JP2010229361A - Polyolefin resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin resin composition excellent in transparency. <P>SOLUTION: The polyolefin resin composition comprises 100 pts.mass of a polyolefin resin, and 0.01-1 pts.mass of a hydrazide compound represented by general formula (I): R<SB>1</SB>-Y<SB>1</SB>-CONHNHCO-Y<SB>2</SB>-R<SB>2</SB>(where R<SB>1</SB>and R<SB>2</SB>are each independently 1-10C alkyl which may be branched and/or may have a substituent, 3-12C cycloalkyl which may have a substituent, or 6-20C aryl which may have a substituent, and Y<SB>1</SB>and Y<SB>2</SB>are each independently a single bond or 1-5C alkylene provided that a hydroxyl group is excluded for the substituent) compounded together. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyolefin resin composition, and more particularly to a polyolefin resin composition exhibiting excellent transparency by blending a specific hydrazide compound.

  Polyolefin resins have the advantage of being excellent in molding processability, heat resistance, mechanical properties, low specific gravity and the like, and are widely used in films, sheets, and various molded products (structural parts, etc.). However, although the polyolefin-based resin has excellent physical properties, depending on the use, application of the polyolefin resin may be limited because the excellent performance inherent in the resin cannot be obtained. Many of the reasons why the application range of the polyolefin resin is limited are derived from the crystallinity of the polyolefin resin. In order to expand the applications of polyolefin resins, various crystal nucleating agents have been actively developed in order to improve transparency and to impart heat resistance and mechanical strength.

  As an example of using a hydrazide compound as a resin, for example, Patent Document 1 describes using a hydrazide compound having a phenol structure as a crystal nucleating agent for a polylactic acid resin.

  Patent Document 2 discloses that an amide compound selected from a chain amide, a cyclic amide, a chain hydrazide and a cyclic hydrazide is blended with polylactic acid to improve the crystallization temperature of the polylactic acid resin composition. Is described.

  Furthermore, in Patent Document 3, a plasticizer comprising an aliphatic ester derivative or an aliphatic polyether derivative and a hydrazide compound such as octanedicarboxylic acid dibenzoyl hydrazide as an organic crystal nucleating agent are used in combination with a polylactic acid resin. Proposed.

  Furthermore, Patent Document 4 proposes the use of a hydrazide compound in order to suppress the release of aldehyde from a polypropylene material clarified with dibenzylidene sorbitol.

  In addition, Patent Document 5 discloses that a hydrazide compound such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine is used as a heavy metal deactivator for crystallinity. It is described that it is used in a polypropylene resin composition.

JP 2004-323742 A JP 2004-352873 A JP 2008-69245 A Special table 2004-50002 gazette JP 2000-319463 A

  However, even if these hydrazide compounds are used in polyolefin resins, there is room for improvement in the transparency of the resulting resin molded products, and today, development of polyolefin resin compositions having further excellent transparency is desired. It was.

  Then, the objective of this invention is providing the polyolefin resin composition excellent in transparency.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by blending a specific hydrazide compound with a polyolefin-based resin, and have completed the present invention. It was.

（式中、Ｒ_１及びＲ_２は、各々独立して、分岐及び／又は置換基を有してもよい炭素原子数１〜１０のアルキル基、置換基を有してもよい炭素原子数３〜１２のシクロアルキル基、又は置換基を有してもよい炭素原子数６〜２０のアリール基を表し、Ｙ_１及びＹ_２は、各々独立して、単結合手、または、炭素原子数１〜５のアルキレン基を表す。ただし、上記置換基は水酸基を除く）で表されるヒドラジド化合物０．０１〜１質量部を配合してなることを特徴とするものである。 That is, the polyolefin resin composition of the present invention is represented by the following general formula (I) with respect to 100 parts by mass of the polyolefin resin.

(In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms which may have a branch and / or a substituent, and 3 carbon atoms which may have a substituent. Represents a cycloalkyl group having 12 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent, and Y ₁ and Y ₂ each independently represent a single bond or 1 carbon atom. Represents an alkylene group of ˜5, wherein 0.01 to 1 part by mass of a hydrazide compound represented by the above substituent is excluded).

In the polyolefin resin composition of the present invention, the hydrazide compound has 3 to 3 carbon atoms in which R ₁ and R ₂ in the following general formula (I) each may have a substituent other than a hydroxyl group. It is preferably a compound having a structure of 12 cycloalkyl groups or a phenyl group which may have a substituent other than a hydroxyl group.

In the polyolefin resin composition of the present invention, the hydrazide compound has 3 to 3 carbon atoms in which R ₁ and R ₂ in the following general formula (I) each may have a substituent other than a hydroxyl group. Twelve cycloalkyl groups, Y ₁ and Y ₂ are preferably a single bond.

（式中、Ｒ_３およびＲ_４は、各々独立に、炭素原子数１〜１２のアルキル基であり、ｎは０または１である。）で表されることが好ましい。 In the polyolefin resin composition of the present invention, the hydrazide compound has the following general formula (II):

(Wherein R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms, and n is 0 or 1).

（式中、Ｒ_５およびＲ_６は、各々独立に、炭素原子数１〜１２のアルキル基であり、ｎは０または１である。）で表されることが好ましい。 Further, in the polyolefin resin composition of the present invention, the hydrazide compound has the following general formula (III),

(Wherein R ₅ and R ₆ are each independently an alkyl group having 1 to 12 carbon atoms, and n is 0 or 1).

（式中、Ｒ_７およびＲ_８は、各々独立に、炭素原子数１〜１２のアルキル基であり、ｎは０または１である。）で表されることが好ましい。 In the polyolefin resin composition of the present invention, the hydrazide compound has the following general formula (IV):

(Wherein R ₇ and R ₈ are each independently an alkyl group having 1 to 12 carbon atoms, and n is 0 or 1).

  The polyolefin resin composition of the present invention preferably further comprises 0.01 to 1 part by mass of a fatty acid metal salt or a fatty acid amide compound. The fatty acid metal salt or the fatty acid amide compound is preferably added. Is preferably selected from the group consisting of lithium stearate, calcium stearate, sodium stearate, ethylene bisstearamide, ethylenebis (12-hydroxystearamide) and stearamide.

  According to the present invention, a polyolefin resin composition having excellent transparency can be obtained.

（式（Ｉ）中、Ｒ_１及びＲ_２は、各々独立して、分岐及び／又は置換基を有してもよい炭素原子数１〜１０のアルキル基、置換基を有してもよい炭素原子数３〜１２のシクロアルキル基、又は置換基を有してもよい炭素原子数６〜２０のアリール基を表し、Ｙ_１及びＹ_２は、各々独立して、単結合または、炭素原子数１〜５のアルキレン基を表す。ただし、上記置換基は水酸基を除く）で表される化合物が挙げられる。 The hydrazide compound used in the present invention is a compound represented by the general formula (I),

(In formula (I), R ₁ and R ₂ are each independently a branched and / or optionally substituted alkyl group having 1 to 10 carbon atoms, and optionally substituted carbon. A cycloalkyl group having 3 to 12 atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent, each of Y ₁ and Y ₂ independently represents a single bond or the number of carbon atoms 1 to 5 represents an alkylene group, provided that the substituent is a compound represented by the above formula except for a hydroxyl group.

Examples of the alkyl group having 1 to 10 carbon atoms that may have a branch and / or a substituent represented by R ₁ or R ₂ in the general formula (I) include a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, isopentyl group, tert-pentyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2 -Heptyl group, 3-heptyl group, isoheptyl group, tertiary heptyl group, n-octyl group, isooctyl group, tertiary octyl group, nonyl group, isononyl group, decyl group and the like can be mentioned.

  These alkyl groups may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, an imino group or the following aryl group, and the hydrogen atom in the alkyl group is a halogen atom, an amino group, a nitro group, Group, cyano group, alkenyl group, alkenyloxy group, alkanoyloxy group, chain aliphatic group such as alkoxycarbonyl group, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, pyridine, pyridazine , Pyrimidine, pyrazine, piperidine, piperazine, morpholine, 2H-pyran, 4H-pyran, phenyl, biphenyl, triphenyl, naphthalene, anthracene, pyrrolidine, pyridine, indolizine, indole, isoindole, indazole, purine Quinolizine, quinoline, isoquinoline, or cyclic aliphatic groups may be substituted, such as cycloalkyl groups below. These interruptions or substitutions may be combined, and these alkyl groups may have an unsaturated bond as a result of the substitution.

Examples of the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent and represented by R ₁ or R ₂ in the general formula (I) include, for example, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. , Cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, etc., and the hydrogen atom in the cycloalkyl group is a halogen atom, alkyl group, alkoxy group, alkenyl group, alkenyloxy group, alkoxyalkyl group, alkanoyloxy A group, an alkoxycarbonyl group, a nitrile group or a cyano group.

In the aryl group having 6 to 20 carbon atoms which may have a substituent, represented by R ₁ or R ₂ in the general formula (I), a hydrogen atom in the aryl group is a halogen atom or a nitro group , A cyano group, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkoxyalkyl group, an alkanoyloxy group, or an alkoxycarbonyl group, these aryl groups include, for example, a phenyl group, 3 , 4,5-trimethoxyphenyl group, 4-tert-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, phenanthryl and the like.

Examples of the alkylene group having 1 to 5 carbon atoms represented by Y ₁ or Y ₂ in the general formula (I) include methylene, ethylene, propylene, 2-methylpropylene, 2-ethylpropylene, butylene, 2- Examples include methylbutylene.

Among the hydrazide compounds described above, in the present invention, in particular, R ₁ and R ₂ in the general formula (I) each have 3 to 12 carbon atoms that may have a substituent other than a hydroxyl group. A compound having a phenyl group structure which may have a group or a substituent other than a hydroxyl group is preferably used.

Among these, in particular, R ₁ and R ₂ in the above general formula (I) may be a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent other than a hydroxyl group, and Y ₁ and Y _2. A compound having a structure in which is a single bond is particularly preferred. Moreover, a good cyclohexyl group or a phenyl group which may have R ₁ and R ₂ in the general formula (I) as a substituent an alkyl group having 1 to 12 carbon atoms, Y ₁ and Y ₂ is a single bond Particularly preferred are compounds of the hand structure.

Specific structures of the hydrazide compounds represented by the general formula (I) include the following compound No. 1-No. 8 is mentioned. However, the present invention is not limited by the following compounds.

  In the polyolefin resin composition of the present invention, the hydrazide compound represented by the general formula (I) is 0.01 to 1 part by mass, preferably 0.05 to 1 part per 100 parts by mass of the polyolefin resin. Part by mass, more preferably 0.1 to 0.5 part by mass is blended. When the amount is less than 0.01 part by mass, the effect of addition is insufficient, and when it is more than 1 part by mass, the effect of the present invention may not be obtained.

  The hydrazide compound represented by the general formula (I) can be produced according to a known synthesis example, but can be generally synthesized according to the following reaction formula (1). That is, it can be easily synthesized by a condensation reaction with a carboxylic acid compound or a reaction with an acid halide with respect to hydrazine or a derivative thereof.

Reaction formula (1)

  Examples of the polyolefin resin used in the polyolefin resin composition of the present invention include low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, Α-olefin polymer such as cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene block or Examples include α-olefin copolymers such as random copolymers.

  Among the above-mentioned polyolefin resins, polypropylene resins that have a remarkable effect of using the crystal nucleating agent of the present invention are preferred, and polypropylene, ethylene / propylene block or random copolymer, and α-olefin / propylene other than ethylene. Blocks or random copolymers and mixtures of these propylene polymers with other α-olefin polymers can also be used.

  In these polyolefin resins, polyolefin resins having an MFR of 8 to 100 g / 10 min when measured according to JIS K7210 can be preferably used because the effects of the present invention can be obtained well. A polyolefin resin having an MFR (melt flow rate) of 8 to 60 g / 10 min is preferable.

  In the polyolefin resin composition of the present invention, it is preferable to add a known neutralizing agent in order to neutralize the residual catalyst in the polyolefin resin. Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or fatty acid amides such as ethylene bis (stearamide), ethylene bis (12-hydroxystearamide), and stearic acid amide. Compounds may be mentioned, and these neutralizing agents may be mixed and used.

  In particular, lithium stearate, sodium stearate, and ethylene bis (12-hydroxystearamide) are preferably used because the transparency of the molded polyolefin-based resin composition is good.

  In addition, the polyolefin resin composition of the present invention may be added with other commonly used additives as necessary within a range not inhibiting the effects of the present invention. Other additives include neopentyl glycol derivatives, polyalkylene glycols and derivatives thereof, polyhydric alcohols and epoxy compounds of derivatives thereof; antioxidants composed of phenolic, phosphorus, sulfur, etc .; hindered amines A light stabilizer comprising a light stabilizer, an ultraviolet absorber, etc .; a hydrocarbon compound, a fatty acid compound, an aliphatic alcohol compound, an aliphatic ester compound, an aliphatic amide compound, an aliphatic carboxylic acid metal salt compound, or Other metal soap lubricants; heavy metal deactivators; antistatic agents composed of cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants; nucleating agents; difficult Filler: Glass fiber, calcium carbonate, etc .; hydrotalcite, fumed silica, fine particle silica, silica, diatom Silicate inorganic additives such as clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, aragonite, attapulgite, talc, mica, minnesotite, pyrophyllite, silica; Pigments, antifogging agents, various fillers, mold release agents, fragrances, foaming agents, antibacterial agents, antifungal agents, and the like. In particular, an antioxidant composed of phenol and phosphorus is preferably used because it has an effect as a coloring inhibitor of the polyolefin resin composition.

  Examples of the phenol-based antioxidant include 2,6-ditertiarybutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditertiarybutyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(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′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-ditert-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-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-to (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyl Oxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acrolate) Yloxy-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) propyl Pioneto], and the like. The usage-amount of the said phenolic antioxidant is 0.001-10 mass parts with respect to 100 mass parts of said polyolefin resin, Preferably, it is 0.01-5 mass parts.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,5-ditert-butylphenyl) phosphite, and tris (nonylphenyl). ) Phosphite, tris (dinonylphenyl) phosphite, tris (mono- and di-mixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite , Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphat , Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentylglycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol Diphosphite, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4- Dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenylphosphite, bis [2,2'-methylenebis (4,6 -Diamylphenyl) -Isopropylidene diphenyl phosphite, tetratridecyl-4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-5- Tert-butyl-4-hydroxyphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylenediphosphonite, tris (2-[(2,4,7,9-tetrakis tert-butyldibenzo [ d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2 -Butyl-2-ethylpropanediol-2,4,6-tritert-butylphenol monophosphite and the like. The usage-amount of the said phosphorus antioxidant is 0.001-10 mass parts with respect to 100 mass parts of said polyolefin resin, Preferably, it is 0.01-5 mass parts.

  Examples of the sulfur-based antioxidant include dialkyl thiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). [Beta] -alkyl mercaptopropionic acid esters. The usage-amount of the said sulfur type antioxidant is 0.001-10 mass parts with respect to 100 mass parts of said polyolefin resin, Preferably, it is 0.01-5 mass parts.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetra Methyl-piperidyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, Lakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl)- Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -bis (tridecyl) -1,2,3,4 Butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 3,9 -Bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxas B [5.5] Undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 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-triazine-6 -Il] -1,5,8 , 12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s -Triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetra) Methyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-) Pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-te Lamethyl-4-piperidylamino) hexane / dibromoethane polycondensate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) decanedioate, bis (2,2,6,6) -Tetramethyl-4-undecyloxypiperidyl) carbonate, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals. The amount of the hindered amine light stabilizer used is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 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-th Octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -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] benzene Zotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxy) Ethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2- Methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) 2- (2-hydroxypheny) such as phenyl] benzotriazole B) benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6 -Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-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- Ditert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert Benzoates such as butyl-4-hydroxy) benzoate, behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxy Substituted oxanilides such as zanilides; 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, especially nickel, chromium salts, or chelates. The usage-amount of the said ultraviolet absorber is 0.001-10 mass parts with respect to 100 mass parts of said polyolefin resin, Preferably, it is 0.01-5 mass parts.

  Examples of the aliphatic amide compound used as the lubricant include monofatty acid amides such as lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, and 12-hydroxystearic acid amide; N, N '-Ethylenebislauric acid amide, N, N'-methylenebisstearic acid amide, N, N'-ethylenebisstearic acid amide, N, N'-ethylenebisoleic acid amide, N, N'-ethylenebisbehenic acid Amide, N, N′-ethylenebis-12-hydroxystearic acid amide, N, N′-butylene bisstearic acid amide, N, N′-hexamethylene bisstearic acid amide, N, N′-hexamethylene bisoleic acid N, N′-biphenyl such as amide, N, N′-xylylenebisstearic acid amide Fatty acid amides; alkylolamides such as stearic acid monomethylolamide, palm oil fatty acid monoethanolamide, stearic acid diethanolamide; N-oleyl stearamide, N-oleyl oleic acid amide, N-stearyl stearic acid amide, N-substituted fatty acid amides such as N-stearyl oleic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide; N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide N, N′-N, N′-dioleyl sebacic acid amide, N, N′-distearyl sebacic acid amide, N, N′-distearyl terephthalic acid amide, N, N′-distearyl isophthalic acid amide, etc. -Substituted dicarboxylic acid amides. You may use these by 1 type or a 2 or more types of mixture. The amount of the lubricant used is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Examples of the nucleating agent include carboxylic acids such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate. Metal salts, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate and lithium-2,2′-methylenebis (4,6-di) Phosphate metal salts such as tert-butylphenyl) phosphate, polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene) sorbitol, N, N ′, N ″ -tris [2-methylcyclohex L] -1,2,3-propanetricarboxamide, N, N ′, N ″ -tricyclohexyl lu 1,3,5-benzenetricarboximide, N, N′-dicyclohexyl-naphthalenedicarboxamide, 1,3 Examples include amide compounds such as 5-tri (dimethylisopropoylamino) benzene. The usage-amount of the said nucleating agent is 0.001-10 mass parts with respect to 100 mass parts of said polyolefin resin, More preferably, it is 0.005-5 mass parts.

  Examples of the flame retardant include aromatic phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate and resorcinol bis (diphenyl phosphate), Phosphonic acid esters such as divinyl phenylphosphonate, diallyl phenylphosphonate and phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- Phosphinic acid esters such as 10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, polyphosphoric acid Lamin, polyphosphate melam, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol Novolac-type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 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, tribromophenylmaleimi , Tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and include brominated flame retardants such as brominated styrene and the like. The usage-amount of the said flame retardant is 1-50 mass parts with respect to 100 mass parts of said polyolefin resin, More preferably, it is 1-20 mass parts.

  In the polyolefin resin composition of the present invention, the method of blending the hydrazide compound and the above-mentioned additives into the polyolefin resin is not particularly limited, and can be performed by a conventionally known method. For example, it may be mixed with polyolefin resin powder or pellets in a dry blend, or a part of the additive may be preblended and then dry blended with the remaining components. After dry blending, for example, mixing may be performed using a mill roll, a Banbury mixer, a super mixer, or the like, and kneading may be performed using a single screw or twin screw extruder. This mixing and kneading is usually performed at a temperature of about 120 to 220 ° C. A method of adding an additive at the polymerization stage of a polyolefin-based resin, after mixing in a desired ratio together with a granulating aid such as a binder, wax, solvent, silica, etc., and then granulating to make a one-pack composite additive, A method of adding the one-pack composite additive to the polyolefin resin, a method of preparing a masterbatch containing the additive at a high concentration, and adding the masterbatch to the polyolefin resin can be used.

  When molding the polyolefin-based resin composition of the present invention, as with general plastics, extrusion molding, injection molding, blow molding, vacuum molding, compression molding, and the like can be performed. Sheets, bars, bottles, Various molded products such as containers can be easily obtained. The polyolefin resin composition of the present invention may be a fiber reinforced plastic by blending glass fibers, carbon fibers and the like. Although the said shaping | molding is influenced by the melt viscosity of resin, the preferable shaping | molding process temperature is the range of 180-230 degreeC, Especially preferably, it exists in the range of 190-220 degreeC. If the temperature is lower than 180 ° C., the polyolefin resin itself cannot be sufficiently dissolved and the molded product may be uneven. If the temperature is 230 ° C. or higher, the effects of the present invention may not be obtained.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples.

[Production Example 1]
For 100 parts by mass of polyolefin resin (ethylene / propylene random copolymer; melt flow value (8 g / 10 min; 230 ° C.)), tetrakis [methylene-3- (3 ′, 5′- Ditertiary butyl-4′-hydroxyphenyl) propionate] 0.1 part by mass of methane, 0.1 part by mass of tris (2,4-ditertiarybutylphenyl) phosphite as a phosphorus antioxidant, neutralizing agent As follows, 0.05 part by mass of calcium stearate, 0.035 part by mass of α, α′-di (t-butylperoxy) diisopropylbenzene, and the following Tables 1 to 3 for adjusting the fluidity of the polyolefin resin The hydrazide compound was mixed with a Henschel mixer (FM200; manufactured by Mitsui Mining Co., Ltd.) at 1000 rpm for 1 minute, and a twin-screw extruder (equipment) PCM-30 manufactured by Ikegai Co., Ltd., extrusion temperature: 240 ° C., screw speed: 160 rpm) to obtain pellets.The pellets containing no nucleating agent were measured at 230 ° C. according to the measurement method of JIS K7210. The melt flow rate (MFR) was measured and found to be 42 g / 10 min The following evaluation was performed on the obtained pellets.

(Degree)
Using the injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.), the following injection conditions (injection temperature: 200 ° C., injection pressure: 70-80 MPa, time for filling the mold: 40 seconds) , Mold temperature: 40 ° C., mold cooling time: 20 seconds), and a 60 mm square square with a thickness of 0.5 mm, 1 mm, or 2 mm was obtained. Immediately after injection molding, these sheets are allowed to stand for 48 hours or more in a thermostatic chamber having a temperature of 23 ° C., and the haze of the test piece is measured with Haze Guard 2 (manufactured by Toyo Seiki Seisakusho Co., Ltd.). did. The degree of transparency indicates that the lower the numerical value, the better the transparency of the test piece. These results are shown in Tables 1 to 3 below.

１）コントロール：結晶核剤無添加
２）比較化合物１：１，３：２，４−ビス（３，４−ジメチルベンジリデン）ソルビトール

1) Control: no addition of crystal nucleating agent 2) Comparative compound 1: 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol

３）比較化合物２：

４）比較化合物３：

５）比較化合物４：

６）比較化合物５：

７）比較化合物６：

８）比較化合物７：

3) Comparative compound 2:

4) Comparative compound 3:

5) Comparative compound 4:

6) Comparative compound 5:

7) Comparative compound 6:

8) Comparative compound 7:

  From the comparison between Example 1-3 and Comparative Example 1-2 in Table 1 above, when the same amount was used, the polyolefin to which the specific hydrazide compound according to the present invention was added, compared to the case where a commercially available nucleating agent was added. It was confirmed that the molded product of the resin-based resin composition was excellent in transparency.

  In addition, from the data of Comparative Example 2-1 and Comparative Examples 2-2 to 2-7 in Table 2 above, when a hydrazide compound is added that is not a specific hydrazide compound according to the present invention, polyolefin It became clear that rather than improving the transparency of the molded product of the resin-based resin composition, it deteriorated rather. On the other hand, from the comparison of Examples 2-1 to 2-7 and Comparative Example 2-1 in Table 2 above, by adding the specific hydrazide compound according to the present invention, a molded article of polyolefin resin composition It was confirmed that the transparency of was improved. Further, from Table 3 above, it was confirmed that the molded article of the polyolefin resin composition according to the present invention was excellent in transparency even when the test piece was thicker.

[Production Example 2]
In the said manufacture example 1, a hydrazide compound is replaced with 0.2 mass part of 1, 2- dicyclohexyl carbonyl hydrazide (compound No. 1), 0.05 mass part of calcium stearate is replaced with the neutralizing agent of following Table 4. Except for the above, a test piece having a thickness of 1 mm was prepared in the same manner as in Production Example 1, and the haze was determined. These results are shown in Table 4 below.

２）コントロール：中和剤無添加

2) Control: No neutralizer added

  From Examples 4-1 to 4-6 in Table 4, the transparency of the molded article of the polyolefin resin composition of the present invention is further improved by adding a neutralizing agent comprising a fatty acid metal salt or a fatty acid amide compound. I was able to confirm.

Claims (8)

The following general formula (I) with respect to 100 parts by mass of the polyolefin resin:

(In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms which may have a branch and / or a substituent, and 3 carbon atoms which may have a substituent. Represents a cycloalkyl group having 12 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent, and Y ₁ and Y ₂ each independently represent a single bond or 1 carbon atom. A polyolefin-based resin composition comprising 0.01 to 1 part by mass of a hydrazide compound represented by (1) to (5), wherein the substituent is a hydroxyl group. In the hydrazide compound, R ₁ and R ₂ in the general formula (I) may each have a substituent other than a hydroxyl group, a cycloalkyl group having 3 to 12 carbon atoms, or a substituent except a hydroxyl group 2. The polyolefin resin composition according to claim 1, which is a compound having a phenyl group structure which may have a group. In the hydrazide compound, R ₁ and R ₂ in the general formula (I) may each have a substituent other than a hydroxyl group, a cycloalkyl group having 3 to 12 carbon atoms, and Y ₁ and Y ₂ The polyolefin resin composition according to claim 1, wherein the polyolefin resin composition is a single bond. The hydrazide compound has the following general formula (II):

(Wherein R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms, and n is 0 or 1). . The hydrazide compound has the following general formula (III):

(Wherein R ₅ and R ₆ are each independently an alkyl group having 1 to 12 carbon atoms, and n is 0 or 1). . The hydrazide compound has the following general formula (IV):

(Wherein R ₇ and R ₈ are each independently an alkyl group having 1 to 12 carbon atoms, and n is 0 or 1). .   Furthermore, the polyolefin-type resin composition as described in any one of Claims 1-6 formed by adding 0.01-1 mass part of fatty acid metal salt or a fatty-acid amide compound.   The fatty acid metal salt or the fatty acid amide compound is selected from the group consisting of lithium stearate, calcium stearate, sodium stearate, ethylene bisstearamide, ethylenebis (12-hydroxystearamide) and stearic amide. The polyolefin resin composition according to claim 7.