WO2019045014A1 - Composition d'agent de clarification, composition de résine oléfinique l'utilisant, et son article moulé - Google Patents

Composition d'agent de clarification, composition de résine oléfinique l'utilisant, et son article moulé 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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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

La présente invention concerne : une composition d'agent de clarification susceptible de faire preuve d'une excellente transparence sans problèmes impliquant l'irritation, la toxicité, l'odeur, etc. ; une composition de résine oléfinique dans laquelle ladite composition est utilisée ; et son article moulé. La présente invention concerne une composition d'agent de clarification contenant de 30 à 100 parties en masse d'un auxiliaire de dispersion (B) pour 100 parties en masse d'un agent de clarification (A) représenté par la formule générale (1) (dans la formule générale (1), R1, R2, et R3 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle en C1 à C4, un groupe alcoxy en C1 à C4, un groupe alcoxycarbonyle en C1 à C4, ou un atome d'halogène ; et s, t, et u représentent chacun indépendamment un nombre entier d'une valeur de 1 à 5), l'auxiliaire de dispersion (B) présentant une valeur SP, telle que calculée selon le procédé de Fedor, de 11,0 ou plus, et un point de fusion de 200 °C ou moins.
PCT/JP2018/032254 2017-08-31 2018-08-30 Composition d'agent de clarification, composition de résine oléfinique l'utilisant, et son article moulé WO2019045014A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01126352A (ja) * 1987-11-12 1989-05-18 Iic Kagaku Kogyo Kk ジ−置換ベンジリデンソルビトール組成物
JPH07173341A (ja) * 1993-12-20 1995-07-11 Tonen Chem Corp 透明性の改良されたポリプロピレン系樹脂組成物
JPH07330389A (ja) * 1994-06-09 1995-12-19 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
JPH1060165A (ja) * 1996-08-12 1998-03-03 New Japan Chem Co Ltd ジベンジリデンソルビトール系組成物及びそれを含むポリオレフィン系樹脂組成物
WO1999018108A1 (fr) * 1997-10-03 1999-04-15 New Japan Chemical Co., Ltd. Composition de diacetal, procede de preparation, agent de nucleation pour polyolefines contenant une telle composition, compositions de resines de polyolefines, et moulages
JP2001001648A (ja) * 1999-06-21 2001-01-09 Fuji Photo Film Co Ltd 熱転写材料及びそれを用いた画像形成材料
JP2008184478A (ja) * 2007-01-26 2008-08-14 Riken Vitamin Co Ltd 帯電防止性ポリプロピレンフィルム
JP2012207211A (ja) * 2011-03-11 2012-10-25 Japan Polypropylene Corp 透明化核剤入りポリプロピレン系樹脂組成物の臭気低減方法
JP2012207212A (ja) * 2011-03-11 2012-10-25 Japan Polypropylene Corp 透明化核剤入りタルク含有ポリプロピレン系樹脂組成物の臭気低減方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01126352A (ja) * 1987-11-12 1989-05-18 Iic Kagaku Kogyo Kk ジ−置換ベンジリデンソルビトール組成物
JPH07173341A (ja) * 1993-12-20 1995-07-11 Tonen Chem Corp 透明性の改良されたポリプロピレン系樹脂組成物
JPH07330389A (ja) * 1994-06-09 1995-12-19 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
JPH1060165A (ja) * 1996-08-12 1998-03-03 New Japan Chem Co Ltd ジベンジリデンソルビトール系組成物及びそれを含むポリオレフィン系樹脂組成物
WO1999018108A1 (fr) * 1997-10-03 1999-04-15 New Japan Chemical Co., Ltd. Composition de diacetal, procede de preparation, agent de nucleation pour polyolefines contenant une telle composition, compositions de resines de polyolefines, et moulages
JP2001001648A (ja) * 1999-06-21 2001-01-09 Fuji Photo Film Co Ltd 熱転写材料及びそれを用いた画像形成材料
JP2008184478A (ja) * 2007-01-26 2008-08-14 Riken Vitamin Co Ltd 帯電防止性ポリプロピレンフィルム
JP2012207211A (ja) * 2011-03-11 2012-10-25 Japan Polypropylene Corp 透明化核剤入りポリプロピレン系樹脂組成物の臭気低減方法
JP2012207212A (ja) * 2011-03-11 2012-10-25 Japan Polypropylene Corp 透明化核剤入りタルク含有ポリプロピレン系樹脂組成物の臭気低減方法

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