JP5714204B2 - Polyolefin resin composition - Google Patents

Description

  The present invention relates to a polyolefin resin composition, and more particularly, to a polyolefin resin composition having improved transparency by adding a predetermined 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, since polyolefin resin has a slow crystallization rate after molding, molding cycle properties are low, and large crystals are generated by the progress of crystallization after heat molding, resulting in insufficient transparency and strength. .

  These disadvantages are all derived from the crystallinity of the polyolefin resin, and are known to be eliminated if the crystallization temperature of the polyolefin resin can be increased and fine crystals can be rapidly generated. .

  For this purpose, it is known to add a crystal nucleating agent or a crystallization accelerator. Conventionally, sodium benzoate, 4-tert-butylaluminum benzoate, sodium adipate and disodium bicyclo [2 2.1] Metal salt of carboxylic acid such as heptane-2,3-dicarboxylate, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-ditert-butyl) Phosphoric acid ester metal salts such as phenyl) phosphate and lithium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (dimethylbenzylidene) sorbitol, etc. Compounds such as polyhydric alcohol derivatives have been used.

Among these compounds, as a compound that is particularly effective in improving the transparency of polyolefin resins,
For example, Patent Document 1, Patent Document 2 and the like propose dibenzylidene sorbitol compounds, and Patent Document 3, Patent Document 4, Patent Document 5 and the like disclose dibenzylidene sorbitol compounds having a substituent on the benzene ring. Proposed. Patent Document 6 proposes an acetal compound having a substituted aryl group.

  Further, Patent Document 7, Patent Document 8, Patent Document 9 and Patent Document 10 propose metal salts of cyclic phosphate esters of alkylidene bisphenols.

  Furthermore, attempts have been made to improve the effect by combining these compounds. For example, Patent Document 11 and Patent Document 12 include a crystalline propylene polymer, a phosphate compound, and dibenzylidene sorbitol. It has been proposed to use a compound in combination, and Patent Document 13 proposes the combined use of a dibenzylidene sorbitol derivative and a metal salt of an aromatic organophosphate for a crystalline synthetic resin.

JP 50-139150 A Japanese Patent Laid-Open No. 51-22740 JP-A-53-117044 JP-A-58-17135 Japanese Patent Laid-Open No. 3-102242 Special table 2007-534827 gazette JP-A-58-1736 JP 59-184252 A Japanese Patent Laid-Open No. 5-140466 Japanese Patent Laid-Open No. 5-156078 JP-A-62-209151 Japanese Patent Laid-Open No. 2-102242 JP-A-8-3364

However, the improvement effect by the combination described in these publications is not yet satisfactory in practical use, and in particular, the improvement of the transparency of the polyolefin resin having a high melt flow rate (MFR) is insufficient. Improvements were sought.
Accordingly, an object of the present invention is to provide a polyolefin resin composition that is excellent in transparency even if it is a polyolefin resin having a high melt flow rate (MFR), solving the above-described problems of the prior art. is there.

  In view of the present situation, the present inventors have made extensive studies to solve the above problems, and as a result, added dibenzylidene sorbitol compound and alkali metal salt of aromatic organophosphate to polyolefin resin at a specific ratio. As a result, the inventors have found that the above object can be achieved, and have completed the present invention.

（式中、ｎは、０乃至２の整数であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、各々独立して、水素原子、ハロゲン原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、炭素原子数２〜４のアルケニル基、炭素原子数１〜４のヒドロキシルアルキル基、炭素原子数１〜４のハロゲン化アルキル基及び炭素原子数１〜４のヒドロキシハロゲン化アルキル基からなる群から選択される）で表されるジベンジリデンソルビトール化合物（Ａ）及び、下記一般式（２）、

（式中、Ｒ^６〜Ｒ^９は各々独立して、水素原子又は炭素原子数１〜９のアルキル基を表し、Ｒ^１０は水素原子又はメチル基を表し、Ｍはアルカリ金属を表す）で表される有機リン酸エステルのアルカリ金属塩化合物（Ｂ）のみを配合してなるものであって、上記ポリオレフィン系樹脂１００質量部に対し、（Ａ）成分と（Ｂ）成分の総和が０．０１〜１．０質量部で、かつ（Ａ）成分と（Ｂ）成分の比率（質量比）が、（Ａ）／（Ｂ）＝９９／１〜８０／２０の範囲内であることを特徴とするものである。 That is, the polyolefin resin composition of the present invention has the following general formula (1) as a crystal nucleating agent for a polyolefin resin having a melt flow rate (MFR) at 230 ° C. of 20 dg / min or more.

(In the formula, n is an integer of 0 to 2, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, or an alkyl having 1 to 4 carbon atoms. A group, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxylalkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms A dibenzylidene sorbitol compound (A) represented by the following formula (2), selected from the group consisting of 4 hydroxyhalogenated alkyl groups:

(Wherein R ^{6 to} R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ¹⁰ represents a hydrogen atom or a methyl group, and M represents an alkali metal). The organic phosphate ester alkali metal salt compound (B) alone is blended, and the total sum of the component (A) and the component (B) is 0.01 with respect to 100 parts by mass of the polyolefin resin. -1.0 part by mass, and the ratio (mass ratio) of the component (A) to the component (B) is in the range of (A) / (B) = 99/1 to 80/20. To do.

In the present invention, the polyolefin resin is preferably a polypropylene resin having a melt flow rate (MFR) at 230 ° C. of 20 to 100 dg / min, and R ^{1 to} R ⁴ in the general formula (1) are It is also preferable that each is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and R ⁵ is a hydrogen atom. Furthermore, in the present invention, those in which M in the general formula (2) is lithium and R ^{6 to} R ⁹ are tertiary butyl groups are preferably used.

  According to the present invention, the polyolefin resin has a high melt flow rate (MFR) by blending a dibenzylidene sorbitol compound and an aromatic organophosphate alkali metal salt compound prepared at a specific ratio. Even if it is polyolefin resin, the polyolefin resin composition excellent in transparency can be provided.

The polyolefin resin composition of the present invention is described in detail below.
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 polyolefin-based resins, a polypropylene resin that has a remarkable effect of using the crystal nucleating agent according to the present invention is suitable. Polypropylene, ethylene / propylene block or random copolymer, α-olefin / propylene other than ethylene Blocks or random copolymers and mixtures of these propylene polymers with other α-olefin polymers are particularly preferably used.

  The above polyolefin-based resin has a melt flow rate (MFR) at 230 ° C. of 20 dg / min or more, and a remarkable effect of the invention can be obtained. In actual molding, the melt flow rate (MFR) is 20 to 100 dg / min. Are more preferred. If it is 20 dg / min or less, the effects of the present invention may not be obtained. However, a polyolefin resin composition having a melt flow rate (MFR) of 100 dg / min or more is difficult to extrude, but does not deny the effect of the present invention, which is an effect of improving the transparency of the polyolefin resin composition. .

  In the polyolefin resin composition of the present invention, a dibenzylidene sorbitol compound represented by the above general formula (1) and an alkali metal salt of an aromatic organophosphate represented by the above general formula (2) as a crystal nucleating agent Is blended.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the general formula (1) include, for example, a methyl group, an ethyl group, a propyl group, Examples include isopropyl group, butyl group, secondary butyl group, tertiary butyl group, and isobutyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the general formula (1) include, for example, a methoxy group, an ethoxy group, a propoxy group, And a butoxy group.

Examples of the alkenyl group having 2 to 4 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the general formula (1) include an allyl group and a 3-methylallyl group. Can be mentioned.

Examples of the hydroxyalkyl group having 1 to 4 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the general formula (1) include 1-hydroxypropyl group, 1, Examples include 2,3-trihydroxypropyl group.

Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the general formula (1) include a 1,2-dibromopropyl group. Etc.

Examples of the hydroxyhalogenated alkyl group having 1 to 4 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the general formula (1) include 1-hydroxy-2-bromopropyl. Groups and the like.

  Examples of the dibenzylidene sorbitol compound used in the present invention include the compounds shown below. However, the present invention is not limited by the following compounds.

Examples of the alkyl group having 1 to 9 carbon atoms represented by R ^{6 to} R ⁹ in the general formula (2) include amyl, tertiary amyl, hexyl, heptyl, octyl, Examples include isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, and the like. Among these, a tertiary butyl group is particularly preferable.

  Examples of the alkali metal salt compound of the aromatic organophosphate used in the present invention include the compounds shown below. However, the present invention is not limited by the following compounds.

  In the polyolefin resin composition of the present invention, when the alkali metal salt compound of the aromatic phosphate ester is used in combination with a fatty acid metal salt soap, particularly a fatty acid lithium salt soap, the effect of the present invention is remarkably obtained. This is preferable.

  In the polyolefin resin composition of the present invention, the sum of the dibenzylidene sorbitol compound and the alkali metal salt compound of the organophosphate is 0.01 to 1.0 mass with respect to 100 parts by mass of the polyolefin resin. Parts, preferably 0.03 to 0.7 parts by mass, more preferably 0.03 to 0.6 parts by mass. When the amount is less than 0.01 part by mass, the effect of addition is insufficient, and when the amount is more than 1.0 part by mass, the surface of a molded product obtained by molding the polyolefin resin composition may be bleed.

  In the polyolefin resin composition of the present invention, the ratio (mass ratio) of the dibenzylidene sorbitol compound (A) and the alkali metal salt compound (B) of the organophosphate is (A) / (B) = 99 / The thing within the range of 1-80 / 20 can acquire the effect of this invention. If it exceeds that range, the transparency may decrease. More preferably, it is within the range of the ratio (mass ratio) of 99/1 to 90/10. The effect of the present invention is remarkable when the divindylidene sorbitol compound is in the range of 90/10 to 99/1 with respect to the alkali metal salt of the organic phosphate ester. If it exceeds the range, the effect of improving transparency may be reduced.

  Further, in the polyolefin resin composition of the present invention, other conventionally known additives that are generally used may be added to the polyester resin composition as necessary, as long as the effects of the present invention are not impaired. Good.

  Other additives include neopentyl glycol derivatives, polyalkylene glycols and derivatives thereof, plasticizers such as polyhydric alcohols and epoxy compounds of the derivatives; 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 and other lubricants; heavy metal deactivators; antistatic agents comprising cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants; halogen compounds; phosphorus Acid ester compounds; phosphoric acid amide compounds; melamine compounds; fluororesins or metal oxides; Flame retardants such as melamine acid and (poly) phosphate piperazine; fillers such as glass fiber and calcium carbonate; hydrotalcite, fumed silica, fine particle silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, silicic acid Silica-based inorganic additives such as calcium, sericite, kaolinite, flint, feldspar, aragonite, attapulgite, talc, mica, minesotite, pyrophyllite, silica, etc .; sodium benzoate, disodium bicyclo [2.2. 1] Nucleating agent such as heptane-2,3-dicarboxylate; Colorant; Pigment; Antifogging agent; Various fillers; Mold release agent; Fragrance; Foaming agent; Antibacterial agent; it can. In particular, an antioxidant composed of phenol and phosphorus is preferably used because it has an effect of preventing coloring of the polyolefin resin composition.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-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- (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-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy Ethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acroyl) Oxy-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) pro Onato], 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 phosphite , Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentylglycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol di Phosphite, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dic (Milphenyl) 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. Tributyl-4-hydroxyphenyl) butanetriphosphite, tetrakis (2,4-ditertiarybutylphenyl) biphenylenediphosphonite, tris (2-[(2,4,7,9-tetrakistertiarybutyldibenzo [d , F] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2- And butyl-2-ethylpropanediol-2,4,6-tritert-butylphenol monophosphite.

  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 antioxidant include dialkylthiodipropionates 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-tetraoxa Pyro [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-) Tetramethyl-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- Toramechiru 4-piperidyl amino) hexane / dibromoethane polycondensate, and the like.

  The usage-amount of the said hindered amine compound 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 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; stearic acid monomethylolamide, palm oil fatty acid monoethanolamide, alkylolamides such as stearic acid diethanolamide; N-oleyl stearic acid amide, 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.

  In the polyolefin resin composition of the present invention, the polyolefin resin includes a dibenzylidene sorbide compound represented by the general formula (1) and an alkali metal salt compound of an organophosphate ester represented by the general formula (2). The method of blending is not particularly limited, and can be performed by a conventionally known method. For example, the polyolefin resin powder or pellets and the additive may be mixed by dry blending, 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 in the polymerization stage of a synthetic resin, a mixture of a binder, a wax, a solvent, a granulation aid such as silica and the like in advance at a desired ratio, and then granulation to obtain a one-pack composite additive. A method of adding a pack composite additive to the polyolefin resin, a method of creating 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.

  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.

  Polyolefin resins listed in Tables 1 to 3 below: 100 parts by mass of an ethylene / propylene random copolymer, phenolic antioxidant; tetrakis [methylene-3- (3 ′, 5′-ditert-butyl- 4′-hydroxyphenyl) propionate] 0.1 part by weight of methane, phosphorus antioxidant: 0.1 part by weight of tris (2,4-ditert-butylphenyl) phosphite, 0.05 part by weight of calcium stearate, and 0.2 parts by mass of a mixture of crystal nucleating agents described in Tables 1 to 3 below (however, Comparative Example 4 is not mixed with a crystal nucleating agent) is 1000 rpm with a Henschel mixer (FM200; manufactured by Mitsui Mining Co., Ltd.) The mixture was mixed for 1 minute, and extruded by a single screw extruder (OEX3024; manufactured by DIM Co., Ltd.) at a processing speed of 240 ° C. and a screw speed of 30 rpm to produce pellets. . The following evaluation was implemented about the obtained pellet.

(Degree)
The obtained pellets were filled into a mold for 40 seconds at an injection temperature of 200 ° C. and an injection pressure of 70-80 MPa using an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.). After cooling in the mold for 20 seconds, injection molding was performed under the condition of taking out the sheet from the mold to obtain a sheet having a square of 60 mm square and a thickness of 1 mm. Immediately after the injection molding, the sheet was allowed to stand for 48 hours or more in a thermostatic bath having a bath temperature of 23 ° C., and then the haze guard 2 (manufactured by Toyo Seiki Seisakusho Co., Ltd.) had a test piece haze. Asked.
In addition, it shows that the transparency of a test piece is so favorable that this figure is low. These results are shown in Tables 1 to 3 below.

１）：比較例４は結晶核剤未配合のポリオレフィン系樹脂組成物

1): Comparative Example 4 is a polyolefin resin composition containing no crystal nucleating agent

  As a reference example, the results of evaluation with a polyolefin resin having a melt flow rate (MFR) at 230 ° C. of 8 dg / min are shown in Table 4 below.

  From Comparative Examples 2 and 3 in Table 2, the polyolefin resin composition in which the ratio of the dibenzylidene sorbitol compound and the alkali metal salt of the organophosphate is not within the range of 99/1 to 80/20 is satisfactory transparency. However, according to Examples 3 to 5 in Table 2, the ratio of the dibenzylidene sorbitol compound and the alkali metal salt of the organophosphate is in the range of 99/1 to 80/20. The polyolefin-based resin composition was excellent in transparency.

  Further, from Reference Examples 2 and 3 in Table 4, even if the ratio of the dibenzylidene sorbitol compound and the alkali metal salt compound of the aromatic organophosphate is within the range of 99/1 to 80/20, When the melt flow rate (MFR) at 230 ° C. was less than 20 dg / min, the effect of the present invention was not obtained.

  As described above, the polyolefin resin composition of the present invention has a melt flow rate (MFR) at 230 ° C. of the polyolefin resin of 20 dg / min or more and an alkali metal salt compound of a dibenzylidene sorbitol compound and an aromatic organic phosphate ester. It was confirmed that by taking the constitution of the present invention within the range of 99/1 to 80/20, an excellent effect of improving transparency was obtained.

Claims (4)

For a polyolefin resin having a melt flow rate (MFR) at 230 ° C. of 20 dg / min or more , the following general formula (1),

(In the formula, n is an integer of 0 to 2, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, or an alkyl having 1 to 4 carbon atoms. A group, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxylalkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms A dibenzylidene sorbitol compound (A) represented by the following formula (2), selected from the group consisting of 4 hydroxyhalogenated alkyl groups:

(Wherein R ^{6 to} R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ¹⁰ represents a hydrogen atom or a methyl group, and M represents an alkali metal). The organic phosphate ester alkali metal salt compound (B) alone is blended, and the total sum of the component (A) and the component (B) is 0.01 with respect to 100 parts by mass of the polyolefin resin. The ratio (mass ratio) of the component (A) and the component (B) is in the range of (A) / (B) = 99/1 to 80/20. A polyolefin-based resin composition.   The polyolefin resin composition according to claim 1, wherein the polyolefin resin is a polypropylene resin having a melt flow rate at 230 ° C of 20 to 100 dg / min. 3. The R ^{1 to} R ⁴ in the general formula (1) are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and R ⁵ is a hydrogen atom. Polyolefin resin composition. The polyolefin resin composition according to any one of claims 1 to 3, wherein M in the general formula (2) is lithium, and R ^{6 to} R ⁹ are tertiary butyl groups.