JPH0621205B2 - Crystalline polypropylene composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a crystalline polypropylene composition from which stretch-molded articles having opacity or light-shielding properties can be obtained.

[Conventional technology]

Generally, opaque or light-shielding plastic molded products are widely used in general packaging materials such as films or containers, synthetic paper, decorative materials, writing / printing paper, and packing materials such as tapes, ribbons or filaments, and woven paper. Is used for. Conventionally, as a method for making a plastic film or a thin-walled molded product opaque, a method of adding a white pigment such as titanium oxide, a pearl pigment, an extender pigment, etc., JP-B-63-24532, and JP-A-63-117043.
As described in Japanese Patent Laid-Open Publication No. 2003-242, there is a method of adding a large amount of an inorganic filler and then stretching it to form a void. These methods are modified mainly by high filling of the inorganic filler, and the fluidity at the time of extrusion is significantly reduced because a large amount of the inorganic filler such as titanium oxide or calcium carbonate is added, The screen pack is clogged, foams due to moisture absorption due to the inorganic filler, and it takes a long time to replace the resin. However, there are drawbacks such as a decrease in the degree, or the stretched product becomes porous, and only a roughened surface can be obtained.

For this reason, the Applicant eliminates these drawbacks of the prior art,
Patent Document 1-Patent application 1-A composition capable of easily producing an opaque and excellent light-shielding polypropylene-based film or a thin-walled molded product, that is, a composition in which crystalline polypropylene is blended with a specific amount of a specific cyclopentadiene-based petroleum resin. 74919
And Japanese Patent Application No. 1-78293.

However, the opaque stretch-molded articles obtained from the compositions proposed in Japanese Patent Application No. 1-74919 and Japanese Patent Application No. 1-78293 have poor light resistance and are exposed to light for a long period of time outdoors or indoors. There is a drawback that the polypropylene-based resin is photo-deteriorated by ultraviolet rays and the value of the molded article is remarkably reduced.

[Problems to be Solved by the Invention]

That is, it is an object of the present invention to provide a crystalline polypropylene composition which provides an opaque stretch molded article with improved light resistance.

[Means for Solving the Problems]

The present inventors provide a crystalline polypropylene composition obtained by mixing crystalline polypropylene with a specific resin and a specific amount of a hindered amine-based light stabilizer, to provide a stretched molded article with improved light resistance and opacity. The present invention has been completed by finding out that it is a composition.

The present invention has the following configurations.

(1) 100 parts by weight of crystalline polypropylene, 5 to 150 parts by weight of the resin shown below, 0.05 to 5 parts by weight of a hindered amine light stabilizer, and fatty acid, fatty acid partial ester of polyol, alkylamine ethylene oxide adduct, alkyl A crystalline polypropylene composition comprising 0.05 to 5 parts by weight of a fatty acid ester of an amine ethylene oxide adduct, an alkyl amide ethylene oxide adduct, a fatty acid monoamide, a fatty acid bisamide or a mixture of two or more thereof.

A component containing the cyclopentadiene-based polymerizing component (A), or the component (A) and a vinyl aromatic hydrocarbon-based polymerizing component (B)
Obtained by polymerization reaction component comprising a weight composition ratio (B) / (A) is 0 to 0.5, weight average molecular weight _(M W)
Is a resin having a value of M _W ≧ 680 + 2200X (where M _W is standard polystyrene conversion and X represents a composition ratio [(B) / [(A) + (B)]]).

(2) The hindered amine light stabilizer is bis (2, 2,
6,6-Tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) Sebacate, screw (1,
2,2,6,6-Pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3,3- Dicarboxylate, bis (1,2,
2,6,6-Pentamethyl-4-piperidyl) -1,5
-Dioxaspiro [5.5] undecane-3,3-dicarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1 , 2, 2, 6, 6
-Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-
Dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, Poly [[6-
[(1,1,3,3-tetramethylbutylimino]-
1,3,5-triazine-2,4-diyl] [(2,
2,6,6-Tetramethyl-4-piperidyl) imino]
Hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]], poly [[6-morpholino-1,3,5-triazine-2,4-diyl] [(2,
2,6,6-Tetramethyl-4-piperidyl) imino]
Hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]], 1,5,8,12-tetrakis [4,6-bis (N- (1,2,2,6,6-pentamethyl-4-piperidyl) -butylamino) -1,
3,5-triazin-2-yl] -1,5,8,12-
The crystalline polypropylene composition according to item (1), which is tetraazadodecane or a mixture of two or more thereof.

(3) 0.05 to 5 parts by weight of a benzophenone-based UV absorber, a benzotriazole-based UV absorber, a hydroxybenzoate-based light stabilizer, or a mixture of two or more of them is added to 100 parts by weight of crystalline polypropylene. The crystalline polypropylene composition according to any one of (1) or (2) above.

(4) The benzophenone-based UV absorber is 2-hydroxy-4-n-octoxybenzophenone, and the benzotriazole-based UV absorber is 2- (2'-hydroxy-3 '.
-T-butyl-5'-methylaphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ',
5'-di-t-butylphenyl) -5-chlorobenzotriazole or a mixture thereof, a hydroxybenzoate light stabilizer is 2,4-di-t-butylphenyl-3 ', 5'-di-t- The crystalline polypropylene composition according to item (3), which is butyl-4'-hydroxybenzoate, n-hexadecyl-3, -5-di-t-butyl-4-hydroxybenzoate or a mixture thereof.

(5) The fatty acid is lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid or a mixture of two or more thereof, and the fatty acid partial ester of polyol is glyceryl monostearate, pentaerythritol distearate, sorbitan monostearate. Rate, sorbitan monooleate or a mixture of two or more thereof, and alkylamine ethylene oxide adducts are N, N-bis (2-hydroxyethyl) laurylamine, N, N-bis (2-hydroxyethyl) tridecyl. Amine, N, N
-Bis (2-hydroxyethyl) pentadecylamine,
N, N-bis (2-hydroxyethyl) palmitylamine, N, N-bis (2-hydroxyethyl) stearylamine, N, N-bis (2-hydroxyethyl) cocoamine, N, N-bis (2- Hydroxyethyl) tallow amine or a mixture of two or more thereof, fatty acid ester of alkylamine ethylene oxide adduct, octadecanoic acid 2-[(2-hydroxyethyl) octadecylamino] ethyl ester, alkylamido ethylene oxide adduct are N , N-bis (2-hydroxyethyl) stearoamide, N, N'-bis (2-hydroxyethyl) oleylamide, N, N-bis (2-hydroxyethyl) cocoamide or a mixture of two or more thereof, fatty acid monoamide But stearic acid amide, oleic acid amide, L Acid amide or mixtures of two or more thereof, fatty acid bisamide, N, N'ethylene -
The crystalline polypropylene composition according to item (1), which is bis-stearoamide.

(6) The above composition further comprising 0.5 to 200 parts by weight of an inorganic filler with respect to 100 parts by weight of crystalline polypropylene.
The weakly crystalline polypropylene composition according to any one of items (1) to (5).

(7) The inorganic filler is calcium carbonate, talc, mica,
Clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, magnesium carbonate,
The crystalline polypropylene composition according to the above (6), which is zinc sulfide, barium sulfate, calcium silicate, aluminum silicate or a mixture of two or more thereof.

The crystalline polypropylene used in the present invention is a homopolymer of propylene, a copolymer with other α-olefin containing propylene as a main component, or a mixture thereof.

The resin blended in the present invention is obtained by polymerizing a component containing a cyclopentadiene-based polymerization component (A) or a component containing the (A) and a vinyl aromatic hydrocarbon-based polymerization component (B), and its weight. The composition ratio (B) / (A) is 0 to 0.5,
The weight average molecular weight (M _W ) has a value of the formula M _W ≧ 680 + 2200X (where, M _W represents standard polystyrene conversion, and X represents a composition ratio [(B) / [(A) + (B)]]). It is a resin.

When this weight average molecular weight (M _W ) satisfies the above formula, it is excellent in compatibility with crystalline polypropylene, stable processing can be performed, and a stretched molded article excellent in whiteness and opacity can be obtained, which is preferable. .

The weight average molecular weight (M _W ) is expressed as a standard polystyrene conversion value measured by ordinary gel permeation chromatography (GPC). That is, in the present invention, Tosoh Corp. HLC-802 type (column: GH8)
P + G400H8 + G3000H8 + G2000H8 x
2) was used and measured under the following analysis conditions.

Solvent: Tetrahydrofuran (THF) Column constant temperature bath temperature: 40 ° C THF flow rate: 1.2 ml / min Sample concentration: 0.005 g resin / 1 ccTHF Detector: Differential refractometer As a component containing the cyclopentadiene-based polymerization component (A) Is, for example, a fraction containing a cyclopentadiene-based polymerization component in an amount of preferably 50% by weight or more (hereinafter referred to as CPD) from a by-product fraction in the case of thermally decomposing petroleum naphtha or the like to produce ethylene.
It is called a fraction. ) Can be mentioned. Most of the CPD fraction is a saturated hydrocarbon that is inert to polymerization except for the cyclopentadiene-based polymerization component, but in addition to this, isoprene copolymerizable with a small amount of the cyclopentadiene-based polymerization component,
Aliphatic diolefins such as pentadiene and butadiene are included. In addition, aliphatic olefins such as butene and pentene, and further, a mixture of these containing a cyclopentadiene-based polymerization component may contain a cyclic olefin or diolefin which has been dimerized by heat. In the present invention, it is preferable that the concentration of these is lower, and it is preferably 1/10 or less of the cyclopentadiene-based monomer in terms of heavy weight.

Specific examples of the component containing the vinyl aromatic hydrocarbon-based polymerization component (B) include styrene, vinyltoluenes, α
-And β-methylstyrene, indene, alkyl-substituted indene or a mixture thereof. Further, like the CPD fraction, a fraction called a C ₉ fraction that is a by-product when ethylene is produced by thermally decomposing petroleum naphtha is mainly composed of the vinyl aromatic hydrocarbon-based polymerization component. It is an advantageous raw material for industrial use.

The resin to be added to the composition of the present invention is obtained by polymerizing a) a component containing a cyclopentadiene-based polymerization component (A),
b) The component containing the polymerization component (A) and the component containing the vinyl aromatic hydrocarbon-based polymerization component (B) are mixed with each other (5).
Copolymerization reaction of 0% or more, c) those obtained by hydrogenating those obtained by these polymerizations,
Or d) a mixture of two or more of these.

The polymerization conditions are benzene, toluene, xylene, n-
220-320 ° C, preferably 240-300 ° C in the presence or absence of a solvent such as hexane or kerosene
Temperature range, under an atmosphere of an inert gas such as nitrogen gas,
It is carried out for 0.1 to 10 hours, preferably 0.2 to 6 hours, under a pressure above which the liquid phase can be maintained.

Further, the polymerization may be carried out in one step, but may be repeated in two or more steps, and in order to adjust the weight average molecular weight, a radical initiator or the like may be added to this reaction system. Such a series of polymerization reactions can be carried out by any of batch method, semi-batch method and continuous method.

After carrying out the polymerization reaction in this way, the pressure of the polymerization system is subsequently lowered to remove the unreacted components and the inert components such as the solvent, whereby the desired resin can be obtained. This polymerization reaction is carried out in the presence of a solvent for the first stage polymerization in the presence of a solvent for 200 to 2 hours for several hours.
After heating at 80 ° C. and after completion of the reaction, unreacted raw materials and solvent are removed, and the second stage polymerization is carried out by holding at 200 to 280 ° C. under reduced pressure for several hours, or each step is repeated twice or more. A multi-stage polymerization method is desirable, and the resin required by the present invention can be obtained in good yield.

A resin obtained by further hydrogenating the resin thus obtained according to a conventionally known method can also be used in the composition of the present invention. For the hydrogenation, the resin obtained by the above-mentioned polymerization is made into a resin solution or a molten state with cyclohexane or the like, and for example, a metal such as nickel, palladium or cobalt, or a hydrogenation catalyst such as a metal oxide is used, and preferably 150 It is carried out under the conditions of a temperature of ~ 300 ° C and a hydrogen pressure of 10-150 kg / cm ² .

The weight composition ratio of the polymerization component is in the range of (B) / (A) = 0 to 0.5. When the weight composition ratio (B) / (A) of the monomers exceeds 0.5, the yield of the resin in the range intended by the present invention is remarkably lowered and the effect intended by the present invention is also lowered. It is not preferable.

The blending ratio of the resin blended in the composition of the present invention is 5 to 150 parts by weight with respect to 100 parts by weight of crystalline polypropylene,
It is preferably 10 to 100 parts by weight. When the amount is less than 5 parts by weight, the effect of improving opacity cannot be sufficiently exhibited, and when the amount exceeds 150 parts by weight, the rigidity and strength are extremely lowered, which is not preferable.

Examples of the hindered amine light stabilizer used in the present invention include 4-hydroxy-2,2,6,6-tetramethylpiperidine and 1-allyl-4-hydroxy-2,2,6,6.
-Tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-
(4-t-Butyl-2-butenyl) -4-hydroxy-
2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-
Pentamethylpiperidine, 1-benzyl-2,2,6
6-tetramethyl-4-piperidyl malate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) succinate, Screw (2, 2, 6,
6-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-)
Piperidyl) fumarate, bis (1,2,3,6-tetramethyl-2,6-diethyl-4-piperidyl) sebacate, bis (1-allyl-2,2,6,6-tetramethyl-4-piperidyl) Phthalate, bis (1, 2, 2,
6,6-pentamethyl-4-piperidyl) sebacate,
1,1 '-(1,2-ethanediyl) bis (3,5,5
5,5-tetramethylpiperazinone), 2-methyl-2
-(2,2,6,6-tetramethyl-4-piperidyl)
Imino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, 2-methyl-2- (1,
2,2,6,6-Pentamethyl-4-piperidyl) imino-N- (1,2,2,6,6-pentamethyl-4-piperidyl) propionamide, 1-propargyl-4-β
-Cyanoethyloxy-2,2,6,6-tetramethylpiperidine, 1-acetyl-2,2,6,6-tetramethyl-4-piperidyl-acetate, trimellitic acid-
Tris (2,2,6,6-tetramethyl-4-piperidyl) ester, 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6) 6-pentamethyl-4-piperidyl) dibutyl malonate, bis (1,2,2,6,6-
Pentamethyl-4-piperidyl) dibenzyl-malonate, bis (1,2,3,6-tetramethyl-2,6-diethyl-4-piperidyl) dibenzyl-malonate, bis (1,2,2,6,6-pentamethyl) -4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (2,2
2,6,6-Tetramethyl-4-piperidyl) -1,5
-Dioxaspiro [5.5] undecane-3,3-dicarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3, 3-dicarboxylate,
Bis (1-acetyl-2,2,6,6-tetramethyl-
4-piperidyl) -1,5-dioxaspiro [5.5]
Undecane-3,3-dicarboxylate, 1,3-bis [2,2 '-[bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-dioxacyclohexane-5, 5-dicarboxylate]], bis (2,2,2
6,6-Tetramethyl-4-piperidyl) -2-[-methylethyl] -1,3-dioxacyclohexane-5,
5-dicarboxylate, 1,2-bis [2,2'-
[Bis (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-1,3-dioxacyclohexane-
5,5-dicarboxylate]], bis (2,2,6,
6-tetramethyl-4-piperidyl) -2-[-(3,
5-di-t-butyl-4-hydroxyphenyl)] ethyl-2-methyl-1,3-dioxacyclohexane-
5,5-dicarboxylate, bis (2,2,6,6-
Tetramethyl-4-piperidyl) -1,5-dioxaspiro [5.11] heptadecane-3,3-dicarboxylate, hexane-1 ′, 6′-bis-4-carbamoyloxy-1-n-butyl-2 , 2,6,6-Tetramethylpiperidine), Toluene-2 ′, 4′-bis (4-
Carbamoyloxy-1-n-butyl-2,2,6,6
-Tetramethylpiperidine), dimethyl-bis (2,
2,6,6-Tetramethylpiperidine-4-oxy)-
Silane, phenyl-tris (2,2,6,6-tetramethylpiperidine-4-oxy) -silane, tris (1-
Propyl-2,2,6,6-tetramethyl-4-piperidyl) -phosphite, tris (1-propyl-2,
2,6,6-tetramethyl-4-piperidyl) -phosphate, phenyl- [bis (1,2,2,6,6-pentamethyl-4-piperidyl)]-phosphonate,
Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-
4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetratocarbonamide, tetrakis ( 1,2,2,6,6-Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarbonamide, 2-dibutylamino-4,6-
Bis (9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] -3-
Undecylmethoxy) -s-triazine, 2-dibutylamino-4,6-bis (9-aza-3-ethyl-8,
8,9,10,10-pentamethyl-1,5-dioxaspiro [5.5] -3-undecylmethoxy) -s-triazine, tetrakis (9-aza-3-ethyl-8,
8,10,10-Tetramethyl-1,5-dioxaspiro [5.5] -3-undecylmethyl) -1,2,3,
4-butane tetracarboxylate, tetrakis (9-
Aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro [5.5] -3-undecylmethyl) -1,2,3,4-butanetetracarboxylate, tridecyl -Tris (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tridecyl tris (1,2,
2,6,6-pentamethyl-4-piperidyl) 1,2,
3,4-butanetetracarboxylate, di (tridecyl) bis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, di (tridecyl) bis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadisspiro [5.1.
11.2] Heneicosan-21-one, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-
Tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1, 2, 2, 6,
6-pentamethyl-4-piperidyloxycarbonyl)
Butylcarbonyloxy} ethyl] -2,4,8,10
-Tetraoxaspiro [5.5] undecane, poly (2,2,6,6-tetramethyl-4-piperidyl acrylate), poly (1,2,2,6,6-pentamethyl-4-piperidyl acrylate), Poly (2,2,6
6-tetramethyl-4-piperidyl methacrylate),
Poly (1,2,2,6,6-pentamethyl-4-piperidyl methacrylate), poly [[bis (2,2,6,6
-Tetramethyl-4-piperidyl) itaconate] [butyl ether]], poly [[bis (1,2,2,6,6
-Pentamethyl-4-piperidyl) itaconate] [vinyl butyl ether]], poly [[bis (2,2,6,
6-Tetramethyl-4-piperidyl) itaconate]
[Vinyl octyl ether]], poly [[bis 1,2,
2,6,6-Pentamethyl-4-piperidyl) itaconate] [vinyl octyl ether]], dimethyl succinate-2- (4-hydroxy-2,2,6,6-tetramethylpiperidyl) ethanol condensate, poly [ [Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Poly [ethylene [(2,2,
6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[1,3,5-triazine-2,4] -Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,
2,6,6-Tetramethyl-4-piperidyl) imino]], poly [[6- (diethylimino) -1,3,5]
-Triazine-2,4-diyl] [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-[(2-ethylhexyl) imino]]-1,3 , 5-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino ]], Poly [[6
-(1,1,3,3-Tetramethylbutyl) imino]-
1,3,5-triazine-2,4-diyl] [(2,
2,6,6-Tetramethyl-4-piperidyl) imino]
Hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]], poly [[6- (cyclohexylimino) -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-
Morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl- 4-piperidyl) imino]], poly [[6-
(Butoxyimino) -1,3,5-triazine-2,4
-Diyl] [((2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6,
6-Tetramethyl-4-piperidyl) imino]], poly [[-[1,1,3,3-tetramethylbutyl) oxy] -1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [oxy [6
-[(1-piperidyl) -1,3,5-triazine-
2,4-diyloxy-1,2-ethanediyl]
[(2,2,6,6-tetramethyl-3-oxo-1,
4-piperidyl) -1,2-ethanediyl] [(3,
3,5,5 tetramethyl-2-oxo-1,4-piperidyl) -1,2-ethanediyl]], poly [oxy [6
-[(1,1,3,3-Tetramethylbutyl) imino] -1,3,5-triazine-2,4-diyloxy-1,2-ethanedil] [(2,2,6,6-tetramethyl -3-Oxo-1,4-piperidyl) -1,2-ethanediyl] [(3,3,5,5-tetramethyl-2-
[Oxo-1,4-piperidyl) -1,2-ethanediyl]], poly [[6-[(ethylacetyl) imino]-
1,3,5-triazine-2,4-diyl] [(2,
2,6,6-Tetramethyl-4-piperidyl) imino]
Hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]], poly [[6- (2,2,2
6,6-Tetramethyl-4-piperidyl) butylimino] -1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], 1,6,11-tris [{4,6-bis (N-butyl-N- (2,2 ，
6,6-Tetramethyl-4-piperidyl) amino)-
1,3,5-triazin-2-yl} amino] undecane, 1,6,11-tris [{4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl- 4-piperidyl) amino) -1,3,5-triazin-2-yl} amino] undecane, 1,6,11-tris [{4,6-bis (N-octyl-N- (2,2,6] ，
6-tetramethyl-4-piperidyl) amino) -1,
3,5-triazin-2-yl} amino] undecane,
1,6,11-Tris [{4,6-bis (N-octyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazine-2 -Yl} amino] undecane, 1,5,8,12-tetrakis [4,6-bis (N- (2,2,6,6-tetramethyl-4-piperidyl) -butylamino) -1,3,3 5-
Triazin-2-yl] -1,5,8,12-tetraazadodecane and 1,5,8,12-tetrakis [4
6-bis (N- (1,2,2,6,6-pentamethyl-
4-piperidyl) -butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane and the like can be exemplified, and particularly bis (2,2,6,6-tetra Methyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1 , 2, 2,
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-
3,3-dicarboxylate, bis (1,2,2,6,
6-Pentamethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3,3-dicarboxylate, tetrakis (2,2,6,6-tetramethyl-)
4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3, 9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-
4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, poly [[6-[(1,1,
3,3-Tetramethylbutyl) imino] -1,3,5-
Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)
Imino]], poly [[6-morpholino-1,3,5-
Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)
Imino]], 1,5,8,12-tetrakis [4,6-
Bis (N- (1,2,2,6,6-pentamethyl-4-
Piperidyl) -butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane is preferred. These hindered amine light stabilizers can be used alone, and two or more hindered amine light stabilizers can be used in combination. The compounding ratio of the hindered amine light stabilizer is 100% crystalline polypropylene.
0.05 to 5% by weight, preferably 0.1
~ 1 part by weight. If the amount is less than 0.05 parts by weight, the effect of improving the light resistance is not sufficiently exerted, and if it exceeds 1 part by weight, further improvement of the light resistance cannot be expected and it is not practical. It is uneconomical again. In the composition of the present invention, a benzophenone-based ultraviolet absorber,
By using a benzotriazole-based ultraviolet absorber, a hydroxybenzoate-based light stabilizer, or a mixture of two or more kinds thereof in combination, the improvement of light resistance can be made more effective. As the benzophenone-based ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone-5-sulphonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl) -4-Hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-
Methoxybenzophenone, 2,2'-dihydroxy-
4,4'-dimethoxybenzophenone, 2,2 ', 4
Examples include 4'-tetrahydroxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. These benzophenone-based UV absorbers may be used alone, or two or more kinds of benzophenone-based UV absorbers may be used in combination. Also,
As a benzotriazole type ultraviolet absorber, 2- (2 '
-Hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (2'-hydroxy-3' , 5'-di-t
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2, 2'-methylene-
Bis [4- (1,3,3-tetramethylbutyl) -6-
(2N-benzotriazol-2-yl) phenol], methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol And 2- (2-hydroxyphenyl) benzotriazole copolymer. These benzotriazole-based UV absorbers may be used alone, or two or more benzotriazole-based UV absorbers may be used in combination. Further, as the hydroxybenzoate-based light stabilizer, 2,4-di-t-butylphenyl-
3 ', 5'-di-t-butyl-4'-hydroxybenzoate, 2,6-di-t-butylphenyl-3', 5 '
Examples include -di-t-butyl-4'-hydroxybenzoate and n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. These hydroxybenzoate-based light stabilizers may be used alone, or two or more hydroxybenzoate-based light stabilizers may be used in combination. The benzophenone-based UV absorber, benzotriazole-based UV absorber, hydroxybenzoate-based light stabilizer, or a mixture ratio of two or more thereof is 0.05 to 5 parts by weight with respect to 100 parts by weight of crystalline polypropylene. It is preferably 0.1 to 1 part by weight.

In the composition of the present invention, a fatty acid, a fatty acid partial ester of a polyol, an alkylamine ethylene oxide adduct, a fatty acid ester of an alkylamine ethylene oxide adduct, an alkylamide ethylene oxide adduct,
By using a fatty acid monoamide, a fatty acid bisamide, or a combination of two or more polar compounds of these, the improvement of light resistance can be made more effective. Fatty acids include acetic acid, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, behenic acid, erucic acid, montanic acid, 1
Examples of such compounds include 2-hydroxystearic acid, ricinoleic acid and stearyl lactic acid, which are usually used as lubricants. These fatty acids may be used alone or in combination of two or more. As the fatty acid partial ester of polyol, glycerin fatty acid monoester, polyglycerin fatty acid partial ester, sorbitan fatty acid monoester, sucrose fatty acid monoester, pentaerythritol fatty acid monoester and ester, polypentaerythritol fatty acid partial ester, trimethylolethane fatty acid monoester Examples thereof include compounds such as esters, trimethylolpropane fatty acid monoesters, polyoxyethylene glycerin fatty acid monoesters, and polyoxyethylene sorbitan fatty acid monoesters (the fatty acids are the above-mentioned fatty acids) that are usually used as antistatic agents. Not only the fatty acid partial esters of these polyols can be used alone, but also the fatty acid partial esters of two or more kinds of polyols can be used in combination. Further, as the alkylamine ethylene oxide adduct, N- (2-hydroxyethyl) laurylamine,
N- (2-hydroxyethyl) tridecylamine, N-
(2-hydroxyethyl) myristylamine, N- (2
-Hydroxyethyl) pentadecylamine, N- (2-
Hydroxyethyl) palmitylamine, N- (2-hydroxyethyl) stearylamine, N- (2-hydroxyethyl) oleylamine, N- (2-hydroxyethyl) docosylamine, N- (2-hydroxyethyl) octacosylamine, N- (2-hydroxyethyl) cocoamine, N- (2-hydroxyethyl) tallowamine,
N-methyl-N- (2-hydroxyethyl) laurylamine, N-methyl-N- (2-hydroxyethyl) tridecylamine, N-methyl-N- (2-hydroxyethyl) myristylamine, N-methyl- N- (2-hydroxyethyl) pentadecylamine, N-methyl-N-
(2-hydroxyethyl) palmitylamine, N-methyl-N- (2-hydroxyethyl) stearylamine,
N-methyl-N- (2-hydroxyethyl) oleylamine, N-methyl-N- (2-hydroxyethyl) docosylamine, N-methyl-N- (2-hydroxyethyl) octacosylamine, N-methyl-N- (2-Hydroxyethyl) cocoamine, N-methyl-N- (2-hydroxyethyl) tallowamine, N, N-bis (2-hydroxyethyl) laurylamine, N, N-bis (2-
Hydroxyethyl) tridecylamine, N, N-bis (2-hydroxyethyl) myristylamine, N, N-
Bis (2-hydroxyethyl) pentadecylamine,
N, N-bis (2-hydroxyethyl) palmitylamine, N, N-bis (2-hydroxyethyl) stearylamine, N, N-bis (2-hydroxyethyl) oleylamine, N, N-bis (2- Hydroxyethyl) docosylamine, N, N-bis (2-hydroxyethyl) octacosylamine, N, N-bis (2-hydroxyethyl) cocoamine, N, N-bis (2-hydroxyethyl) tallowamine, polyoxyethylenelauryl Amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene cocoamino ether, polyoxyethylene tallow amino ether, N, N, N ', N'-tetra (2-hydroxyethyl) -1 , 3-diaminopropane, N, N, N ', N - tetra (2-hydroxyethyl) -1,6-diaminohexane, N- lauryl -N,
N ', N'-tris (2-hydroxyethyl) -1,3
-Diaminopropane, N-stearyl-N, N ', N'
-Tris (2-hydroxyethyl) -1,3-diaminopropane, N-coco-N, N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N-tallow-N, N' , N'-Tris (2-hydroxyethyl) -1,3-diaminopropane, N, N-dicoco-
N ', N'-bis (2-hydroxyethyl) -1,3-
Diaminopropane, N, N-ditallow-N ', N'-bis (2-hydroxyethyl) -1,3-diaminopropane, N-coco-N, N', N'-tris (2-hydroxyethyl)- 1,6-diaminohexane, N-tallow-
N, N ', N'-tris (2-hydroxyethyl)-
1,6-diaminohexane, N, N-dicoco-N ',
Cross-charge consisting of N'-bis (2-hydroxyethyl) -1,6-diaminohexane and N, N-ditallow-N ', N'-bis (2-hydroxyethyl) -1,6-diaminohexane The compound used as an inhibitor can be illustrated. These alkylamine ethylene oxide adducts may be used alone, or two or more kinds of alkylamine ethylene oxide adducts may be used in combination. Examples of the fatty acid ester of the alkylamine ethylene oxide adduct include compounds that are usually used as antistatic agents and are composed of partial esters and complete esters of the above-mentioned alkylamine ethylene oxide adduct and the above-mentioned fatty acids. The fatty acid ester of these alkylamine ethylene oxide adducts may be used alone, or two or more kinds of alkylamine ethylene oxide adducts may be used in combination. The fatty acid ester of an alkylamine ethylene oxide adduct is N, N-bis (2-hydroxyethyl) laurylamide, N, N-bis (2-hydroxyethyl) tridecylamide, N, N-bis (2- Hydroxyethyl) myristylamide, N, N-bis (2-hydroxyethyl) pentadecylamide, N, N-bis (2-hydroxyethyl) palmitylamide, N, N-bis (2-hydroxyethyl) stearylamide, N, N-bis (2-hydroxyethyl) oleylamide, N, N-bis (2-hydroxyethyl) docosylamide, N, N-bis (2-hydroxyethyl) octacosylamide, N, N-bis (2 -Hydroxyethyl) cocoamide, N, N-bis (2-hydroxyethyl) tallowamide, polyoxyethylene Lauryl amide ether, polyoxyethylene stearyl amide ether, polyoxyethylene oleyl amide ether, a compound usually used as an antistatic agent comprising a polyoxyethylene coco amido ether, and polyoxyethylene tallow amido ether can be exemplified. These alkylamine ethylene oxide adducts may be used alone, or two or more kinds of alkylamine ethylene oxide adducts may be used in combination. As fatty acid monoamide, a compound usually used as a lubricant, such as lauric acid amide, myristic acid amide, palmitic acid amide, palmitoleic acid amide, stearic acid amide, oleic acid amide, behenic acid amide, erucic acid amide and montanic acid amide. Can be illustrated. These fatty acid monoamides may be used alone or in combination of two or more fatty acid monoamides. Also, as the fatty acid bisamide, N,
N'-methylene-bis-lauric acid amide, N, N'-
Methylene-bis-myristic acid amide, N, N'-methylene-bis-palmitic acid amide, N, N'-methylene-bis-palmitoleic acid amide, N, N'-methylene-bis-stearoamide, N, N'- Methylene-bis-
Oleic acid amide, N, N'-methylene-bis-behenic acid amide, N, N'-methylene-bis-erucic acid amide, N, N'-methylene-bis-montanic acid amide,
N, N'-ethylene-bis-lauric acid amide, N,
N'-ethylene-bis-myristic acid amide, N, N '
-Ethylene-bis-palmitic acid amide, N, N'-ethylene-bis-palmitoleic acid amide, N, N'-ethylene-bis-stearoamide, N, N'-ethylene-
Bis-oleic acid amide, N, N'-ethylene-bis-
Examples of compounds that are usually used as lubricants include behenic acid amide, N, N'-ethylene-bis-erucic acid amide and N, N'-ethylene-bis-montanic acid amide. These fatty acid bisamides can be used alone or in combination of two or more kinds. The fatty acid, a partial fatty acid ester of a polyol, an alkylamine ethylene oxide adduct, a fatty acid ester of an alkylamine ethylene oxide adduct, an alkylamine ethylene oxide adduct, a fatty acid monoamide, a fatty acid bisamide, or a compounding ratio of two or more kinds thereof. Is 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight, relative to 100 parts by weight of crystalline polypropylene.

In the composition of the present invention, by using an inorganic filler in combination, it is possible to improve the opacity, writability, printability and the like of the obtained stretch-molded article.

As inorganic filler, calcium carbonate, talc, mica,
Clay, wollastonite, zeolite, kaolin, hydrotalcite, bentonite, perlite, diatomaceous earth, silas balloon, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide,
Examples thereof include magnesium oxide, aluminum oxide, magnesium carbonate, barium carbonate, zinc sulfide, magnesium sulfate, calcium sulfate, barium sulfate, calcium silicate and aluminum silicate. Further, surface treatment agents (for example, higher fatty acids, metal soaps, higher fatty acid esters, higher alcohols, higher fatty acid monoamides, higher fatty acid bisamides, higher aliphatic metal phosphates, silane coupling agents, titanate coupling agents, boron-based agents. Examples of the inorganic filler used for the porosification of the crystalline polypropylene such as the above-mentioned inorganic filler surface-treated with a coupling agent, an aluminate-based coupling agent, a zircoaluminate-based coupling agent, etc. Particularly preferred are calcium carbonate, talc, clay, silicon dioxide, titanium dioxide, calcium silicate and aluminum silicate having an average particle size of 10 μm or less. These inorganic fillers may be used alone or in combination of two or more. The blending ratio of the inorganic filler is
0.5-2 based on 100 parts by weight of crystalline polypropylene
The amount is 00 parts by weight, preferably 1 to 150 parts by weight.

In the composition of the present invention, various additives that are usually added to crystalline polypropylene, for example, phosphorus acid inhibitors,
Phenol type antioxidant, hydroxylamine type antioxidant, thioether type antioxidant, light stabilizer, heavy metal deactivator, clarifying agent, nucleating agent, lubricant, antistatic agent, antifogging agent, antiblocking agent , Drop-free agents, flame retardants, flame retardant aids, antibacterial agents, pigments, radical generators such as peroxides, halogen scavengers, dispersants or neutralizing agents such as metal soaps, or organic fillers (eg, wood). Powder, pulp, waste paper,
Synthetic fibers, natural fibers, thermosetting resins, melamine / (iso) cyanuric acid adducts, etc.) and various thermoplastic resins can be used together within the range not impairing the object of the present invention.

Examples of the metallic soaps include lithium stearate, sodium stearate, magnesium stearate, calcium stearate, calcium montanate, and the like.

The composition of the present invention is prepared by adding a predetermined amount of each of the crystalline polypropylene, the resin, the hindered amine-based antioxidant, and the above-mentioned various additives that are usually added to the crystalline polypropylene to a conventional mixing device such as a Henschel mixer (trade name). ), Using a super mixer, a ribbon blender, etc., for easy mixing. In addition, it is particularly preferable to use as a pelletized composition for various moldings described below, and a temperature of not less than the crystalline melting point of the crystalline polypropylene with an ordinary single-screw extruder, twin-screw extruder, Brabender, Banbury mixer or roll. so,
Preferably, a pelletized composition can be obtained by melt-kneading and pelletizing at 170 ° C to 300 ° C.

Further, the resin according to the composition of the present invention and the hindered amine-based antioxidant to the crystalline polypropylene or other resin, individually or in combination, in large amounts to form a masterbatch, and then the masterbatch is crystallized. It is also useful to use a mixed composition in which it is blended with the polypropylene.

The obtained composition can be formed into desired molded articles such as films, ribbons and containers by various molding methods such as extrusion molding method, coextrusion molding method, blow molding method and injection molding method. By uniaxially and biaxially stretching, the opacity and the light-shielding property which are the objects of the present invention are further improved, which is preferable.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The methods for evaluating the properties used in the examples and comparative examples were as follows.

1) Weight average molecular weight: Tosoh Corp. HLC-802 type (column: GH8P + G400H8 + G3000H8 +)
G2000H8 × 2) means the standard polystyrene conversion value measured under the above-mentioned conditions.

2) Iodine value: According to JIS K _0070-1966 . It refers to the number of grams of iodine added to unsaturated bonds in 100 g of a sample.

3) Total light transmittance: According to JIS K6714.

(Unit:%) 4) Light resistance: An accelerated light resistance test of the film was performed using a Sunshine and a weather meter (black panel temperature 83 ° C., no water spray).

The light resistance was evaluated from the irradiation time required until the appearance of abnormal appearance such as cracks on the surface of the film and the occurrence of cracks on the film when the film was bent. (Unit: time) 5) MFR (melt flow rate): JIS K 72
Condition 14 of Table 1 of _10-1976 (230 ° C, 2.16 kg
According to f). (Unit: g / 10 minutes) The resins used in Examples and Comparative Examples are as follows.

Cyclopentadiene-based petroleum resin (abbreviated as P): Contains 75.3% by weight of dicyclopentadiene obtained by steam cracking of petroleum naphtha, and contains a small amount of aliphatic olefin, diolefin, and co-dimer of these and cyclopentadiene. The first-stage thermal polymerization of 600 g of a CPD fraction containing the body and most of the rest consisting of saturated hydrocarbons was carried out by a known method in xylene under a nitrogen atmosphere at 260 ° C. for 3 hours. After the reaction is completed, the unreacted raw materials and the solvent are kept under normal pressure for 20
After distilling out of the system at 0 ° C, under reduced pressure of 50 Torr, 22
It was kept at 0 ° C. for 2 hours to carry out the second stage polymerization. Then, it was cooled to room temperature and solidified to obtain P.

Cyclopentadiene-based petroleum resin hydride (referred to as HP): The above P was dissolved in cyclohexane to form a 50 wt% solution, and a nickel-based catalyst was added in an amount of 5 wt% based on the resin weight.
Hydrogenation was carried out in an autoclave at 250 ° C. under a hydrogen pressure of 70 kg / cm ² (G) for 5 hours.

The reaction liquid was taken out of the system, the catalyst was filtered, and then cyclohexane was distilled off under normal pressure and then under reduced pressure to obtain solid HP.

Cyclopentadiene-Vinyl Aromatic Hydrocarbon Copolymer Petroleum Resin (abbreviated as PC ₉ ): 500 g of CPD distillate used in the production method of P, and styrene, α, obtained by steam cracking of petroleum naphtha.
24.8% by weight of vinyl aromatic monomers such as β-methylstyrene, o, m, p-vinyltoluene and indene
C ₉ cut 5 containing aromatic balance of inert hydrocarbon
Copolymerization with 00 g was carried out at 270 ° C. for 3 hours in a nitrogen atmosphere to carry out the first stage thermal polymerization. After completion of the reaction, inactive components and unreacted fractions in the raw material were distilled out of the system at 240 ° C, and then the mixture was kept under reduced pressure of 50 Torr at 250 ° C for 3 hours to carry out the second stage thermal polymerization. And solidify by cooling to room temperature
It was obtained -C _9.

Cyclopentadiene-vinyl aromatic hydrocarbon-based petroleum resin hydride 1 (referred to as H-PC ₉ -1): 600 g of CPD fraction and 400 g of C ₉ fraction used in the production method of PC ₉ , The first stage thermal polymerization was carried out at 260 ° C. for 3 hours,
Further, except that the second-stage polymerization was carried out at 250 ° C. for 2 hours, the polymerization was carried out in the same manner as in the production method of PC ₉ , and then the nickel-based catalyst was produced in substantially the same manner as in the production method of HP. with 5 wt%, rows 6 hours hydrogenation at 220 ° C., to obtain a _H-PC 9 -1 solid.

Cyclopentadiene - (. Referred to as _H-PC 9 -2) vinyl aromatic hydrocarbon copolymer petroleum resin hydrides 2: _H-PC 9 CPD fraction 500g used in -1 manufacturing method of
And _{C 9} and fraction 400 g, the second stage of three hours at 250 ° C. The polymerization, except for using 4 hours hydrogenation time H-PC ₉ -
In one manufacturing method substantially similar manner, solid H-PC ₉ -
Got 2.

Cyclopentadiene-vinyl aromatic hydrocarbon-based copolymer petroleum resin hydride 3 (referred to as H-PC ₉ -3): CPD fraction 500 g used in the method for producing H-PC ₉ -1.
And C ₉ fraction 400 g, solid H-PC ₉ -3 was prepared in the same manner as in H-PC ₉ -1, except that the second-stage polymerization was carried out at 260 ° C for 2 hours. Obtained.

Cyclopentadiene-vinyl aromatic hydrocarbon copolymer hydride 4 of petroleum resin 4 (referred to as H-PC ₉ -4): HP except that the second stage polymerization was carried out at 240 ° C for 2 hours.
A solid HP was prepared by a method similar to that of C ₉ -1.
To obtain a C ₉ -4.

Cyclopentadiene - (. Referred to as _H-PC 9 -5) hydrides 5 vinyl aromatic hydrocarbon copolymer petroleum resin: _H-PC 9 CPD fraction 500g used in -1 manufacturing method of
Except that the using a _{C 9} fraction 400g in substantially the same manner as the manufacturing method of the _H-PC 9 -1, to obtain a _H-PC 9 -5 solid.

The abbreviation symbols and names shown in Tables 1 to 4 of the hindered amine light stabilizers and inorganic fillers used in Examples and Comparative Examples are shown below.

Abbreviated symbols and names of hindered amine light stabilizers are as follows.

HALS-1: Bis (2,2,6,6-tetramethyl-
4-piperidyl) succinate HALS-2: bis (1,2,2,6,6-pentamethyl-4-piperidyl) succinate HALS-3: bis (2,2,6,6-tetramethyl-
4-piperidyl) sebacate HALS-4: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate HALS-5: bis (2,2,6,6-tetramethyl-
4-piperidyl) -1,5-dioxaspiro [5.5]
Undecane-3,3-dicarboxylate HALS-6: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,5-dioxaspiro [5.
5] Undecane-3,3-dicarboxylate HALS-7: Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate HALS-8: Tetrakis ( 1,2,2,6,6-Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate HALS-9: 3,9-bis [1,1-dimethyl-2-
{Tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy}
Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane HALS-10: poly [[6-[(1,1,3,3-tetramethylbutyl) imino] -1,3 5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2
2,6,6-Tetramethyl-4-piperidyl) imino]] HALS-11: Poly [[6-morpholino-1,3,3
5-triazine-2,4-diyl] [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] HALS-12: 1,5,8,12-tetrakis [4.
6-bis (N- (1,2,2,6,6-pentamethyl-
The abbreviation symbols and names of the 4-piperidyl) -butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecanebenzophenone-based UV absorbers are as follows.

UVA-1: 2-hydroxy-4-n-octoxybenzophenone The abbreviation symbols and names of the benzotriazole-based UV absorbers are as follows.

UVA-2: 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole UVA-3: 2- (2'-hydroxy-3 ', 5'-di -T-Butylphenyl) -5-chlorobenzotriazole Abbreviation symbols and names of hydroxybenzoate-based light stabilizers are as follows.

HBz-1: 2,4-di-t-butylphenyl-3 ',
5'-di-t-butyl-4'-hydroxybenzoate HBz-2: n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate Abbreviation of antistatic agent consisting of fatty acid partial ester of polyale The names are as follows.

AS-1: glyceryl monostearate AS-2: pentaerythritol distearate AS-3: sorbitan monostearate AS-4: sorbitan monooleate The abbreviations and names of antistatic agents consisting of alkylamine ethylene oxide adducts are: It is as follows.

AS-5: N, N-bis (2-hydroxyethyl) laurylamine AS-6: N, N-bis (2-hydroxyethyl) tridecylamine AS-7: N, N-bis (2-hydroxyethyl) Pentadecylamine AS-8: N, N-bis (2-hydroxyethyl) palmitylamine AS-9: N, N-bis (2-hydroxyethyl) stearylamine AS-10: N, N-bis (2- Hydroxyethyl) cocoamine AS-11: N, N-bis (2-hydroxyethyl) tallowamine The abbreviations and names of antistatic agents consisting of fatty acid esters of alkylamine ethylene oxide adducts are as follows.

AS-12: Octadecanoic acid 2-[(2-hydroxyethyl) octadecylamino] ethyl ester The abbreviations and names of the antistatic agents consisting of alkylamine ethylene oxide adducts are as follows.

AS-13: N, N-bis (2-hydroxyethyl) stearoamide AS-14: N, N-bis (2-hydroxyethyl) oleylamide AS-13 :: N, N-bis (2-hydroxyethyl)
The abbreviation symbols and names of lubricants composed of cocoamide fatty acid are as follows.

LU-1: Lauric acid LU-2: Myristic acid LU-3: Palmitic acid LU-4: Stearic acid LU-5: Oleic acid Abbreviations and names of the lubricants consisting of fatty acid monoamides are as follows.

LU-6: stearic acid amide LU-7: oleic acid amide LU-8: erucic acid amide Abbreviation symbols and names of lubricants composed of fatty acid bisamides are as follows.

LU-9: N, N'-ethylene-bis-stearoamide The following were used as the inorganic filler.

TiO ₂ : titanium dioxide (rutile type, average particle size 1.2)
μ) CaCO ₃ : Heavy calcium carbonate (average particle size 1.8 μ) The abbreviations and names of phosphorus antioxidants are as follows.

P-1: Distearyl-pentaerythritol-diphosphite P-2: Bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite P-3: Bis (2,6-di-t) -Butyl-4-methylphenyl) -pentaerythritol-diphosphite P-4: bis (2,4,6-tri-t-butylphenyl) -pentaerythritol-diphosphite P-5: tetrakis (2,4) -Di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite P-6: tris (2,4-di-t-butylphenyl) phosphite P-7: 2,2'-ethylidene -Bis (4,6-di-t
-Butylphenyl) fluorophosphite P-8: 2,2'-methylene-bis (4,6-di-t-
(Butylphenyl) -octylphosphite P-9: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide The abbreviations and names of hydroxylamine antioxidants are as follows.

HA-1: N, N-bis (cured tallow) hydroxylamine The abbreviations and names of phenolic antioxidants are as follows.

AO-1: n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate AO-2: tris (3,5-di-t-butyl-4-hydroxybenzyl) ) Isocyanurate AO-3: tetrakis [methylene-3- (3 ', 5'-
Di-t-butyl-4'-hydroxyphenyl) propionate] methane AO-4: 3,9-bis [1,1-dimethyl-2- {β
-(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,1
The following were used as 0-tetraoxaspiro [5.5] undecane metal soaps.

Ca-St: Calcium stearate Examples 1 to 6 To 100 parts by weight of powdery crystalline propylene homopolymer having an unstabilized MFR of 2.0 g / 10 min, the resin shown in Table 1 and a hindered amine light stabilizer, And other additives in the blending amounts shown in Table 1 respectively in a Henschel mixer (trade name) and mixed for 3 minutes, then melt-kneaded at 230 ° C. in a single screw extruder with a diameter of 40 mm to form pellets. A composition of

The pelletized composition thus obtained was melt extruded at a resin temperature of 250 ° C. using an extruder having a diameter of 40 mm and a T-die having a width of 30 cm, and was rapidly cooled by a cooling roll kept at 40 ° C. to have a thickness of 1 mm.
To obtain an unstretched sheet. Next, this sheet was cut into squares, and stretched 5.2 times in both directions at the same time at a temperature of 155 ° C. using a pantograph type biaxial stretching machine, and heat-treated under tension at the same temperature for 15 seconds. Thickness about 40μ
A biaxially stretched film of was obtained.

The characteristic values of the obtained film are also shown in Table 1.

Comparative Examples 1 to 5 Comparative Examples 1 and 2 do not use a hindered amine light stabilizer, and Comparative Example 3 has a resin content outside the range of the present invention. Further, in Comparative Example 4, the weight average molecular weight of the resin is outside the range of the present invention and no hindered amine light stabilizer is used, and in Comparative Example 5, the weight average molecular weight of the resin is outside the range of the present invention. It is a thing. The procedure was carried out according to Example 1 based on the blending amounts shown in Table 1.

The results are shown in Table 1.

As is clear from Table 1, the films of Examples 1 to 6 and Comparative Examples 1 and 2 using the composition of the present invention both have low total light transmittance, are extremely opaque and have excellent light-shielding properties.
Although a large number of fine foam particles are formed inside, Examples 1 to 6
It is clear that while Comparative Example 1 and 2 are excellent in light resistance, Comparative Examples 1 and 2 are clearly inferior in light resistance. Further, Comparative Example 3 has the same light resistance as those of Examples 1 to 6, but it is found that the total light transmittance is high and the opacity and the light blocking property are poor. Further, it can be seen that Comparative Example 4 has a high total light transmittance, and is inferior in opacity, light shielding property, and light resistance. Further, it can be seen that Comparative Example 5 is excellent in light resistance, but is high in total light transmittance, and is inferior in opacity and light shielding property.

Examples 7 to 14 100 parts by weight of powdery crystalline propylene homopolymer having an unstabilized MFR of 4.0 g / 10 min were added with a resin, a hindered amine light stabilizer, and other additives shown in Table 2. Put them in the Henkel mixer (trade name) with the blending amounts shown in Table 2 and stir and mix for 3 minutes.
Melt kneading was carried out at 230 ° C. with a twin-screw extruder having a diameter of 30 mm to obtain a pelletized composition.

The pelletized composition thus obtained was melt extruded at a resin temperature of 250 ° C. using an extruder having a diameter of 40 mm and a T-die having a width of 30 cm, and was rapidly cooled by a cooling roll kept at 40 ° C. to have a thickness of 1 mm.
To obtain an unstretched sheet. Next, this sheet was cut into a square shape and stretched by a pantograph-type biaxial stretching machine at a temperature of 155 ° C. at a temperature of 155 ° C. in each of two directions in the vertical and horizontal directions by 5.2 times.
Heat-treated under tension at the same temperature for 15 seconds to a thickness of about 40μ 2.
An axially stretched film was obtained.

The characteristic values of the obtained film are also shown in Table 2.

Comparative Examples 6 to 10 Comparative Examples 6 and 7 do not use a hindered amine light stabilizer, and Comparative Example 8 has a resin content outside the range of the present invention. Further, in Comparative Example 9, the weight average molecular weight of the resin is outside the range of the present invention, no hindered amine light stabilizer is used, and in Comparative Example 10, the weight average molecular weight of the resin is outside the range of the present invention. Is.

The procedure was carried out according to Example 7, except that the blending amount shown in Table 2 was used.

The results are shown in Table 2.

The same effect as in Table 1 was confirmed from Table 2.

Examples 15 to 20 100 parts by weight of powdered crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight) of unstabilized MFR 3.0 g / 10 min, the resin shown in Table 3, The hindered amine light stabilizer and other additives were added to the Henschel mixer (trade name) in the amounts shown in Table 3, and the mixture was stirred and mixed for 3 minutes.
The composition was melted and kneaded at 230 ° C. with a 0 mm single screw extruder to obtain a pelletized composition.

The pelletized composition thus obtained was melt extruded at a resin temperature of 250 ° C. using an extruder having a diameter of 40 mm and a T-die having a width of 30 cm, and was rapidly cooled by a cooling roll kept at 40 ° C. to have a thickness of 1 mm.
To obtain an unstretched sheet. Next, this sheet was cut into squares and stretched 5.2 times in both directions at a temperature of 140 ° C. in both directions at a temperature of 140 ° C. using a Pandagraph type biaxial stretching machine, and heat-treated under tension at the same temperature for 15 seconds. And thickness is about 40μ
A biaxially stretched film of was obtained.

The characteristic values of the obtained film are also shown in Table 2.

Comparative Examples 11 to 15 Comparative Examples 11 and 12 do not use a hindered amine light stabilizer, and Comparative Example 13 has a resin content outside the range of the present invention. Further, Comparative Example 14 has a resin weight average molecular weight outside the range of the present invention and does not use a hindered amine light stabilizer, and Comparative Example 15 has a resin weight average molecular weight outside the range of the present invention. It is a thing.

The procedure was carried out according to Example 17, except that the blending amount shown in Table 3 was used. The results are shown in Table 3.

From Table 3, the same effect as in Table 1 was confirmed.

Examples 21 to 28 100 parts by weight of powdered crystalline ethylene-propylene block copolymer (ethylene content 8.0% by weight) of unstabilized MFR 4.0 g / 10 min, the resin described in Table 4, The hindered amine light stabilizer and other additives were added to the Henschel mixer (trade name) in the amounts shown in Table 4, and mixed for 3 minutes with stirring.
The composition was melted and kneaded at 230 ° C. with a 0 mm single screw extruder to obtain a pelletized composition.

The pelletized composition thus obtained was melt extruded at a resin temperature of 250 ° C. using an extruder having a diameter of 40 mm and a T-die having a width of 30 cm, and was rapidly cooled by a cooling roll kept at 40 ° C. to obtain a 1 mm thick unstretched sheet. Obtained. Next, this sheet was cut into squares and stretched 5.2 times in both directions at a temperature of 155 ° C. using a pantograph type biaxial stretching machine,
Heat-treated under tension at the same temperature for 15 seconds to a thickness of about 40μ 2.
An axially stretched film was obtained.

The characteristic values of the obtained film are also shown in Table 4.

Comparative Examples 16 to 20 Comparative Examples 16 and 17 do not use a hindered amine light stabilizer, and Comparative Example 18 has a resin content outside the range of the present invention. Further, Comparative Example 19 has a resin weight average molecular weight outside the range of the present invention and does not use a hindered amine light stabilizer, and Comparative Example 20 has a resin weight average molecular weight outside the range of the present invention. It is a thing.

The procedure of Example 21 was repeated except that the blending amount shown in Table 4 was used.

The results are shown in Table 4.

From Table 4, it is clear that the same effect as in Table 1 was confirmed.

〔The invention's effect〕

Films and thin-walled molded products obtained by using the composition of the present invention, particularly stretch-molded products, are generally packaging materials, decorative materials, and synthetic materials by taking advantage of their excellent light resistance and unique texture such as opacity and light-shielding properties. Used for paper and copy-printed paper,
Also packed as tapes, ribbons, monofilaments,
It is also useful for woven paper.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08K 5/00 KEW 7242-4J KFB 7242-4J C08L 45/00 LKB 7921-4J // C08J 5/18 CES 9267 -4F (C08K 5/00 5: 3435 5:10 5:07 5:17 5:20)

Claims (7)

[Claims] 1. A crystalline polypropylene of 100 parts by weight, a resin shown below of 5 to 150 parts by weight, a hindered amine light stabilizer of 0.05 to 5 parts by weight, and a fatty acid, a fatty acid partial ester of a polyol, and an alkylamine ethylene oxide adduct. A crystalline polypropylene composition comprising 0.05 to 5 parts by weight of a fatty acid ester of an alkylamine ethylene oxide adduct, an alkylamide ethylene oxide adduct, a fatty acid monoamide, a fatty acid bisamide, or a mixture of two or more thereof. A component containing the cyclopentadiene-based polymerizing component (A), or the component (A) and a vinyl aromatic hydrocarbon-based polymerizing component (B)
And a weight composition ratio (B) / (A) of which is 0 to 0.5, and a weight average molecular weight (M _W ) is represented by the formula M _W ≧ 680 + 2200X (where M _W is a standard Polystyrene conversion, X is a resin having a value of composition ratio [(B) / [(A) + (B)]]. 2. A hindered amine light stabilizer is bis (2,2,6,6-tetramethyl-4-piperidyl) succinate or bis (1,2,2,6,6-pentamethyl-4-piperidyl) succinate. , Screw (2, 2, 6,
6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 5-Dioxaspiro [5.
5] undecane-3,3-dicarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-
3,3-dicarboxylate, tetrakis (2,2,
6,6-Tetramethyl-4-piperidyl) 1,2,3
4-butane tetracarboxylate, tetrakis (1,
2,2,6,6-pentamethyl-4-piperidyl) 1,
2,3,4-butane tetracarboxylate, 3,9-
Bis [1,1-dimethyl-2- {tris (1,2,2,
6,6-Pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,
10-Tetraoxaspiro [5.5] undecane, poly [[6-[(1,1,3,3-tetramethylbutyl) imino] -1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-morpholino-1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], 1,5,8,12
-Tetrakis [4,6-bis (N- (1,2,2,6,
6-pentamethyl-4-piperidyl) -butylamino)
-1,3,5-triazin-2-yl] -1,5,8,
The crystalline polypropylene composition according to claim 1, which is 12-tetraazadodecane or a mixture of two or more thereof. 3. A benzophenone-based UV absorber, a benzotriazole-based UV absorber, a hydroxybenzoate-based light stabilizer or 0.05 to 5 parts by weight of a mixture of two or more of them with respect to 100 parts by weight of crystalline polypropylene. The crystalline polypropylene composition according to any one of claims (1) and (2), which is further compounded. 4. A benzophenone-based UV absorber is 2-hydroxy-4-n-octoxybenzophenone, and a benzotriazole-based UV absorber is 2- (2'-hydroxy-3'-t-butyl-5'-. Methylphenyl) -5-
Chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole or a mixture thereof, a hydroxybenzoate light stabilizer is 2,4-di-t-butylphenyl-3', 5'-di -T-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t-
The crystalline polypropylene composition according to claim 3, which is butyl-4-hydroxybenzoate or a mixture thereof. 5. A fatty acid is lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid or a mixture of two or more thereof, and a fatty acid partial ester of a polyol is glyceryl monostearate, pentaerythritol distearate, sorbitan. Monostearate, sorbitan monooleate or a mixture of two or more thereof, alkylamine ethylene oxide adduct is N,
N-bis (2-hydroxyethyl) laurylamine,
N, N-bis (2-hydroxyethyl) tridecylamine, N, N-bis (2-hydroxyethyl) pentadecylamine, N, N-bis (2-hydroxyethyl) palmitylamine, N, N-bis (2-hydroxyethyl)
Stearylamine, N, N-bis (2-hydroxyethyl) cocoaminine, N, N-bis (2-hydroxyethyl) tallowamine or a mixture of two or more thereof,
The fatty acid ester of alkylamine ethylene oxide adduct is octadecanoic acid 2-[(2-hydroxyethyl) octadecylamino] ethyl ester, and the alkylamide ethylene oxide adduct is N, N-bis (2-
Hydroxyethyl) stearamide, N, N-bis (2
-Hydroxyethyl) oleylamide, N, N-bis (2-hydroxyethyl) cocoamide or a mixture of two or more thereof, fatty acid monoamide may be stearic acid amide, oleic acid amide, erucic acid amide or two or more thereof. Mixture, fatty acid bisamide, N,
N'-Ethylene-bis-stearoamide.
The crystalline polypropylene composition according to (1). 6. The crystalline polypropylene according to claim 1, wherein 0.5 to 200 parts by weight of an inorganic filler is further mixed with 100 parts by weight of crystalline polypropylene. Composition. 7. The inorganic filler is calcium carbonate, talc,
Mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, magnesium carbonate, zinc sulfide, barium sulfate, silicic acid calcium,
The crystalline polypropylene composition according to claim 6, which is aluminum silicate or a mixture of two or more of these.