好ましくは、０．０１～３質量部である。 The hydrotalcites may be natural products or may be synthetic products. As a method for synthesizing hydrotalcites, JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, JP-A-61-174270. Examples thereof include known methods described in JP-A-5-179052. In addition, hydrotalcites can be used without being limited to the crystal structure, crystal particles and the like. One of these may be used alone, or two or more may be used in combination. The blending amount of the hydrotalcites is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the olefin resin.
　帯電防止剤としては、例えば、脂肪酸第四級アンモニウムイオン塩、ポリアミン四級塩等のカチオン系帯電防止剤；高級アルコールリン酸エステル塩、高級アルコールＥＯ付加物、ポリエチレングリコール脂肪酸エステル、アニオン型のアルキルスルホン酸塩、高級アルコール硫酸エステル塩、高級アルコールエチレンオキシド付加物硫酸エステル塩、高級アルコールエチレンオキシド付加物リン酸エステル塩等のアニオン系帯電防止剤；多価アルコール脂肪酸エステル、ポリグリコールリン酸エステル、ポリオキシエチレンアルキルアリルエーテル等のノニオン系帯電防止剤；アルキルジメチルアミノ酢酸ベタイン等の両性型アルキルベタイン、イミダゾリン型両性活性剤等の両性帯電防止剤、ポリエーテルエステルポリアミド等の高分子型帯電防止剤が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。帯電防止剤を配合する場合の配合量は、オレフィン系樹脂１００質量部に対して、０．０３～２質量部が好ましく、より好ましくは、０．１～０．８質量部である。 Examples of antistatic agents include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, alkyl of anionic type Anionic antistatic agents such as sulfonates, higher alcohol sulfuric acid ester salts, higher alcohol ethylene oxide adduct sulfuric acid ester salts, higher alcohol ethylene oxide adduct phosphoric acid ester salts; polyhydric alcohol fatty acid esters, polyglycol phosphoric acid esters, polyoxy acids Nonionic antistatic agent such as ethylene alkyl allyl ether; amphoteric alkyl betaine such as alkyl dimethylamino acetic acid betaine, amphoteric antistatic agent such as imidazoline type amphoteric surfactant, and high molecular weight such as polyether ester polyamide Type antistatic agents. One of these may be used alone, or two or more may be used in combination. The blending amount of the antistatic agent is preferably 0.03 to 2 parts by mass, and more preferably 0.1 to 0.8 parts by mass with respect to 100 parts by mass of the olefin resin.
　顔料としては、市販の顔料を用いることもでき、例えば、ピグメントレッド１、２、３、９、１０、１７、２２、２３、３１、３８、４１、４８、４９、８８、９０、９７、１１２、１１９、１２２、１２３、１４４、１４９、１６６、１６８、１６９、１７０、１７１、１７７、１７９、１８０、１８４、１８５、１９２、２００、２０２、２０９、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、２５４；ピグメントオレンジ１３、３１、３４、３６、３８、４３、４６、４８、４９、５１、５２、５５、５９、６０、６１、６２、６４、６５、７１；ピグメントイエロー１、３、１２、１３、１４、１６、１７、２０、２４、５５、６０、７３、８１、８３、８６、９３、９５、９７、９８、１００、１０９、１１０、１１３、１１４、１１７、１２０、１２５、１２６、１２７、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５１、１５２、１５３、１５４、１６６、１６８、１７５、１８０、１８５；ピグメントグリーン７、１０、３６；ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：５、１５：６、２２、２４、２９、５６、６０、６１、６２、６４；ピグメントバイオレット１、１５、１９、２３、２７、２９、３０、３２、３７、４０、５０等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。 As the pigment, commercially available pigments can also be used. For example, pigment red 1, 2, 3, 9, 10, 17, 22, 23, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224 226, 227, 228, 240, 254; pigment oranges 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71 Pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 00, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, Pigment green 7, 10, 36; pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 29, 56, 60, 61, Pigment violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, 50, and the like. One of these may be used alone, or two or more may be used in combination.
　蛍光増白剤とは、太陽光や人工光の紫外線を吸収し、これを紫～青色の可視光線に変えて輻射する蛍光作用によって、成形体の白色度や青味を助長させる化合物である。蛍光増白剤としては、ベンゾオキサゾール系化合物Ｃ．Ｉ．Ｆｌｕｏｒｅｓｃｅｎｔ　Ｂｒｉｇｈｔｎｅｒ１８４；クマリン系化合物Ｃ．Ｉ．Ｆｌｕｏｒｅｓｃｅｎｔ　Ｂｒｉｇｈｔｎｅｒ５２；ジアミノスチルベンジスルフォン酸系化合物Ｃ．Ｉ．Ｆｌｕｏｒｅｓｃｅｎｔ　Ｂｒｉｇｈｔｎｅｒ２４、８５、７１等が挙げられる。蛍光増白剤を用いる場合の配合量は、オレフィン系樹脂１００質量部に対して、０．００００１～０．１質量部が好ましく、より好ましくは、０．００００５～０．０５質量部である。 The fluorescent whitening agent is a compound that absorbs the ultraviolet rays of sunlight or artificial light, converts the light into a violet to blue visible light and emits the visible light, thereby promoting the whiteness and bluishness of the molded product. As the brightening agents, benzoxazole compounds C.I. I. Fluorescent Brightner 184; coumarin compound C.I. I. Fluorescent Brightner 52; diaminostilbenedisulfonic acid compound C.I. I. Fluorescent Brightner 24, 85, 71 etc. are mentioned. The blending amount in the case of using the fluorescent whitening agent is preferably 0.00001 to 0.1 part by mass, and more preferably 0.00005 to 0.05 part by mass with respect to 100 parts by mass of the olefin resin.
　染料としては、アゾ染料、アントラキノン染料、インジゴイド染料、トリアリールメタン染料、キサンテン染料、アリザリン染料、アクリジン染料、スチルベン染料、チアゾール染料、ナフトール染料、キノリン染料、ニトロ染料、インダミン染料、オキサジン染料、フタロシアニン染料、シアニン染料等が挙げられ、これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。 As dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazolyl dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And cyanine dyes and the like, and these may be used alone or in combination of two or more.
　本発明のオレフィン系樹脂組成物を成形する場合、公知の成形方法を用いて成形することができる。例えば、射出成形法、押出成形法、ブロー成形法、真空成形法、インフレーション成形法、カレンダー成形法、スラッシュ成形法、ディップ成形法、発泡成形法等を用いて成形品を得ることができる。 When shaping | molding the olefin resin composition of this invention, it can shape | mold using a well-known shaping | molding method. For example, a molded article can be obtained using an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calendar molding method, a slush molding method, a dip molding method, a foam molding method or the like.
　本発明のオレフィン系樹脂組成物の用途としては、バンパー、ダッシュボード、インパネ等自動車材料、冷蔵庫、洗濯機、掃除機等のハウジング用途、食器、バケツ、入浴用品等の家庭用品、玩具等の雑貨品、タンク類等の貯蔵、保存用容器等の成形品や、フィルム、繊維等が挙げられる。 Applications of the olefin resin composition of the present invention include automotive materials for bumpers, dashboards, instrument panels, etc., housing applications such as refrigerators, washing machines, vacuum cleaners, household goods such as dishes, buckets, bathing articles, etc. Articles, storage of articles such as tanks, molded articles such as containers for preservation, films, fibers and the like can be mentioned.
　以下、実施例を挙げて、本発明をさらに具体的に説明するが、本発明は以下の実施例等によって何ら制限を受けるものではない。 Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited at all by the following examples and the like.
　下記表１に示す試験化合物の融点およびｓｐ値を以下の手順で測定した。評価に用いた試験化合物の融点とｓｐ値について、表１にそれぞれ併記する。 The melting points and the sp values of the test compounds shown in Table 1 below were measured by the following procedures. The melting point and the sp value of the test compound used for the evaluation are shown together in Table 1 respectively.
＜融点＞
　示差走査熱量測定機（ＤＳＣ）を用いて、窒素雰囲気下、１０℃／ｍｉｎで昇温時の吸熱ピーク温度を融点として評価した。 <Melting point>
Using a differential scanning calorimeter (DSC), the endothermic peak temperature at the time of temperature rising at 10 ° C./min in a nitrogen atmosphere was evaluated as the melting point.
＜ｓｐ値＞
　Ｆｅｄｏｒｓ法により算出した。各原子または原子団の２５℃における蒸発エネルギーは、「R.F.Fedors;Polym.Eng.Sci.,14[2],147-154(1974)」に記載されているデータを用いて、ｓｐ値を算出した。  <Sp value>
Calculated by the Fedors method. The evaporation energy at 25 ° C. of each atom or group was calculated using the data described in “RF Fedors; Polym. Eng. Sci., 14 [2], 147-154 (1974)” to calculate the sp value. .
Figure JPOXMLDOC01-appb-T000014
 ＤＭＤＢＳ：１，３：２，４－ビス（３，４－ジメチルベンジリデンソルビトール）
ＥＢＳＡ：Ｎ．Ｎ’－エチレンビスステアリン酸アミド
ＢＡ：ベヘン酸アミド
ＳＡ：ステアリン酸アミド
ＯＡ：オレイン酸アミド
ＧＭＳ：ステアリン酸モノグリセライド
ＰＶ１００：理研ビタミン株式会社製　商品名「ポエム　ＰＶ－１００」（ステアリン酸グリセライドとパルミチン酸グリセライドとの混合物（質量比：１：１））
ＬＡ－１２：株式会社ＡＤＥＫＡ製　商品名「ＡＤＫ　Ｓｔａｂ　ＬＡ－１２」
ｔＢＰＳ：ｔｅｒｔ－ブチルフェニルサリチレート
Figure JPOXMLDOC01-appb-T000014
 DMDBS: 1,3: 2,4-bis (3,4-dimethylbenzylidene sorbitol)
EBSA: N. N'-ethylenebisstearic acid amide BA: behenic acid amide SA: stearic acid amide OA: oleic acid amide GMS: stearic acid monoglyceride PV100: manufactured by Riken Vitamin Co., Ltd. trade name "POEM PV-100" (glyceride stearate and palmitic acid Mixture with glycerol (mass ratio: 1: 1))
LA-12: Made by ADEKA Co., Ltd. Brand name "ADK Stab LA-12"
tBPS: tert-Butyl phenyl salicylate
〔実施例１－１～１－３、比較例１－１～１－８〕
　（Ａ）透明化剤および（Ｂ）分散助剤を、表２に記載の割合でドライブレンドした後、ＤＳＣで、融点を測定した。これらの結果についてそれぞれ、表２に示す。 [Examples 1-1 to 1-3, Comparative Examples 1-1 to 1-8]
After dry blending of (A) the clarifying agent and (B) the dispersion aid in the proportions described in Table 2, the melting point was measured by DSC. Each of these results is shown in Table 2.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
〔実施例２－１～２－３、比較例２－１、２－２〕
　オレフィン系樹脂として、ＭＦＲ＝１２ｇ／ｍｉｎのランダム－ポリプロピレン、酸化防止剤および中和剤を、表３に記載の配合量で準備し、ヘンシェルミキサーを用いて、ドライブレンドした。ブレンド後、押出機を用いて、樹脂温度２００℃の条件で、造粒し、ペレットを得た。得られたペレットは、６０℃の恒温器で８時間乾燥させた。乾燥後、２００℃でプレスし、シートにした。得られたシートに、表２記載の透明化剤組成物を少量乗せ、温調付偏光顕微鏡（鋭敏色板使用、４０倍観察）を用いて透明性能を確認した。なお、表３中の配合量の単位は質量部である。 [Examples 2-1 to 2-3, Comparative Examples 2-1 and 2-2]
As an olefin resin, a random-polypropylene of MFR = 12 g / min, an antioxidant and a neutralizing agent were prepared in the amounts described in Table 3, and dry-blended using a Henschel mixer. After blending, the mixture was granulated using an extruder under conditions of a resin temperature of 200 ° C. to obtain pellets. The obtained pellet was dried in a 60 ° C. incubator for 8 hours. After drying, it was pressed at 200 ° C. to form a sheet. A small amount of the clarifying agent composition described in Table 2 was placed on the obtained sheet, and the transparency performance was confirmed using a temperature-controlled polarization microscope (use of a sensitive color plate, 40 × observation). In addition, the unit of the compounding quantity in Table 3 is a mass part.
　透明性能は、以下の手順で評価した。１００℃／ｍｉｎの条件で、２００℃までシートを加熱し、２００℃を１ｍｉｎ保持した後、室温まで、１０℃／ｍｉｎの速度で冷却した。冷却するときに、偏光顕微鏡で確認して、透明化剤組成物の境界で、オレフィン系樹脂の偏光が確認された場合は、透明性能あり、偏光が確認できない場合は、透明性能なしとして評価した。これらの結果について、それぞれ表３に示す。 The transparency performance was evaluated by the following procedure. The sheet was heated to 200 ° C. under the conditions of 100 ° C./min, held at 200 ° C. for 1 min, and then cooled to room temperature at a rate of 10 ° C./min. When cooling, it was confirmed by a polarization microscope, and when polarization of the olefin resin was confirmed at the boundary of the clarifying agent composition, it was evaluated as having transparency performance, and when polarization could not be confirmed, no transparency performance . The results are shown in Table 3 respectively.
Figure JPOXMLDOC01-appb-T000016
 ＡＯ－６０：テトラキス［３－（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピニルオキシメチル］メタン
２１１２：トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト
Ｃａ－Ｓｔ：ステアリン酸カルシウム
Figure JPOXMLDOC01-appb-T000016
 AO-60: tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxymethyl] methane 2112: tris (2,4-di-tert-butylphenyl) phosphite Ca-St: stea Calcium phosphate
　実施例２－１～２－３より、本発明のオレフィン系樹脂組成物は、オレフィン樹脂に対して核剤効果を発揮していることが確認された。また、透明化剤が０．１６質量部となるように調整した実施例２－１～２－３の樹脂組成物について、それぞれ、ヘンシェルミキサーを用いてドライブレンドし、ブレンド後、押出機を用いて、樹脂温度２００℃の条件で、造粒し、得られたペレットを６０℃の恒温器で８時間乾燥させてから、射出成形機を用いて、２００℃の射出温度で１ｍｍ厚のシートを成形したところ、２００℃の低温加工でも透明性が良好であり、臭気も発生していなかった。 From Examples 2-1 to 2-3, it was confirmed that the olefin resin composition of the present invention exerts a nucleating agent effect on the olefin resin. In addition, each of the resin compositions of Examples 2-1 to 2-3 adjusted to 0.16 parts by mass of the clarifying agent is dry-blended using a Henschel mixer, and after blending, an extruder is used. And pelletize the obtained pellet in a thermostat at 60 ° C. for 8 hours, and then use an injection molding machine to make a 1 mm thick sheet at an injection temperature of 200 ° C. When molded, transparency was good even at low temperature processing at 200 ° C., and no odor was generated.
　以上より、本発明の透明化剤組成物は、ジベンジリデンソルビトール化合物の融点を大きく低下させることができる。そして、低温成形が可能になり、臭気が抑制され、優れた透明性を有する成形品を提供できることを確認した。 From the above, the clarifying agent composition of the present invention can significantly lower the melting point of the dibenzylidene sorbitol compound. Then, it was confirmed that low temperature molding was possible, odor was suppressed, and molded articles having excellent transparency could be provided.

Claims (5)

  1. 　（Ａ）一般式（１）、
    Figure JPOXMLDOC01-appb-I000001
    （一般式（１）中、Ｒ１、Ｒ２およびＲ３は、各々独立して、水素原子、炭素原子数１～４のアルキル基、炭素原子数１～４のアルコキシ基、炭素原子数１～４のアルコキシカルボニル基、または、ハロゲン原子を表し、ｓ、ｔおよびｕは、各々独立して、１～５の整数を表す）で表される透明化剤１００質量部に対し、（Ｂ）分散助剤を、３０～１００質量部含有する透明化剤組成物であって、（Ｂ）分散助剤が、Ｆｅｄｏｒｓ法で算出したＳＰ値が、１１．０以上であり、かつ、融点が２００℃以下であることを特徴とする透明化剤組成物。     (A) General formula (1),
    Figure JPOXMLDOC01-appb-I000001
    In the general formula (1), R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom (B) relative to 100 parts by mass of a clarifying agent represented by the alkoxycarbonyl group of to 4 or a halogen atom, and s, t and u each independently represent an integer of 1 to 5) A clarifying agent composition containing 30 to 100 parts by mass of a dispersion aid, wherein (B) the dispersion aid has an SP value calculated by Fedors method of 11.0 or more, and a melting point of 200 A clearing agent composition characterized by having a temperature of not higher than ° C.
  2. 　（Ａ）成分が、１，３：２，４－ビス（３，４－ジメチルベンジリデンソルビトール）である請求項１記載の透明化剤組成物。 2. The clarifying agent composition according to claim 1, wherein the component (A) is 1,3: 2,4-bis (3,4-dimethylbenzylidene sorbitol).
  3. 　（Ｂ）成分が、ｔｅｒｔ－ブチルフェニルサリチレート、ニコチンアミド、３－フェノキシ－１，２－プロパンジオールからなる群から選択される少なくとも１種の化合物を含有する請求項１または２記載の透明化剤組成物。 The transparent material according to claim 1 or 2, wherein the component (B) contains at least one compound selected from the group consisting of tert-butylphenyl salicylate, nicotinamide, 3-phenoxy-1,2-propanediol. Agent composition.
  4. 　オレフィン系樹脂１００質量部に対し、（Ａ）成分が、０．００１～１０質量部となるように請求項１～３のうちいずれか一項記載の透明化剤組成物を含有することを特徴とするオレフィン系樹脂組成物。 The transparentizing agent composition according to any one of claims 1 to 3 is characterized in that component (A) is 0.001 to 10 parts by mass with respect to 100 parts by mass of the olefin resin. And an olefin resin composition.
  5. 　請求項４記載のオレフィン系樹脂組成物を用いてなることを特徴とする成形品。 A molded article comprising the olefin resin composition according to claim 4.
PCT/JP2018/032254 2017-08-31 2018-08-30 Clarifying agent composition, olefinic resin composition using same, and molded article thereof WO2019045014A1 (en)

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Citations (9)

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JPH01126352A (en) * 1987-11-12 1989-05-18 Iic Kagaku Kogyo Kk Di-substituted benzylidienesorbitol composition
JPH07173341A (en) * 1993-12-20 1995-07-11 Tonen Chem Corp Polypropylene-based resin composition having improved transparency
JPH07330389A (en) * 1994-06-09 1995-12-19 Sekisui Chem Co Ltd Intermediate membrane for laminated glass and laminated glass
JPH1060165A (en) * 1996-08-12 1998-03-03 New Japan Chem Co Ltd Dibenzylidenesorbitol composition and polyolefin resin composition containing the same
WO1999018108A1 (en) * 1997-10-03 1999-04-15 New Japan Chemical Co., Ltd. Diacetal composition, process for the preparation of the same, nucleating agent for polyolefins containing the same, polyolefin resin compositions, and moldings
JP2001001648A (en) * 1999-06-21 2001-01-09 Fuji Photo Film Co Ltd Heat-transfer material, and image forming material using the same
JP2008184478A (en) * 2007-01-26 2008-08-14 Riken Vitamin Co Ltd Antistatic polypropylene film
JP2012207211A (en) * 2011-03-11 2012-10-25 Japan Polypropylene Corp Odor abatement method of polypropylene-based resin composition with transparency nucleating agent included therein
JP2012207212A (en) * 2011-03-11 2012-10-25 Japan Polypropylene Corp Odor abatement method of talc-containing polypropylene-based resin composition with transparency nucleating agent included therein

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01126352A (en) * 1987-11-12 1989-05-18 Iic Kagaku Kogyo Kk Di-substituted benzylidienesorbitol composition
JPH07173341A (en) * 1993-12-20 1995-07-11 Tonen Chem Corp Polypropylene-based resin composition having improved transparency
JPH07330389A (en) * 1994-06-09 1995-12-19 Sekisui Chem Co Ltd Intermediate membrane for laminated glass and laminated glass
JPH1060165A (en) * 1996-08-12 1998-03-03 New Japan Chem Co Ltd Dibenzylidenesorbitol composition and polyolefin resin composition containing the same
WO1999018108A1 (en) * 1997-10-03 1999-04-15 New Japan Chemical Co., Ltd. Diacetal composition, process for the preparation of the same, nucleating agent for polyolefins containing the same, polyolefin resin compositions, and moldings
JP2001001648A (en) * 1999-06-21 2001-01-09 Fuji Photo Film Co Ltd Heat-transfer material, and image forming material using the same
JP2008184478A (en) * 2007-01-26 2008-08-14 Riken Vitamin Co Ltd Antistatic polypropylene film
JP2012207211A (en) * 2011-03-11 2012-10-25 Japan Polypropylene Corp Odor abatement method of polypropylene-based resin composition with transparency nucleating agent included therein
JP2012207212A (en) * 2011-03-11 2012-10-25 Japan Polypropylene Corp Odor abatement method of talc-containing polypropylene-based resin composition with transparency nucleating agent included therein

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