JPH10120848A - Crystalline polyolefin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. which gives a molded item improved in clarity by compounding a crystalline polyolefin with specified amts. of a specific phosphate compd. and a composite lithium aluminum carbonate. SOLUTION: 100 pts.wt. crystalline polyolefin is compounded with 0.01-1 pt.wt. phosphate compd. represented by the formula [wherein R is 1-4C alkylidene; Ar1 and Ar2 are each arylene or alkarylene; M is a metal atom of the group II to IV; and when M is a metal atom of the group III, then X is not present or it is OH, and when M is a metal atom of the group IV, then X is O or (OH)2 ] and 0.01-1 pt.wt. composite lithium aluminum carbonate represented by the formula: (Li2 O)x Al2 O3 (CO3 )y Az .kH2 O (wherein A is an at least divalent org. acid anion; 0<x<0.2; 0.01<=y<1; 0<=z<1; 2<=k<10; and 0.1<=y+z<1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline polyolefin composition from which a molded article having excellent transparency can be obtained.
More specifically, the present invention relates to a crystalline polyolefin composition which is obtained by blending a crystalline polyolefin with a phosphate compound having a specific structure and a lithium aluminum composite carbonate in a specific amount, respectively, and thereby obtaining a molded article having excellent transparency.

[0002]

2. Description of the Related Art Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties.
It is used for the production of various molded products such as hollow molded products, films, sheets and fibers. However, while crystalline polyolefins have excellent mechanical properties, they have the drawback that their use is limited due to poor transparency due to the high crystallinity of the crystalline polyolefins.
For this reason, conventionally, for the purpose of improving the transparency of the crystalline polyolefin, various nucleating agents such as sodium benzoate, monobasic aluminum 4-t-butylbenzoate, metal carboxylate such as sodium adipate, sodium
-Bis (4-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl)
Acid phosphate metal salts such as phosphates, 1, 3,
Polyhydric alcohol derivatives such as 2,4-dibenzylidene sorbitol and 1,3,2,4-bis (4-methylbenzylidene) sorbitol are used.

[0003] Among these compounds, JP-A-58-1736
Metallic salts of cyclic phosphoric acid esters of alkylidene bisphenols described in JP-A-59-184252 and JP-A-59-184252 are widely used because they have a large effect and do not generate an odor such as a benzaldehyde odor.

Attempts have also been made to improve the effect by using a metal salt compound or a derivative thereof of a cyclic phosphate of an alkylidene bisphenol compound in combination with another metal compound. JP-A-63-69853 discloses an alkaline earth metal phosphate-based nucleating agent and an alkaline earth metal carboxylate such as calcium stearate to prevent a decrease in rigidity when used in combination. A method using a hydrotalcite or an alkali metal carboxylate in place of the metal carboxylate has been proposed, and Japanese Patent Application Laid-Open Nos. 1-129050 and 1-129051 related to the application of the present applicant disclose cyclic methods. A method has been proposed in which an organic phosphoric acid ester metal salt is used in combination with an aliphatic carboxylic acid group II metal salt of the periodic table. JP-A-3-79649 and JP-A-3-81368 propose a method in which an acidic organic phosphoric acid ester compound and a metal salt of an aliphatic carboxylic acid are used in combination. It is described that a wetting agent, a filler and the like can be added. Further, JP-A-3-43437 discloses an alkali metal, an alkaline earth metal or an aluminum group metal in order to prevent a decrease in pH at the time of immersion in hot water after irradiation in the case of using a cyclic diaryl phosphate metal salt. It has been proposed to use a combination of hydroxides.

[0005] However, the improvement effect of these combinations is not yet practically satisfactory.
In particular, further improvement has been demanded from the viewpoint of improving the transparency of the crystalline polyolefin.

Further, the inventor of the present invention disclosed in Japanese Unexamined Patent Publication No. Hei.
JP 101356, JP-A 1-104638, JP-A 1-10
No. 4639 and JP-A-1-104647 propose to use a monobasic aluminum salt of an aromatic phosphate diester, and a comparative example of these publications discloses a monobasic aluminum salt of a cyclic aromatic phosphate diester. Compositions using two salts each are described. However, when these two kinds of monobasic aluminum salts are used, the effect of improving transparency is hardly recognized.
It has been considered that such a monobasic polyvalent metal salt compound is poor in the effect of improving the transparency of the crystalline polyolefin.

For this reason, JP-A-5-140466, JP-A-5-156078, JP-A-7-48473 and JP-A-8-120116 disclose crystalline synthetic resins such as crystalline polyolefins. By adding an alkali metal organic carboxylate, an alkali metal β-diketonate or an alkali metal β-ketoacetate and a cyclic organic phosphate metal salt or a cyclic organic phosphate basic polyvalent metal salt, A crystalline synthetic resin composition having significantly improved transparency and also increased mechanical strength has been proposed. In this publication, the crystalline synthetic resin composition contains, as necessary, hydrotal It states that sites can be added.

On the other hand, JP-A-8-41076 and JP-A-8-231557 disclose a stable dried aluminum hydroxide gel having a large antacid activity which can be usefully used in the field of acid adsorbents. Is disclosed.

Japanese Patent Application Laid-Open No. 63-69853 discloses that hydrotalcites used in combination with an aromatic metal phosphate-based nucleating agent are Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O. There is no description or suggestion that the use of dried aluminum hydroxide gel as hydrotalcites improves the transparency of a molded article obtained from the crystalline polyolefin composition. In addition, the above-mentioned JP-A-3-79.
Japanese Unexamined Patent Publication (Kokai) No. 649 and JP-A-3-81368 describe that a neutralizing agent or a filler can be used in combination as an additional component, but dry aluminum hydroxide gel is used as the neutralizing agent or the filler. There is no description or suggestion that improving the transparency of a molded article obtained from a crystalline polyolefin composition by using a dry aluminum hydroxide gel instead of a metal salt of an aliphatic carboxylic acid. Further, JP-A-3-43437 discloses that a crystalline polyolefin is obtained by using a dry aluminum hydroxide gel as a hydroxide of an alkali metal, an alkaline earth metal or an aluminum group metal in combination with a cyclic diaryl phosphate metal salt. There is no description or suggestion of improving the transparency of a molded article obtained from the composition.
The above-mentioned JP-A-5-140466 and JP-A-5-1560 are disclosed.
No. 78, JP-A-7-48473 and JP-A-8-12011
No. 6 describes that hydrotalcites can be used in combination as an additional component.However, it is possible to use dry aluminum hydroxide gel as hydrotalcites, or to use an alkali metal organic carboxylate, an alkali metal. There is no description or suggestion that the use of a dry aluminum hydroxide gel instead of the β-diketonate or alkali metal β-ketoacetate to improve the transparency of a molded article obtained from the crystalline polyolefin composition.

[0010]

SUMMARY OF THE INVENTION The present inventor has disclosed in
-140466, JP-A-5-156078, JP-A-7-
Without being satisfied with the crystalline synthetic resin compositions proposed in JP-A-48473 and JP-A-8-120116, intensive studies have been made to obtain a crystalline polyolefin composition which gives a molded article with further improved transparency. As a result, the inventor
Molded article in which a crystalline polyolefin composition comprising a specific amount of a phosphate-based compound having a specific structure in a crystalline polyolefin and a lithium-aluminum composite carbonate containing lithium as a dry aluminum hydroxide gel has improved transparency. The present invention has been found based on this finding. As is apparent from the above description, an object of the present invention is to provide a crystalline polyolefin composition having improved transparency when molded.

[0011]

The present invention has the following arrangement. (1) A phosphate compound represented by the following general formula (1) (hereinafter, referred to as compound A) and a lithium aluminum complex carbonate (hereinafter, referred to as compound B) represented by the following general formula (1) per 100 parts by weight of the crystalline polyolefin. .) In an amount of 0.01 to 1 part by weight.

Embedded image _{(Li 2 O) x Al 2} O 3 (CO 3) y A z · kH 2 O ( wherein R is an alkylidene group having 1 to 4 carbon atoms, Ar ₁ and Ar ₂ are arylene or alkylarylene group And M represents a metal atom belonging to Group II to Group IV of the periodic table, and when M represents a metal atom belonging to Group II of the periodic table, m represents 2;
When n represents 0 and M represents a metal atom belonging to Group III of the periodic table, m represents 3, n represents 0, or m represents 2, n represents 1, or m. Represents 1, n represents 2, and X represents OH. When M represents a metal atom of Group IV of the periodic table, m represents 2, n represents 1, and X represents =
O or (OH) ₂ is shown, respectively. A represents an anion of a divalent or higher organic acid, x represents 0 <x <0.2, and y represents 0.0.
1 ≦ y <1, z is 0 ≦ z <1, k is 2 ≦ k <10,
y and z indicate 0.1 ≦ y + z <1, respectively. )

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The crystalline polyolefin used in the present invention is ethylene, propylene, butene-1, pentene-
Crystalline homopolymers of α-olefins such as 1,4-methyl-pentene-1, hexene-1, and octene-1, and crystalline or low-crystalline random copolymers or crystals of two or more of these α-olefins Block copolymers, copolymers of the above-mentioned α-olefins with vinyl acetate or acrylate, saponified products of the copolymers, copolymers of these α-olefins with unsaturated silane compounds, these α-olefins A copolymer of an olefin with an unsaturated carboxylic acid or an anhydride thereof, a reaction product of the copolymer with a metal ion compound, a crystalline homopolymer of the above-mentioned α-olefin, or a crystalline or low crystalline random copolymer. Modified polyolefin obtained by modifying a polymer or a crystalline block copolymer with an unsaturated carboxylic acid or a derivative thereof, a crystalline homopolymer of the above-mentioned α-olefin, a crystalline or low crystalline lander Silane-modified polyolefins obtained by modifying a copolymer or a crystalline block copolymer with an unsaturated silane compound, and the like. These crystalline polyolefins can be used alone, or two or more crystalline polyolefins can be used. They can be used in combination.

The above-mentioned crystalline polyolefin may be replaced with various synthetic rubbers (for example, amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene 3).
Original copolymer, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-
Styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-
Styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, ethylene-ethylene-
Butylene-ethylene block copolymer, ethylene-propylene-butylene-ethylene block copolymer, etc.) or thermoplastic synthetic resin (eg, amorphous ethylene-cyclic alkene copolymer (eg, amorphous ethylene-tetracyclododecene) Copolymer), polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyvinyl chloride, fluorine resin, petroleum resins (e.g. C ₅ petroleum resins, hydrogenated C ₅ petroleum resins, C ₉ petroleum resins,
Hydrogenated C ₉ petroleum resin, C ₅ -C ₉ copolymerized petroleum resin, hydrogenated C _5-
C ₉ copolymerized petroleum resin, acid-modified C ₉ petroleum resin), DC
PD resin (for example, cyclopentadiene-based petroleum resin, hydrogenated cyclopentadiene-based petroleum resin, cyclopentadiene
-C ₅ copolymer petroleum resin, hydrogenated cyclopentadiene -C ₅ copolymer petroleum resin, cyclopentadiene -C ₉ copolymer petroleum resin,
Hydrogenated cyclopentadiene -C ₉ copolymer petroleum resin, cyclopentadiene -C ₅ -C ₉ copolymer petroleum resin, softening point 80 to 200 ° C., such as hydrogenated cyclopentadiene -C ₅ -C ₉ copolymer petroleum resin
And the like) can also be used as a mixture.

A crystalline propylene homopolymer, a crystalline propylene copolymer containing at least 70% by weight of a propylene component, comprising a crystalline ethylene-propylene random copolymer and a crystalline propylene-butene-1 random copolymer Particularly, a crystalline ethylene-propylene-butene-1 terpolymer, a crystalline propylene-hexene-butene-1 terpolymer and a mixture of two or more thereof are particularly preferably used.
In particular, the present invention can be applied irrespective of the intrinsic viscosity, isotactic pentad fraction, density, molecular weight distribution, melt flow rate, crystallinity, rigidity, etc. of the crystalline propylene polymer. For example, JP-A-63-3714
No. 8, JP-A-63-37152, JP-A-63-90552, JP-A-63-210152, JP-A-63-213547, JP-A-63-243150, JP-A-63-243152, JP-A-63-260943, JP-A-63-260944, JP-A-63-264650, JP-A-1-178541, JP-A-2-49047 JP-A-2-102242, JP-A-2-251548, JP-A-2-279746, JP-A-3-195751 Also preferably used for crystalline propylene-based polymer as described in can do.

Further, as the crystalline polyolefin used in the present invention, a highly active catalyst composition containing a titanium halide catalyst component supported on magnesium halide and an organoaluminum catalyst component, in particular, an electron donor catalyst component The use of a crystalline propylene-based polymer (preferably a deashed process) obtained by polymerization in the presence of a highly active and highly stereoregular catalyst composition further combining This is preferred because the properties are further improved.

[0016] The general formula as the compound A used in the present invention (1), the alkylidene group having 1 to 4 carbon atoms represented by R, methylene, ethylidene, propylidene, etc. butylidene may be mentioned, Ar ₁ and Examples of the arylene group or alkylarylene group represented by Ar ₂ include phenylene and alkylphenylene (alkyl groups include methyl, ethyl, propyl, i-propyl, butyl, s-butyl, t-butyl, amyl, t-amyl, Hexyl, heptyl, octyl, i-octyl, t-octyl, 2-
Ethylhexyl, nonyl, i-nonyl, decyl, i-decyl, undecyl, dodecyl, t-dodecyl) and the like. Examples of metal atoms of Groups II to IV of the periodic table represented by M include magnesium, calcium, strontium, barium, zinc, aluminum, gallium, germanium, tin, titanium, zirconium, hafnium, and the like. Particularly, aluminum is preferable.

Accordingly, as compound A, 2,2′-methylene-bis (4,6-di-t-butylphenyl) acid phosphate, 2,2′-methylene-bis (4-methyl-6-t -Butylphenyl) acid phosphate, 2,2′-methylene-bis (4-ethyl-6-t-butylphenyl) acid phosphate, 2,
2'-methylene-bis (4,6-dimethylphenyl) acid phosphate, 2,2'-methylene-bis (4,6-diethylphenyl) acid phosphate, 2,2'-methylene-bis (4,6 -
(Di-t-amylphenyl) acid phosphate, 2,2'-
Ethylidene-bis (4,6-di-t-amylphenyl) acid phosphate, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) acid phosphate, 2,2'-ethylidene-
Bis (4-s-butyl-6-t-butylphenyl) acid phosphate, 2,2′-ethylidene-bis (4-i-propyl-6-t-butylphenyl) acid phosphate, 2,2′- Butylidene-bis (4,6-dimethylphenyl) acid phosphate, 2,2'-butylidene-bis (4,6-di-t-butylphenyl)
Acid phosphate, calcium-2,2'-methylene-
Bis (4,6-di-t-butylphenyl) phosphate, magnesium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, zinc-2,2'-methylene- Screw (4,6-
Di-t-butylphenyl) phosphate, aluminum-
2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, calcium-2,2'-methylene-bis (4-methyl-6
-t-butylphenyl) phosphate, calcium-2,2'-
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, aluminum hydroxy-2,2'-methylene-bis
(4,6-di-t-butylphenyl) phosphate, titanium dihydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, tindihydroxy-2,2 ' -Methylene-bis (4,6-di-t-butylphenyl) phosphate, zirconiumoxy-2,2'-methylene-bis (4,6-di-t
-Butylphenyl) phosphate, aluminum hydroxy-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, aluminum hydroxy-2,2 '
-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, aluminum dihydroxy-2,2'-methylene-
Bis (4,6-di-t-butylphenyl) phosphate, aluminum dihydroxy-2,2'-methylene-bis (4-methyl
-6-t-butylphenyl) phosphate and aluminum dihydroxy-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, and especially 2,2'-
Methylene-bis (4,6-di-t-butylphenyl) acid phosphate, 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) acid phosphate, calcium-2,2'- Methylene-bis (4,6-di-t-butylphenyl) phosphate, aluminum-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, aluminum hydroxy-2,2 '-Methylene-bis (4,6-di-t-butylphenyl) phosphate, aluminum dihydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate are preferred.

Compound A is disclosed in JP-A-5-140466,
It can be obtained by the production method described in JP-A-5-156078, JP-A-7-48473 or JP-A-8-120116. That is, phosphorus oxychloride and 2,2'-
After reacting with an alkylidene bisphenol, reacting with an oxide or hydroxide of a polyvalent metal, or forming an alkali metal salt and then reacting with a halide of the polyvalent metal, or A method in which an alkali metal salt of an organic phosphate is reacted with a polyvalent metal halide or (aqueous) oxidized polyvalent metal halide, and then, if necessary, hydrolyzed, an acidic cyclic organic phosphate and a polyvalent metal alkoxide. And then, if necessary, hydrolysis. The compound A is not particularly limited with respect to its particle size. For example, those having an average particle size of 0.01 to 50 μm can be used.To achieve uniform dispersion, the average particle size is 10 μm or less. In particular, it is preferable to pulverize the particles into particles having a size of 3 μm or less. The compound A can be used alone, or two or more types of the compound A can be used in combination. The compounding ratio of the compound A is from 0.01 to 1 part by weight based on 100 parts by weight of the crystalline polyolefin in terms of transparency.
Preferably it is 0.05 to 0.5 parts by weight.

The compound B used in the present invention has a substantially stoichiometric composition as shown above. Compound B is disclosed in JP-A-8-41076 or JP-A-8-2.
It can be obtained by the production method described in JP-A-31557. That is, a soluble aluminum compound and a carbonate ion supplying compound are used as essential raw materials, and these raw materials are pH 5 to 10
And washing under the conditions of After this washing, wet pulverization is performed, followed by drying. When an anion of an organic acid is introduced, an organic acid and / or a salt thereof is added together with a soluble aluminum compound and a carbonate ion-supplying compound to pH.
It becomes possible by reacting under conditions of 5 to 10. Examples of the soluble aluminum compound include one or more of aluminum chloride, aluminum nitrate, aluminum sulfate, metal aluminum, aluminum ammonium sulfate, aluminum bromide, aluminum fluoride, aluminum lithium lithium, aluminum isopropoxide, lithium aluminate, and the like. Two or more types can be selected. As carbonate ion supplying compounds, lithium carbonate,
One or more of urea, carbon dioxide and the like can be used. As the divalent or higher organic acid, tartaric acid,
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, divalent aliphatic saturated carboxylic acids such as sebacic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc. A divalent aromatic carboxylic acid such as a divalent aliphatic unsaturated carboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid can be used alone or as a mixture. In addition, citric acid can be used alone or as a mixture with a divalent organic acid as a trivalent organic acid. Further, in the present invention, these organic acids may be used in the form of a salt.

The reaction between the soluble aluminum compound and the carbonate ion-supplying compound and the reaction between these compounds and the organic acid and / or its salt can be carried out in water or a lower alcohol solvent at pH 5 to 10. it can. Basic substances such as ammonia, ammonium hydroxide and lithium hydroxide can be used for pH adjustment during the reaction. The aluminum hydroxide gel produced by the reaction is washed with water, and then wet-milled. For this wet pulverization, it is possible to use a pulverizer such as a rolling type, a vibration type, a planetary type ball mill, a tower type, a stirring tank type, a flow tube type, an annular type medium stirring type pulverizer, a colloid mill, and a high-pressure homogenizer. it can. After this wet pulverization, drying is performed by an appropriate drying means such as natural drying, hot air drying, reduced pressure drying, and spray drying. Thereby, compound B can be obtained.
The compound B is not particularly limited with respect to its particle size. For example, a compound having an average particle size of 0.01 to 50 μm can be used.
It is preferable that the particles are pulverized into fine particles of 10 μm or less, particularly 3 μm or less. These compounds B can be used alone, or two or more compounds B can be used in combination. The compounding ratio of the compound B is 0.01 to 1 part by weight, preferably 100 parts by weight of the crystalline polyolefin, from the viewpoint of transparency, preferably
It is 0.05 to 0.5 parts by weight.

In the composition of the present invention, various additives usually added to the crystalline polyolefin, for example, phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, heavy metal deactivators ( Copper damage inhibitor), 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-bis (4-methylbenzylidene) sorbitol, 1,3,2,4-bis (3,4-dimethyl Clarifying agents such as benzylidene) sorbitol, sodium-bis (4-t-butylphenyl) phosphate, and sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate Nucleating agent (excluding compound A), lubricant, antistatic agent, antifogging agent, antiblocking agent, non-dropping agent, radical generator such as organic peroxide, flame retardant, flame retardant auxiliary, pigment, halogen Scavenger (however, except for Compound B), dispersion of metallic soaps Or neutralizing agents, organic and inorganic antibacterial agents, inorganic fillers (such as talc, mica, clay -, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, magnesium carbonate,
Aluminum hydroxide, magnesium hydroxide, hydrotalcite, silicon dioxide, titanium dioxide, magnesium oxide, zinc oxide, calcium oxide, zinc sulfide, barium sulfate, magnesium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate , Carbon fibers, carbon black, graphite, metal fibers, etc.) and coupling agents (for example, silane, titanate, boron, aluminate, zircoaluminate, etc.). A filler or an organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) can be used in combination as long as the object of the present invention is not impaired.

The composition of the present invention is prepared by adding a predetermined amount of each of the above-mentioned compounds A and B and the above-mentioned various additives usually added to the crystalline polyolefin to a crystalline polyolefin by using a conventional mixing apparatus such as a Henschel mixer (trade name). ), Using a super mixer, ribbon blender, Banbury mixer, etc.
It can be obtained by melt-kneading pelletizing at a melt-kneading temperature of 150 ° C. to 300 ° C., preferably 180 ° C. to 270 ° C. using a screw extruder, a Brabender or a roll. The obtained composition is used for production of a target molded article by various molding methods such as an injection molding method, an extrusion molding method, and a blow molding method.

The composition of the present invention may be used for various post-treatments, for example, for medical use (pharmaceutical solutions, infusions,
Applications that are sterilized by radiation, such as blood transfusion devices, syringes, injection needle bases, medical devices such as blood collection devices) or food packaging (use of phosphorous antioxidants and hindered amine light stabilizers in combination) It can also be used for applications in which low-temperature plasma treatment, corona discharge treatment, etc. are performed after molding to improve surface properties such as paintability and printability.

[0024]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation method used in the examples and comparative examples was based on the following method. Transparency: using the obtained pellets, length 50 mm, width 25 m
A test piece having a thickness of 1 mm and a thickness of 1 mm was prepared by an injection molding method, and the test piece was evaluated for haze (according to ASTM D-1003-61). A highly transparent material has a small haze value.

Examples 1 to 13 and Comparative Examples 1 to 10 As a crystalline polyolefin, 100 parts by weight of an unstabilized powdery crystalline propylene homopolymer having an MFR of 6.0 g / 10 min and 2,2 ′ as a compound A -Methylene-bis (4,6-di-t-
(Butylphenyl) acid phosphate, calcium-
2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, magnesium-2,2'-methylene-bis (4,6-di-t
-Butylphenyl) phosphate, aluminum hydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl)
Phosphate, titanium dihydroxy-2,2'-methylene
-Bis (4,6-di-t-butylphenyl) phosphate, aluminum dihydroxy-2,2'-methylene-bis (4,6-di-t
-Butylphenyl) phosphate or aluminum dihydroxy-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium aluminum complex carbonate having the composition described below as compound B and other A predetermined amount of each of the additives was placed in a Henschel mixer (trade name) at a mixing ratio shown in Table 1 below, and stirred and mixed for 3 minutes, followed by melt-kneading at 200 ° C. with a twin-screw extruder having a diameter of 30 mm. Pelletized. As Comparative Examples 1 to 10, MFR
Are mixed with 100 parts by weight of an unstabilized powdery crystalline propylene homopolymer of 6.0 g / 10 min, each of the additives described in Table 1 described below, according to Examples 1 to 13. Pellets were obtained by melt kneading. A test piece used for evaluation of transparency was prepared by injection molding the obtained pellet at a resin temperature of 250 ° C. and a mold temperature of 50 ° C. The transparency was evaluated by the test method using the obtained test piece. The results are shown in Table 1.

Examples 14 to 26, Comparative Examples 11 to 20 As crystalline polyolefin, an unstabilized powdery crystalline ethylene-propylene random copolymer having an MFR of 7.0 g / 10 min (ethylene content 4.0% by weight) 100 Weight parts,
As compound A, 2,2′-ethylidene-bis (4,6-di-t-amylphenyl) acid phosphate, zinc-2,2′-methylene-bis (4,6-di-t-butylphenyl) phospho Fate,
Aluminum-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, tindihydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate Fate, zirconiumoxy-2,2'-methylene-bis (4,6-di-t
-Butylphenyl) phosphate, aluminum dihydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate or aluminum dihydroxy-2,
The prescribed amounts of 2′-propylidene-bis (4,6-di-t-amylphenyl) phosphate, lithium aluminum complex carbonate having the following composition as compound B, and other additives are shown in Table 2 below. Into a Henschel mixer (trade name) at the specified mixing ratio, and mixed by stirring for 3 minutes.
The mixture was melt-kneaded at 200 ° C. with a 30 mm twin-screw extruder to form pellets. Further, as Comparative Examples 11 to 20, 100 parts by weight of an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content: 4.0% by weight) having an MFR of 7.0 g / 10 min. A predetermined amount of each additive was blended, and the mixture was melt-kneaded according to Examples 14 to 26 to obtain pellets. A test piece used for evaluation of transparency was prepared by injection molding the obtained pellet at a resin temperature of 250 ° C. and a mold temperature of 50 ° C. The transparency was evaluated by the test method using the obtained test piece. Table 2 shows the results.

Examples 27 to 39, Comparative Examples 21 to 30 As a crystalline polyolefin, 15% by weight of an unstabilized powdery crystalline propylene homopolymer having an MFR of 6.0 g / 10 min and a stability of MFR of 7.0 g / 10 min 80% by weight of an unmodified powdered crystalline ethylene-propylene-butene-1 terpolymer (ethylene content 4.0% by weight, butene-1 content 4.5% by weight) and MI (load: 2.16 kg at 190 ° C.) Discharge rate of molten resin for 10 minutes when added) Unstabilized powdered Ziegler-Natta high-density ethylene with 5.0 g / 10 minutes
Propylene copolymer (density 0.950 g / cm ³ , methyl branch 3.0
To a total of 100 parts by weight consisting of 5 parts by weight
As compound A, 2,2′-butylidene-bis (4,6-dimethylphenyl) acid phosphate, calcium-2,2′-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, calcium 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, aluminum hydroxy-2,2′-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, Aluminum hydroxy-2,2'-
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, aluminum dihydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate or aluminum dihydroxy-2 , 2'-butylidene-bis (4,6-di
(t-octylphenyl) phosphate, a lithium aluminum composite carbonate having the following composition as compound B, and other additives in a prescribed amount shown in Table 3 below in a Henschel mixer (trade name). After stirring and mixing for 3 minutes, the mixture was melt-kneaded at 200 ° C. with a twin-screw extruder having a diameter of 30 mm to form pellets. Comparative Examples 21 to 30
15% by weight of an unstabilized powdery crystalline propylene homopolymer having an MFR of 6.0 g / 10 min and an MFR of 7.0 g / min.
80 minutes by weight of an unstabilized powdery crystalline ethylene-propylene-butene-1 terpolymer (ethylene content 4.0% by weight, butene-1 content 4.5% by weight) and MI of 10 minutes
5.0 g / 10 min unstabilized powdered Ziegler-Natta high-density ethylene-propylene copolymer (density 0.950
g / cm ³ , 3.0 methyl branches / 1000 carbons) and 5% by weight, respectively, and a predetermined amount of each of the additives described in Table 3 described below was blended with 100 parts by weight, according to Examples 27 to 39. Pellets were obtained by melt kneading. The test piece used for the evaluation of the transparency, the obtained pellets resin temperature 250 ℃, mold temperature 50 ℃
Was prepared by injection molding. The transparency was evaluated by the test method using the obtained test piece. Table 3 shows the results.

The compounds and additives according to the present invention shown in Tables 1 to 3 are as follows. Compound A [1]: 2,2′-methylene-bis (4,6-di-t-butylphenyl) acid phosphate Compound A [2]: 2,2′-ethylidene-bis (4,6-di- t-Amylphenyl) acid phosphate Compound A [3]: 2,2′-butylidene-bis (4,6-dimethylphenyl) acid phosphate Compound A [4]: Calcium-2,2′-methylene-bis ( 4,6-di
-t-butylphenyl) phosphate Compound A [5]: magnesium-2,2'-methylene-bis (4,6-
Di-t-butylphenyl) phosphate Compound A [6]: Zinc-2,2'-methylene-bis (4,6-di-t-
Butylphenyl) phosphate Compound A [7]: Aluminum-2,2'-methylene-bis (4,6-
Di-t-butylphenyl) phosphate Compound A [8]: Calcium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate Compound A [9]: Calcium-2,2 '-Ethylidene-bis (4,6-
Di-t-butylphenyl) phosphate Compound A [10]: Aluminum hydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate Compound A [11]: Titanium dihydroxy -2,2'-methylene-
Bis (4,6-di-t-butylphenyl) phosphate compound A [12]: tindihydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate compound A [ 13]: zirconiumoxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate Compound A [14]: aluminum hydroxy-2,2'-methylene-bis (4-methyl -6-t-butylphenyl) phosphate Compound A [15]: Aluminum hydroxy-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate Compound A [16]: Aluminum dihydro Oxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate Compound A [17]: Aluminum dihydroxy-2,2'-ethylidene-bis (4,6-di-t -Butylphenyl) phosphate Compound A [18]: Aluminum dihydroxy-2,2'-propylidene-bis (4,6-di-t-amylphenyl) phosphate Feto Compound A [19]: aluminum dihydroxy-2,2'-butylidene - bis (4,6-di -t- octylphenyl) phosphate

Compound B [1]: (Li ₂ O) _0.13 Al ₂ O ₃ (CO
₃ ) _0.88 • 2.80 H ₂ O Compound B [2]: (Li ₂ O) _0.1 Al ₂ O ₃ (CO ₃ ) _0.6 A _0.17 •
2.82 H ₂ O (A: anion of succinic acid) Compound B [3]: (Li ₂ O) _0.1 Al ₂ O ₃ (CO ₃ ) _0.87 A _0.005
2.84 H ₂ O (A: anion of citric acid) Compound B [4]: (Li ₂ O) _0.09 Al ₂ O ₃ (CO ₃ ) _0.52 A _0.02
・ 3.02H ₂ O (A: anion of citric acid)

Phenolic antioxidant 1: tetrakis
[Methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane phenolic antioxidant 2: 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene phenolic antioxidant 3: Tris (3,5-di-t-butyl-4) -4
-Hydroxybenzyl) isocyanurate Phosphorus antioxidant 1: bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite Phosphorus antioxidant 2: Tetrakis (2,4- Di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite Phosphorus antioxidant 3: Tris (2,4-di-t-butylphenyl) phosphite Phosphorus antioxidant 4: Tris [2,2'-bis (4,6-di-t-butylphenyl)]-triethanolamine-triphosphite Phosphorus antioxidant 5: 2,2'-ethylidene-bis (4,6-di- t-
Butylphenyl) fluorophosphite HALS1: 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]] HALS2: 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 Clarifying agent 1: 1.3,2,4-dibenzylidenesorbitol Clarifying agent 2: 1,3,2,4 -Bis (4-methylbenzylidene) sorbitol clarifying agent 3: 1,3,2,4-bis (3,4-dimethylbenzylidene)
Sorbitol nucleating agent 1: sodium-2,2'-methylene-bis (4,6-di-t-
Butylphenyl) phosphate nucleating agent 2: aluminum-bis (4-t-butylphenyl) phosphate nucleating agent 3: aluminum hydroxy-bis (4-t-butylphenyl) phosphate hydrotalcite: basic magnesium・ Aluminum hydroxy carbonate hydrate (Mg _4.5
Al ₂ (OH) ₁₃ CO ₃ · 3.5 H ₂ O) [DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.]

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

The examples and comparative examples shown in Table 1 are cases where a crystalline propylene homopolymer is used as the crystalline polyolefin. As can be seen from Table 1, Examples 1 to 13
Is a blend of the compound A and the compound B according to the present invention. When comparing Examples 1 to 13 and Comparative Example 1 (without blending the compound A and the compound B), Example 1
It can be seen that the samples No. to No. 13 have remarkably excellent transparency. Also,
Comparing Comparative Examples 2 and 3 in which only Compound A was blended with Examples 1 to 13, the effect of improving the transparency of Comparative Examples 2 and 3 was recognized to some extent as apparent from Comparative Example 1. It is significantly inferior to Examples 1 to 13. Similarly,
Comparing Comparative Example 4 containing only Compound B with Examples 1 to 13, it is understood that Comparative Example 4 has almost no effect of improving transparency. Further, in Examples 1 to 13, Compound B
Examples 5 and 6 and Comparative Examples 5 and 6 in which the hydrotalcite was used instead of
Comparing with Comparative Examples 13 to 13, the effect of improving the transparency of Comparative Examples 5 to 6 is almost the same as that of Comparative Examples 2 and 3, and even when the hydrotalcite is used in combination with Compound A, the effect of improving the transparency is almost recognized. You can see that it cannot be done. Further, Comparative Examples 7 to 8 in which Compound A was replaced with a non-cyclic organic phosphate metal salt or a non-cyclic organic phosphate monobasic polyvalent metal salt, that is, nucleating agents 2-3 in Comparative Example 3 and Examples Compared with Examples 1 to 13, the effect of improving the transparency of Comparative Examples 7 and 8 is slightly superior to Comparative Example 3, but is significantly inferior to Examples 1 to 13. In comparison with Comparative Examples 9 to 10 in which Compound A was replaced with nucleating agents 2 and 3 in Examples 1 to 13 and Examples 1 to 13, the effect of improving the transparency of Comparative Examples 9 to 10 was the compound. Despite the combined use of B, the results are similar to those of Comparative Examples 7 and 8, and the compound B is a non-cyclic organic phosphate metal salt of the compound A or a non-cyclic organic phosphate monobasic polyvalent metal salt. It can be seen that even when nucleating agents 2 and 3 are used in combination, almost no effect of improving transparency is observed. Therefore, it is clear that each comparative example that does not simultaneously satisfy the combination of the two components of the compound A and the compound B according to the present invention does not exhibit the effects of the present invention. That is, it can be said that the transparency obtained in the present invention is a unique effect that can be seen only when compound A and compound B are blended with the crystalline polyolefin. Tables 2 and 3 are each a crystalline ethylene-propylene random copolymer as a crystalline polyolefin,
It is a mixture of crystalline propylene homopolymer, crystalline ethylene-propylene-butene-1 terpolymer and high-density ethylene-propylene copolymer, and the same effects as described above have been confirmed for these. Was.

[0035]

According to the crystalline polyolefin composition of the present invention, the transparency is greatly improved.

Claims (1)

[Claims] 1. A crystal comprising 100 parts by weight of a crystalline polyolefin and 0.01 to 1 part by weight of a phosphate compound represented by the following general formula (1) and a lithium aluminum complex carbonate represented by the following formula: Polyolefin composition. Embedded image _{(Li 2 O) x Al 2} O 3 (CO 3) y A z · kH 2 O ( wherein R is an alkylidene group having 1 to 4 carbon atoms, Ar ₁ and Ar ₂ are arylene or alkylarylene group And M represents a metal atom belonging to Group II to Group IV of the periodic table, and when M represents a metal atom belonging to Group II of the periodic table, m represents 2;
When n represents 0 and M represents a metal atom belonging to Group III of the periodic table, m represents 3, n represents 0, or m represents 2, n represents 1, or m. Represents 1, n represents 2, and X represents OH. When M represents a metal atom of Group IV of the periodic table, m represents 2, n represents 1, and X represents =
O or (OH) ₂ is shown, respectively. A represents an anion of a divalent or higher organic acid, x represents 0 <x <0.2, and y represents 0.0.
1 ≦ y <1, z is 0 ≦ z <1, k is 2 ≦ k <10,
y and z indicate 0.1 ≦ y + z <1, respectively. )