TW201920412A - Composition, olefin resin composition using same, and molded article of same - Google Patents

Abstract

Provided are a composition whereby excellent transparency can be imparted to an olefin resin, an olefin resin composition having excellent transparency in low-temperature processing in which the composition is used, and a molded article of the olefin resin composition. A composition in which a salicylate-based UV absorber (C) and 10-200 parts by mass of an amide compound (B) are blended with respect to 100 parts by mass of a sorbitol compound (A) represented by general formula (1) (In 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 to 5.), wherein the blended amount of component (C) is equal to or less than the blended amount of component (B) and is more than 0 part by mass, and a glycerin fatty acid ester (D) is also blended in an amount equal to or less than the blended amount of component (C).

Description

Composition, olefin resin composition using the same, and molded article thereof

The present invention relates to a composition, an olefin-based resin composition using the same, and a molded product thereof, and in particular, to a specific combination of a dibenzylidene sorbitol compound and an auxiliary agent, which can impart excellent properties to an olefin-based resin. A transparent composition, an olefin-based resin composition using the same, and a molded article thereof.

A dibenzylidene sorbitol compound obtained by condensing an aromatic aldehyde and sorbitol with an acetal in the presence of an acid catalyst is used as a transparent agent for improving the transparency of an olefin resin. With regard to such two benzylidene sorbitol compounds, for example, 1,3: 2,4: -bis (O-benzylidene) sorbitol, 1,3: 2,4-bis (p-chlorophosphine) are known. Benzyl) sorbitol, 1,3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-dimethylbenzylidene sorbitol) Sugar alcohol) and so on.

The mechanism of action of these dibenzylidene sorbitol compounds as a transparent agent is thought to be due to the heating accompanying the molding of the olefin-based resin composition, and the crystal structure of the dibenzylidene sorbitol compounds undergoes a collapse process (colloid- Sol transition), after the dibenzylidene sorbitol compound is dissolved in the olefin-based resin, in the cooling step, a new network structure of the dibenzylidene sorbitol compound is formed in the olefin-based resin (from sol to colloid ), By using it as a nucleating agent, a transparency effect can be exhibited.

In order to improve the transparency of an olefin-based resin by using such a transparentizer, in the molding step, the dibenzylidene sorbitol compound must be heated to a temperature above the melting temperature. However, 1,3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-dimethylbenzylidenesorbitol) have 270 A high melting point of ~ 275 ° C, when processed at a high temperature, the dibenzylidene sorbitol compound has the problem of generating thermal decomposition and producing strong benzaldehyde. From the viewpoint of protecting the working environment or energy saving, processing at low temperatures (below 200 ° C) is pursued.

In order to use a dibenzylidene sorbitol compound for low temperature processing, a review was conducted to lower the melting point of the dibenzylidene sorbitol compound. For example, Patent Document 1 proposes 1,3-O-3,4-dimethylbenzylidene-2,4-O-benzylidene sorbitol and / or 1, which has a melting point of 275 to 280 ° C. 3-O-benzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, mixed with bis (O-3,4-dimethylbenzylidene) having a melting point of 215 ~ 220 ° C Sorbitol).

Patent Document 2 proposes a method in which a dibenzylidene sorbitol compound is mixed with an aliphatic carboxylic acid amine and / or an aromatic carboxylic acid amine and the surface of the dibenzylidene sorbitol compound is aliphatic. Carboxamide and / or an aromatic carboxamide coated composition.

Patent Document 3 proposes a composition in which a dibenzylidene sorbitol compound is dispersed with a sulfate salt and an aliphatic carboxylic acid. Patent Document 4 proposes the use of a transparent agent having a colloid-sol transition temperature of 180 ° C or lower.

In addition, Non-Patent Document 1 discloses that if a sorbitol-based transparentizer is heated, the morphology of the sorbitol-based transparentizer changes at a temperature much lower than the melting point, which affects the transparency of the sorbitol-based transparentizer. The solubility of the agent in polypropylene. Prior Art Literature Patent Literature

Patent Document 1: JP 7-278362 Patent Document 2: Patent 3343754 Patent Document 3: Patent 3358659 Patent Document 4: JP 2010-254882 Non-Patent Document

Non-Patent Document 1: The Royal Society of Chemistry, 2014, 4, 19737-19745

[Problems to be Solved by the Invention]

However, the methods described in Patent Documents 1 to 3 are for 1,3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-dimethyl Benzylidene sorbitol) is insufficient, and further improvements are sought. In particular, the use of an aliphatic carboxylic acid or an anionic surfactant has problems in terms of irritation, harmfulness, and odor. In addition, although the compound described in Patent Document 4 has been proposed to use the brand name "Millad NX8000" manufactured by Milliken & Company, it is still insufficient to seek further improvement.

Furthermore, Non-Patent Document 1 discloses that the solubility of a sorbitol-based transparentizer is closely related to the core density of polypropylene. When the solubility of a sorbitol-based transparentizer increases, the transparency of polypropylene is improved, but the transparency is reduced. The melting point of sorbitol-based transparentizers has not been fully reviewed.

Therefore, an object of the present invention is to provide a composition which can provide excellent transparency to olefin-based resins without problems such as irritation, harmfulness, odor, and the like, and an olefin-based resin having excellent transparency at low temperature processing using the composition. Composition and molded article thereof. [Means to solve the problem]

As a result of an intensive review by the present inventors in order to solve the above-mentioned problems, they have found that the above-mentioned problems can be solved by preparing a composition in which a specific auxiliary agent is mixed in a specific ratio with respect to a dibenzylidene sorbitol compound, and the present invention has been completed.

That is, the composition of the present invention is compared with the following general formula (1) In formula (1), R ¹ , R ^2, and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkane having 1 to 4 carbon atoms. 100 parts by mass of the sorbitol compound (A) represented by an oxycarbonyl group or a halogen atom, s, t, and u each being an integer of 1 to 5), and 10 to 200 parts by mass of the amidine compound (B) And a salicylate-based ultraviolet absorber (C), characterized in that the component (C) is the blending amount of the component (B) or less but more than 0 parts by mass, and the glycerin fatty acid ester (D) is ( C) The amount of components to be blended is configured below.

In the composition of the present invention, the component (A) is preferably 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol. In the composition of the present invention, the component (C) is preferably tert-butyl salicylate.

The olefin-based resin composition of the present invention is characterized by containing the composition of the present invention so that the component (A) becomes 0.001 to 10 parts by mass relative to 100 parts by mass of the olefin-based resin.

The molded article of the present invention is characterized by using the olefin-based resin composition of the present invention. [Effect of the invention]

According to the present invention, it is possible to provide a composition capable of imparting excellent transparency to an olefin-based resin without causing problems such as irritation, harmfulness, odor, and the like, and an olefin-based resin composition having excellent transparency at low temperature processing using the composition. Objects and their shaped articles.

[Best Mode for Implementing Invention]

Hereinafter, embodiments of the present invention will be described in detail. First, the sorbitol compound (A) represented by general formula (1) (henceforth a "(A) component") is demonstrated. The component (A) of the present invention is represented by the general formula (1) Represents the second benzylidene sorbitol compound. Here, in the general formula (1), R ¹ , R ^2, and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 carbon atom. An alkoxycarbonyl group or a halogen atom of ~ 4, s, t, and u are each independently an integer of 1 to 5.

In the general formula (1), the alkyl group having 1 to 4 carbon atoms represented by R ¹ , R ^2, and R ³ may be, for example, methyl, ethyl, propyl, isopropyl, butyl, or sec-butyl. And tert-butyl.

In the general formula (1), the alkoxy group having 1 to 4 carbon atoms represented by R ¹ , R ^2, and R ³ may be, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butan group. Oxygen, etc.

In the general formula (1), the alkoxycarbonyl group having 1 to 4 carbon atoms represented by R ¹ , R ² and R ³ may be, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, or isopropyl group. Oxycarbonyl and the like.

Examples of the halogen atom represented by R ¹ , R ^2, and R ^{3 in} the general formula (1) include a fluorine atom, a chlorine atom, and a bromine atom.

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.

Specific examples of the (A) component include the following compounds. However, the present invention is not limited to these compounds.

DBS: 1,3: 2,4-bis (O-benzylidene) sorbitol Melting point 218 ° C

MDBS: 1,3: 2,4-bis (p-methylbenzylidene) sorbitol Melting point 255-262 ℃

1,3-O-benzylidene-2,4-O-3,4-dimethylbenzylidenesorbitol

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

Next, the amidine compound (B) (hereinafter also referred to as "(B) component") will be described. In the composition of the present invention, the structure of the amidine compound is not particularly limited. Among these, ammonium salt compounds of saturated fatty acids such as capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and octacosanoic acid, etc. Ammonium salt compounds of unsaturated fatty acids such as hexaenoic acid, erucic acid, oleic acid, and trans octadecenoic acid, ammonium methylene distearate, ammonium bisoleate, ethylene bis Difatty acid ammonium compounds such as ammonium stearate and ammonium ethylene oleate may impart excellent transparency to olefin resins.

The blending amount of the component (B) used in the composition of the present invention is 10 to 200 parts by mass, preferably 10 to 150 parts by mass, and more preferably 12 to 90 parts by mass with respect to 100 parts by mass of the component (A). When the blending amount of the component (B) is outside the range of 10 to 200 parts by mass, the effect of the present invention may be lacking.

Next, a salicylate-based ultraviolet absorber (C) (hereinafter, also referred to as "(C) component") will be described. The component (C) includes, for example, phenyl salicylate, phenyl 4-methylsalicylate, phenyl 4-tert-butylsalicylate, octylsalicylate, 2-ethylhexylsalicylate, p-isopropanol phenyl salicylate, amyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. UV absorber with salicylic acid structure. In the composition of the present invention, tert-butyl salicylate is particularly preferred.

In the composition of the present invention, the blending amount of the component (C) is equal to or less than the blending amount of the (B) component and is not at least zero. Since the blending amount of the component (C) is larger than the blending amount of the (B) component, the effect of the present invention cannot be obtained.

Next, the glycerin fatty acid ester (D) (hereinafter, also referred to as "(D) component") will be described. Glycerin fatty acid ester refers to an ester compound of glycerol and fatty acid. Specific examples of the component (D) include the following general formula (2) Monoglycerin fatty acid ester represented by general formula (3) Diglyceride fatty acid ester represented by general formula (4) Triglyceride fatty acid ester and the like. R in the general formulae (2) to (4) is a linear or branched alkyl group having 1 to 20 carbon atoms.

Monoglyceride fatty acid esters include, for example, caprylic monoglyceride, lauric monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, 12-hydroxystearic acid monoglyceride, oleic acid monoglyceride, Lauryl monoglyceride, etc.

Examples of the diglyceride fatty acid ester include diglyceryl caprylate, diglyceryl palmitate, diglyceryl stearate, diglyceryl oleate, and diglyceryl behenate.

Examples of the triglyceride fatty acid ester include triglyceride fatty acid esters such as triglyceryl octanoate and triglyceride 2-ethylhexanoate.

In the composition of the present invention, monoglyceride fatty acid ester, diglyceride fatty acid ester, and triglyceride fatty acid ester can be used, but the monoglyceride fatty acid ester having two unesterified hydroxyl groups in the molecule has a multiplicative effect. Excellent point is better. Among the monoglyceride fatty acid esters, lauric monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, 12-hydroxystearic acid monoglyceride, and behenyl monoglyceride are particularly preferred.

In the composition of the present invention, the blending amount of the (D) component is equal to or less than the blending amount of the (C) component, and the (D) component is not necessarily an indispensable component. That is, the composition of the present invention may not contain the (D) component, but when the (D) component contains more than 0 parts by mass, it is equal to or less than the blending amount of the (C) component. Since the blending amount of the (D) component is larger than the blending amount of the (C) component, the effect of the present invention may not be obtained.

Next, the olefin-based resin composition of the present invention will be described. The olefin-based resin composition of the present invention is 100 parts by mass of the olefin-based resin, and the component (A) has a composition of the present invention such that the blending amount of the component (A) is 0.005 to 5 parts by mass is more preferable, and a range of 0.01 to 0.5 parts by mass is more preferable. If it is less than 0.001 parts by mass, the effect of improving the transparency of the olefin resin may be insufficient. If it is more than 10 parts by mass, the components of the composition may overflow from the molded product.

Examples of the olefin resin used in the olefin-based resin composition of the present invention include low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), high density polyethylene (HDPE), isotactic polypropylene, Syndiotactic polypropylene, semi-isotactic polypropylene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4- Α-olefin polymers such as methyl-1-pentene, ethylene / propylene block or random copolymer, impact copolymer polypropylene, ethylene-methacrylate copolymer, ethylene-methacrylate copolymer Materials, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-vinyl acetate copolymers, α-olefin copolymers such as ethylene-vinyl alcohol resin (EVOH), etc., may also be elastic body. In the olefin-based resin composition of the present invention, two or more of these may be mixed and used, a block copolymer may be formed and used in a block polymer type, and the resin may be alloyed. In addition, a chloride of such an olefin-based resin may be used.

For the elastomer of the olefin resin, for example, an elastomer obtained by mixing a polyolefin such as polypropylene or polyethylene as a hard segment and a rubber such as ethylene-propylene rubber as a soft segment, or an elastomer obtained by mixing these, or An elastomer obtained by dynamic crosslinking.

The hard segment may be at least one selected from, for example, a polypropylene homopolymer, a polypropylene block copolymer, and a polypropylene random copolymer.

As for the soft segment, for example, ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and vinyl acetate homopolymer can be mentioned. These can be used in combination of two or more kinds.

The manufacturing method of the above olefin resin is based on Ziegler catalyst, Ziegler-Natta catalyst, metallocene catalyst, various other polymerization catalysts, promoters, catalyst carriers, chain transfer agents, and In various polymerization methods such as gas phase polymerization, solution polymerization, emulsion polymerization, and block polymerization, it is appropriate to select various polymerization conditions such as temperature, pressure, concentration, flow rate, and removal of catalyst residues to obtain physical properties suitable for the intended product. It is produced by using a resin that is suitable for the physical properties of the molded product of the intended product. Number average molecular weight, weight average molecular weight, molecular weight distribution, melt flow rate (MFR), melting point, melting peak temperature, isotacticity, syndiotacticity, etc. of olefin-based resins, stereoregularity, presence or degree of branching, specific gravity, and various solvents The ratio of dissolved components, Haze, gloss, impact strength, flexural modulus, Olson rigidity, other characteristics, and whether each characteristic value satisfies a specific formula can be appropriately selected depending on the desired characteristics.

The composition of the present invention or the olefin-based resin composition may optionally contain conventional resin additives (such as phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, and the like) within a range that does not significantly impair the effects of the present invention. Salicylate-based UV absorbers other UV absorbers, hindered amine compounds, core agents different from (A) components, flame retardants, flame retardant auxiliaries, slip agents, fillers, rhombic magnesium aluminum Stone, antistatic agent, pigment, fluorescent whitening agent, dye, etc.).

Examples of the phenolic antioxidant include 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 (octylmercaptomethyl) phenol, 2,2'-isobutylenebis (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) propanamide, 2,2'-oxapyrazine-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-phenylpropanoic acid, and C13-15 alkyl ester, 2,5-di-tert-pentylhydroquinone, polymer of hindered phenol (ADEKA POLYMER ADDITIVES EUROPE SAS, trade name "AO.OH.98"), 2,2'- Methylene bis [6- (1-methylcyclohexyl) -p-cresol], 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methyl Benzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentyl Phenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butylbenzo [ d, f] [1,3,2] -dioxaphosphaheptane, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, Bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphate] calcium salt, 5,7-bis (1,1-dimethylethyl) -3-hydroxy- Reaction product of 2 (3H) -benzofuranone and 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-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl) 4-hydroxybenzyl) phosphate, tridecyl-3,5-tert-butyl-4-hydroxybenzyl thioacetate, thiodiethylene bis [(3,5-di-tert-butyl 4-hydroxyphenyl) propionate] 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-bis (3,5-di-tert-butyl-4-hydroxybenzene (Oxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis (3,3-bis (4-hydroxy-3-tert-butyl Phenyl) butyric acid] glycol, 4,4'-butylene bis (2,6-di-tert-butylphenol), 4,4'-butylene bis (6-tert-butyl-3 -Methylphenol), 2,2'-ethylenebis (4,6-di-tert-butylphenol), 1,1,3-ginseng (2-methyl-4-hydroxy-5-tert- Butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] p-xylylene Acid ester, 1,3,5-ginseng (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-ginseng (3,5- Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6 -Trimethylbenzene, 1,3,5-ginseng [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, methylene [methylene 3--3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-propenefluorene Oxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy Methyl-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 ) Amido propionate, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, myristyl-3- (3,5-di-tert-butyl 3- (3,5-di) methylammonium propionate, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ammonium propionate, etc. Alkyl-4-hydroxyphenyl) propionic acid derivatives and the like. These can be used alone or in combination of two or more. The blending amount when blending with a phenolic antioxidant is preferably 0.001 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, relative to 100 parts by mass of the olefin-based resin.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diisooctyl phosphite, fluorene (dipropylene glycol) triphosphite, triisodecyl phosphite, and diphenyl isooctyl phosphite. , Diisooctylphenyl phosphite, diphenyltridecylphosphite, triisooctylphosphite, trilaurylphosphite, diphenylphosphite, ginseng (dipropylene glycol) phosphorous acid Ester, diisodecyl pentaerythritol diphosphite, diolenyl hydrophosphite, trilauryl trithiophosphite, bis (tridecyl) phosphite, ginseng (isodecyl) phosphite Ginseng (tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bis (nonylphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyl Dipropylglycol diphosphite, ginsyl nonylphenyl phosphite, ginseng (2,4-di-tert-butylphenyl) phosphite, ginseng (2,4-di-tert-butyl -5-methylphenyl) phosphite, ginseng [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylbenzene Group) phosphite, tri (decyl) phosphite, octyl diphenyl phosphite, bis ( Base) monophenylphosphite, distearylpentaerythritol diphosphite, mixture of distearylpentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, di (ten Triyl) pentaerythritol diphosphite, bis (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-diiso Propylphenylphenyl) pentaerythritol diphosphite, tetraphenyl-tetrakis (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl Phosphite, tetrakis (tridecyl) isopropylidene diphosphite, tetrakis (tridecyl) -4,4'-n-butylenebis (2-tert-butyl-5-methyl Phenol) diphosphite, hexa (tridecyl) -1,1,3-ginseng (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, (2, 4-di-tert-butylphenyl) phenylene diphosphonate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1 -Propenyl-3- fork) ginseng (1,1-dimethylethyl)- 5-methyl-4,1-phenylene) hexa (tridecyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) -2-ethyl Hexyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) -octadecyl phosphite, 2,2'-ethylenebis (4,6 -Di-tert-butylphenyl) fluorophosphite, 4,4'-butylenebis (3-methyl-6-tert-butylphenylbis (tridecyl)) phosphite, ginseng (2-[(2,4,8,10-tert-tert-butyldibenzo [d, f] [1,3,2] dioxoheteroheptin-6-yl) oxy] ethyl ) Amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 2,4 1,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly4,4'-isopropylidene diphenol C12-15 alcohol Phosphate esters, etc. These can be used alone or in combination of two or more. The amount of the phosphorus antioxidant used is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the olefin resin.

As the sulfide-based antioxidant, for example, [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) sulfur) Propargyloxy] 5-tert-butylphenyl) sulfide, bis (tridecyl) -3,3'-thiodipropionate, dilauryl-3,3'-thio Dipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl / stearylthiothiodi Propionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-thiobis (6-tert-butyl-p-cresol), dihard Lipidyl-disulfide. These can be used alone or in combination of two or more. The amount of the sulfide-based antioxidant is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 0.5 parts by mass relative to 100 parts by mass of the olefin resin.

As for other ultraviolet absorbents, for example, 2-hydroxydibenzophenone, 2,5'-methylenebis (2-hydroxy-4-methoxybenzophenone), and the like can be mentioned. Benzophenones; 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-chlorobenzene Benzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriene) Oxazolyl), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, polyethylene glycol esters, 2- [2-hydroxy-3- (2-propenefluorene) Ethoxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methylpropenyloxyethyl) -5-tert-butylphenyl] Benzotriazole, 2- [2-hydroxy-3- (2-methacryloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-Methacryloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloxyethyl) Phenyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-pentyl-5- (2-methylpropenyloxyethyl) phenyl] benzotriazole, 2- [2- Hydroxy-3-tert-butyl-5- (3-methacryloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methylpropene Methoxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [ 2- (2-hydroxyphenyl) benzotriazoles such as 2-hydroxy-4- (3-methacryloxypropyl) phenyl] benzotriazole; resorcinol monobenzoic acid Ester, 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-4-hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate Esters, benzoic acid (3,5-di-tert-butyl-4-hydroxy) benzoic acid esters, etc .; 2-ethyl-2'-ethoxyoxadibenzidine, 2-ethoxy-4'-dodecyl stilbenes and other substituted stilbenes; Cyanoacrylates such as methyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various Metal salts or metal chelates, especially nickel, chromium salts, or chelates. These can be used alone or in combination of two or more. The amount of the ultraviolet absorber is preferably 0.001 to 10 parts by mass relative to 100 parts by mass of the olefin resin, and more preferably 0.01 to 0.5 parts by mass.

In the case of hindered amine compounds, for example, 2,2,6,6-tetramethyl-4-piperidylstearate, 1,2,2,6,6-pentamethyl-4-piperidinylstearate Fatty acid esters, 2,2,6,6-tetramethyl-4-piperidinylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (2,2,6,6-tetramethyl-4-piperidinyl) -1,2,3,4-butane tetracarboxylate, (1,2,2,6,6-penta Methyl-4-piperidinyl) -1,2,3,4-butanetetracarboxylic acid ester, bis (2,2,6,6-tetramethyl-4-piperidinyl) fluorenylbis (tridecyl ) -1,2,3,4-butane tetracarboxylic acid ester, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) -bis (tridecyl) -1, 2,3,4-butane tetracarboxylic acid ester, bis (1,2,2,4,4-pentamethyl-4-piperidinyl) -2-butyl-2- (3,5-di- tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensation Polymer, 1,6-bis (2,2,6,6-tetramethyl-4-piperidinylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate 1,6-bis (2,2,6,6-tetramethyl-4-piperidinylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine Polycondensate, 1,5,8,12-([2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidinyl) amino) -s -Triazine-6-yl] -1,5,8,12-tetraazadodeca , 1,5,8,12-[[2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidinyl) amino) -s -Triazine-6-yl] -1,5,8-12-tetraazadodecane, 1,6,11-ginseng [2,4-bis (N-butyl-N- (2,2, 6,6-tetramethyl-4-piperidinyl) amino) -s-triazin-6-yl] aminoundecane, 1,6,11-reference [2,4-bis (N-butane -N- (1,2,2,6,6-pentamethyl-4-piperidinyl) amino) -s-triazin-6-yl] aminoundecane, bis {4- (1 -Octyloxy-2,2,6,6-tetramethyl) piperidinyl} decanedione ester, bis {4- (2,2,6,6-tetramethyl-1-undecyl) Oxy) piperidinyl) carbonate and the like. These can be used alone or in combination of two or more. The 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 relative to 100 parts by mass of the olefin resin.

As the core agent different from the component (A), for example, sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, lithium-2,2'- Methylenebis (4,6-di-tert-butylphenyl) phosphate, aluminum hydroxybis [2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate ], Sodium benzoate, 4-tert-butyl aluminum benzoate, sodium adipate and 2 sodium bicyclic [2.2.1] heptane-2,3-dicarboxylic acid metal salts, N, N ', N ”-gins [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N', N” -tricyclohexyl-1,3,5-benzenetricarboxamidine Amine compounds such as amines, N, N'-dicyclohexylnaphthalenedicarboxylic acid amines, 1,3,5-tris (dimethylisopropylamino) benzene, and the like. These can be used alone or in combination of two or more. The amount of the nucleating agent different from the component (A) is preferably 0.001 to 10 parts by mass, and more preferably 0.005 to 5 parts by mass, relative to 100 parts by mass of the olefin resin. Within range.

Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and cresyl-2,6-xylene. Phosphate, resorcinol bis (diphenyl phosphate), (1-methylethylene) -4,1-phenylene tetraphenyldiphosphate, 1,3-phenylene phosphate ( 2,6-dimethylphenyl) phosphate, aromatic phosphate esters of ADEKA Corporation under the trade names "ADK STAB FP-500", "ADK STAB FP-600", "ADK STAB FP-800", phenyl Phosphonic acid divinyl, phenylphosphonic acid diallyl, phenylphosphonic acid (1-butene), phosphonates, etc. Phosphinic acid phenyl, diphenylphosphine (Phosphinic acid) methyl, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, etc. Phosphinic acid ester, bis (2-allylphenoxy) couple Phosphorous nitrogen compounds such as phosphorus nitrogen, xylenyl azophosphine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate Azine, phosphorus vinyl benzyl And flame retardants such as phosphorous flame retardants, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A epoxy resin, brominated novolac epoxy resin, hexabromobenzene, Pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromo Cyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, and 2,4,6-para (tribromophenoxy) -1 , 3,5-triazine, tribromophenylmaleimide, tribromophenylacrylate, tribromophenylmethacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl Brominated flame retardants such as acrylate and brominated styrene. These can be used alone or in combination of two or more. These flame retardants are preferably used in combination with anti-dripping agents such as fluororesin, or flame retardant additives such as polyhydric alcohol and magnesite. The blending amount when blended with a flame retardant is preferably 1 to 100 parts by mass, and more preferably 10 to 70 parts by mass relative to 100 parts by mass of the olefin resin.

The lubricant is added for the purpose of imparting slippage to the surface of the molded body and improving the effect of preventing scratches. In terms of lubricants, unsaturated fatty acids such as ammonium oleate and ammonium erucate; saturated fatty acid ammonium such as behenyl behenate and ammonium stearate; butyl stearate; Stearyl alcohol, monoglyceryl stearate, sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, hardened castor oil, ammonium stearate, oil Amidoamine, ethylenebisstearate, etc. These can be used alone or in combination of two or more. The blending amount of the lubricant is preferably 0.01 to 2 parts by mass, and more preferably 0.03 to 0.5 parts by mass, relative to 100 parts by mass of the olefin resin.

Examples of fillers include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, and white cloud Stone, silica, alumina, potassium titanate whiskers, calcareous silica, fibrous magnesium oxysulfate, etc., can be used by selecting the particle diameter (in the fibrous form, fiber diameter or fiber length and aspect ratio). These can be used alone or in combination of two or more. As the filler, a surface treatment may be used as necessary. The amount of the filler used is preferably 1 to 80 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass, relative to 100 parts by mass of the olefin resin.

Magnesite is a compound salt compound consisting of magnesium, aluminum, hydroxyl, carbonate, and any crystal water known as natural or synthetic materials. Part of magnesium or aluminum is alkali metal or zinc. Those substituted with another metal or those in which a hydroxyl group or a carbonic acid group is substituted with another anionic group. Specifically, for example, those in which the metal of the magnesite is represented by the following general formula (5) are substituted with an alkali metal. In the case of Al-Li-based magnesite, a compound represented by the following general formula (6) can also be used.

Here, in the general formula (5), x1 and x2 are each a number that satisfies the condition represented by the following formula 0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 ≦ 20, and p is 0 or a positive number.

Here, in the general formula (6), A ^q- is a q-valent anion, and p is 0 or a positive number. In addition, the carbonate anions in these magnesite may be partially substituted by other anions.

The magnesite can be dehydrated from crystal water, or it can be an organic metal salt such as stearic acid, a higher fatty acid, an oleic acid alkali metal salt, and a higher alkali metal salt of dodecylbenzenesulfonic acid. Covered with sulfonic acid metal salt, higher fatty acid amidine, higher fatty acid ester or wax.

The magnesite may be natural or synthetic. As for the synthetic method of the magnesite, for example, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, and Japanese Patent Publication No. 61 -174270, Japanese Unexamined Patent Publication No. 5-179052, and other known methods. Moreover, magnesite can be used without being limited to its crystal structure, crystal particles, and the like. These can be used alone or in combination of two or more. The amount of blended magnesite is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the olefin resin.

As the antistatic agent, for example, cationic antistatic agents such as fatty acid quaternary ammonium ion and polyamine quaternary salt; higher alcohol phosphate salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, Anionic antistatic agents such as anionic alkyl sulfonate, higher alcohol sulfate, higher alcohol ethylene oxide adduct sulfate, higher alcohol ethylene oxide adduct phosphate, etc .; polyol Nonionic antistatic agents such as fatty acid esters, polyglycol phosphates, polyoxyethylene alkyl allyl ethers; amphoteric alkyl betaines such as alkyl dimethylaminoacetic acid betaine, and imidazoline type Amphoteric antistatic agents such as amphoteric active agents. These can be used alone or in combination of two or more. The amount of the antistatic agent is preferably 0.03 to 2 parts by mass, more preferably 0.1 to 0.8 parts by mass, relative to 100 parts by mass of the olefin resin.

In terms of pigments, commercially available pigments can also be used, such as Pigment Red 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; 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, 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; 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, 62, 64; pigment violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc. These can be used alone or in combination of two or more.

In terms of dyes, azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, perylene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro Dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, etc. may be used alone or in combination of two or more.

Fluorescent brightener is a compound that absorbs ultraviolet rays from sunlight or artificial light, converts them into visible light from purple to blue, and performs radiant fluorescent effect, thereby promoting the whiteness or bluishness of the formed body. As the fluorescent whitening agent, for example, a benzoxazole-based compound C.I. Fluorescent Brightner 184; a coumarin-based compound C.I. Fluorescent Brightner 52; a diaminophosphonium difluoride-based compound C.I. Fluorescent Brightner 24, 85, 71 and the like. The amount of the fluorescent whitening agent used is preferably 0.00001 to 0.1 parts by mass, and more preferably 0.00005 to 0.05 parts by mass, relative to 100 parts by mass of the olefin resin.

When molding the olefin-based resin composition of the present invention, it can be molded using a conventional molding method. A molded product can be obtained by using, for example, an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an expansion molding method, a calender molding method, a condensation molding method, a dip molding, and a foam molding method.

The application of the olefin-based resin composition of the present invention includes, for example, automotive materials such as protective cases, dashboards, and dashboards, housing applications for refrigerators, washing machines, and vacuum cleaners, electrical and mechanical parts, food utensils, buckets, bathing supplies, and the like. Household goods, toys, stationery and other miscellaneous goods, disposable syringes sterilized by heat or radiation, transfusion / blood transfusion kits, medical appliances such as blood collection devices, clothing cabinets, and various storage cabinets for clothing storage Food packaging cups, soft canned food, microwave ovens, beverages, seasonings, cosmetics, pharmaceuticals, washing bottles or packaging containers and lids, rice, bread, stains Shaped products such as food cabinets, storage tanks, bottles, films, sheets, fibers, etc. Examples

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples and the like.

[Production Examples 1 to 16] (1) A component (A), a component (B), a component (C), and a component (D) were mixed in the amounts shown in Table 1 to prepare a composition.

DMDBS: 1,3: 2,4-bis (3,4-dimethylbenzylidene sorbitol) EBSA: N.N'-ethylenebisstearate BA: BA behenate SA: Ammonium stearate tBPS: tert-butyl salicylate PV-100: a mixture of glyceryl stearate and glyceryl palmitate (mass ratio: 1: 1)

[Examples 1 to 4, Comparative Examples 1 to 12] As olefin resin, 100 parts by mass of random-polypropylene with MFR = 12 g / min was prepared in the blending amount described in Table 2, phenolic antioxidant (product made by ADEKA Corporation) (Named "ADK STAB AO-60") 0.05 parts by mass, phosphorus-based antioxidant (trade name "ADK STAB 2112" manufactured by ADEKA Corporation) 0.1 parts by mass, 0.05 parts by mass of calcium stearate, and Preparation Examples 1 to 16 The composition was dry-mixed using a Henschel mixer. After mixing, pelletizing was performed using an extruder under conditions of a resin temperature of 200 ° C. The obtained pellets were dried in a thermostat at 60 ° C for 8 hours. After drying, a 1-mm-thick sheet was formed using an injection molding machine (EC100-2A; manufactured by Toshiba Machinery Co., Ltd.) at an injection temperature of 200 ° C.

From the obtained sheet, a test piece having a size of 10 mm × 10 mm × 1 mm was produced, and after standing at a constant temperature machine at 23 ° C. for more than 48 hours, the test was measured with haze-gard 2 [manufactured by Toyo Seiki Co., Ltd.] and measured in accordance with ASTM D 1003. (Haze). These results are shown in Table 2 below. Regarding these results, FIG. 1 is a graph showing the relationship between the total amount of the composition of the present invention and Haze (%) with respect to the olefin-based resin. In the same chart, the horizontal axis is the total amount of the composition, and the vertical axis is Haze (%).

The parameters (I) to (III) described in Table 2 will be described. (I) is "○" when the blending amount of the component (B) with respect to 100 parts by mass of the component (A) is in the range of 10 to 200 parts by mass, and "*" is displayed outside the range. (II) means that the component (C) is equal to or less than the component (B) component, and exceeds "0" when it exceeds 0 parts by mass; otherwise, it indicates "x". (III) is "○" when the component (D) is below the blending amount of the (C) component, and "×" when it is outside this range.

From FIG. 1, it was confirmed that the composition of the present invention satisfying all the parameters (I), (II), and (III) can exhibit an excellent transparency improvement effect even at a low temperature processing even with a small amount of addition. Moreover, the obtained sheet did not generate odor.

From the above, it can be seen that the composition of the present invention can provide a molded product that can be molded at a low temperature by using a dibenzylidene sorbitol compound, has an odor suppressed, and has excellent transparency.

[Fig. 1] A graph showing the relationship between the total amount of the composition of the present invention and the olefin-based resin and Haze (%).

Claims (5)

A composition with respect to the following general formula (1) (In formula (1), R ¹ , R ^2, and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. 100 parts by mass of a sorbitol compound (A) represented by an alkoxycarbonyl group or a halogen atom, s, t, and u each being an integer of 1 to 5), and 10 to 200 parts by mass of a amide compound (B) And a salicylate-based ultraviolet absorber (C), which is characterized in that the component (C) is the blending amount of the component (B) or less but more than 0 parts by mass, and the glycerin fatty acid ester (D) is (C) The amount of components to be blended is configured below. The composition according to claim 1, wherein the component (A) is 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol. The composition according to claim 1 or 2, wherein the component (C) is tert-butyl salicylic acid phenyl ester. An olefin-based resin composition characterized in that it contains the composition described in any one of claims 1 to 3 so that the component (A) becomes 0.001 to 10 parts by mass relative to 100 parts by mass of the olefin-based resin. A molded product characterized by using the olefin-based resin composition according to claim 4.