JPH07216142A - Crystalline polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain the subject compsn. which gives a molding excellent in transparency. CONSTITUTION:This compsn. comprises 100 pts.wt. crystalline polyolefin, 0.01-1 pt.wt. phosphate compd. of the formula [wherein R is a 1-4C alkylidene; Ar1 and Ar2 are each arylene or alkarylene; M is H or a metal of the group II, III, or IV; and X is OH, =O, or (OH)2], and 0.01-1 pt.wt. composite lithium- aluminum hydroxide salt represented by [Al2Li(OH)6]hA.kH2O (wherein A is an inorg. or org. anion; (h) is the valency of A; and (k) is 0 or a positive number of 3 or lower).

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 capable of obtaining a molded article having excellent transparency. More specifically, the present invention relates to a crystalline polyolefin composition capable of obtaining a molded article having excellent transparency, which is obtained by blending a crystalline polyolefin with a phosphate compound having a specific structure and a lithium aluminum complex hydroxide salt in specific amounts. .

[0002]

2. Description of the Related Art Generally, crystalline polyolefins are relatively inexpensive and have excellent mechanical properties.
It is used to manufacture various molded products such as hollow molded products, films, sheets and fibers. However, while the crystalline polyolefin has excellent mechanical properties, it has a drawback that its use is limited because its transparency is poor due to the high crystallinity of the crystalline polyolefin.
Therefore, for the purpose of improving the transparency of the crystalline polyolefin conventionally, various nucleating agents sodium benzoate, monobasic 4-t-butylbenzoic acid aluminum salt, carboxylic acid metal salts 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 phosphate, 1,3,
Polyhydric alcohol derivatives such as 2,4-dibenzylidene sorbitol and 1,3,2,4-bis (4-methylbenzylidene) sorbitol are used.

Among these compounds, JP-A-58-1736
The metal salts of cyclic phosphoric acid esters of alkylidene bisphenols described in JP-A No. 59-184252 and the like 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 of a cyclic phosphoric acid ester of these alkylidene bisphenols or a derivative thereof in combination with another metal compound. JP-A-63-69853 discloses that in order to prevent a decrease in rigidity when an aromatic metal phosphate-based nucleating agent and an alkaline earth metal carboxylate such as calcium stearate are used in combination, A method using a hydrotalcite or an alkali metal carboxylate in place of the metal carboxylate has been proposed, and in JP-A-1-129050 and JP-A-1-129051 relating to the application of the present applicant, cyclic A method has been proposed in which an organic phosphoric acid ester metal salt and an aliphatic carboxylic acid Group II metal salt of the periodic table are used in combination. Further, JP-A-3-79649 and JP-A-3-813
No. 68 proposes a method in which an acidic organic phosphate compound and an aliphatic carboxylic acid metal salt are used in combination, and the publication states that a neutralizing agent, a filler and the like can be added as additional components. Has been done. Furthermore, JP-A-3-4343
No. 7 discloses that a hydroxide of an alkali metal, an alkaline earth metal or an aluminum group metal is used in combination in order to prevent a decrease in PH upon immersion in hot water after irradiation when a cyclic diaryl phosphate metal salt is used. Is proposed.

However, the improvement effect of these combinations is not yet satisfactory in practical use,
In particular, further improvement has been required from the viewpoint of improving the transparency of crystalline polyolefin.

[0006] Further, the present inventor has disclosed that in order to improve the rigidity and heat resistance of the high-rigidity propylene polymer,
-101356, JP-A-1-104638, JP-A-1-
In 104639 and JP-A-1-104647,
It has been proposed to use a monobasic aluminum salt of an aromatic phosphoric acid diester, and comparative examples of these publications describe a composition using a monobasic aluminum salt of a cyclic aromatic phosphoric acid diester. However, when two types of monobasic aluminum salts such as these are used respectively, almost no transparency improving effect is observed, and such monobasic polyvalent metal salt compounds improve the transparency of crystalline polyolefin. It was thought that the effect was poor.

Therefore, in JP-A-5-140466 and JP-A-5-156078, a crystalline synthetic resin such as a crystalline polyolefin, an alkali metal organic carboxylate,
Alkali metal β-diketonate or alkali metal β-
By adding a ketoacetic acid ester salt and a cyclic organic phosphoric acid ester metal salt or a cyclic organic phosphoric acid ester basic polyvalent metal salt, the transparency of the resin was significantly improved and the mechanical strength was also increased. A crystalline synthetic resin composition has been proposed, and the publication describes that hydrotalcites can be added to the crystalline synthetic resin composition, if necessary.

On the other hand, JP-A-5-179052 discloses a composition in which an olefin resin is mixed with a lithium aluminum complex hydroxide salt as a stabilizer for a resin, a nonmetal stabilizer, an antioxidant, and Light stabilizer, nucleating agent, filler,
It is disclosed that an epoxy stabilizer and the like can be used in combination.

[0009]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention JP-A-63-69853
In the publication, the hydrotalcites used in combination with the aromatic metal phosphate-based nucleating agent are Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5.
A crystalline polyolefin composition, which is a compound represented by H ₂ O, wherein a lithium aluminum complex hydroxide salt called lithium hydrotalcite obtained by substituting magnesium for this compound with lithium is used as hydrotalcites. There is no description or suggestion of improving the transparency of the molded product obtained from. Further, JP-A-3-79649 and JP-A-3-81368 describe that a neutralizing agent or a filler can be used in combination as an additional component. However, as the neutralizing agent or the filler, Using a lithium aluminum complex hydroxide salt,
Alternatively, there is no description or suggestion of improving the transparency of a molded article obtained from the crystalline polyolefin composition by using a lithium aluminum complex hydroxide salt instead of the aliphatic carboxylic acid metal salt. Furthermore, in the above-mentioned JP-A-3-43437, by using a lithium aluminum complex hydroxide salt as a hydroxide of an alkali metal, alkaline earth or aluminum group metal used in combination with a cyclic diaryl phosphate metal salt,
There is no description or suggestion of improving the transparency of a molded product obtained from the crystalline polyolefin composition. And, the above-mentioned JP-A-5-140466 and JP-A-5-1560.
Although Japanese Patent Publication No. 78 describes that hydrotalcites can be used in combination as an additional component, it is preferable to use a lithium aluminum complex hydroxide salt called lithium hydrotalcite as hydrotalcites. ,
Or alkali metal organic carboxylate, alkali metal β
-There is no description or suggestion that the use of a lithium aluminum complex hydroxide salt instead of a diketonate or an alkali metal β-ketoacetic acid ester salt improves the transparency of a molded product obtained from a crystalline polyolefin composition. .

The lithium aluminum complex hydroxide salt as described in JP-A-5-179052 is a substance completely different from hydrotalcite. That is, in the lithium aluminum complex hydroxide salt, it is said that in the aluminum hydroxide having a gibbsite structure, lithium ions enter into the vacancy (vacant) of the octahedral layer, and an anion is incorporated to supplement the charge. That is, lithium ion has the smallest ionic radius among cations,
Moreover, since it is an exceptionally hexacoordinated ion as a monovalent ion, it is recognized that it enters the above vacancy and takes the above structure. This lithium-aluminum composite hydroxide salt has a layered structure and exhibits a structure and properties similar to hydrotalcite, such as exhibiting ion exchangeability with anions, and therefore, it is a hydrotalcite-like compound or lithium hydrotalcite. Although hydrotalcite is referred to as “hydrotalcite”, it is recognized that hydrotalcite is a brusite structure in which a part of magnesium is isomorphically substituted with aluminum, and thus both are completely different in chemical composition and structure.

Further, Japanese Patent Application Laid-Open No. 5-179052, which discloses a composition in which an olefin resin is mixed with a lithium aluminum complex hydroxide salt, discloses that the composition contains acidic organic phosphorus as a nucleating agent. By using an acid ester compound, a cyclic organic phosphoric acid ester metal salt or a cyclic organic phosphoric acid ester basic polyvalent metal salt in combination, there is no description that the transparency of a molded product obtained from the crystalline polyolefin composition is improved. There is no suggestion.

The present inventor is not satisfied with the crystalline synthetic resin compositions proposed in JP-A-5-140466 and JP-A-5-156078, and provides a molded product with further improved transparency. An intensive study was conducted to obtain a crystalline polyolefin composition. As a result, a crystalline polyolefin composition comprising a crystalline polyolefin having a specific structure and a lithium aluminum complex hydroxide salt having a specific structure in a specific amount is a composition giving a molded article with improved transparency. Based on this finding, the present invention has been completed. As is clear from the above description, an object of the present invention is to provide a crystalline polyolefin composition in which the transparency of a molded product is improved.

[0013]

The present invention has the following constitution. With respect to 100 parts by weight of the crystalline polyolefin, a phosphate compound represented by the following chemical formula 2 (hereinafter referred to as compound A) and a lithium aluminum complex hydroxide salt represented below (hereinafter referred to as compound B) are respectively used. A crystalline polyolefin composition obtained by blending 0.01 to 1 part by weight.

[Chemical 2] [Al ₂ Li (OH) ₆ ] _h A · kH ₂ O (wherein R represents an alkylidene group having 1 to 4 carbon atoms,
Ar ₁ and Ar _{2 each} represent an arylene group or an alkylarylene group, M represents hydrogen or a metal atom of Group II to Group IV of the periodic table, and when M represents hydrogen, m represents
Represents 1 and n represents 0, and when M represents a metal atom of Group II of the periodic table, m represents 2 and n represents 0, and M represents a metal of Group III of the periodic table. When an atom is shown, m is 3, n is 0, or m is 2.
, N is 1, X is —OH, and M is a metal atom of Group IV of the periodic table, m is 2 and n is 1
And X represents ═O or (OH) ₂ . A is an inorganic or organic anion, and h is an anion A.
, K is a positive number of 3 or less or 0, respectively. )

The crystalline polyolefin used in the present invention is
Crystalline homopolymers of α-olefins such as ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1 and octene-1, and crystallinity of two or more of these α-olefins Alternatively, a low crystalline random copolymer or a crystalline block copolymer, a copolymer of the above α-olefin and vinyl acetate or an acrylic ester, a saponified product of the copolymer, these α-olefin and an unsaturated silane. Copolymers with compounds, copolymers of these α-olefins with unsaturated carboxylic acids or their anhydrides, reaction products of the copolymers with metal ion compounds, crystalline homopolymers of the above α-olefins. Coalesced, crystalline or low-crystalline random copolymer or modified block copolymer modified with unsaturated carboxylic acid or its derivative, and the above-mentioned α-olefin Crystalline homopolymer,
It is possible to exemplify a silane-modified polyolefin or the like in which a crystalline or low-crystalline random copolymer or a crystalline block copolymer is modified with an unsaturated silane compound, and it goes without saying that these crystalline polyolefins are used alone.
It is also possible to use a mixture of two or more crystalline polyolefins.

Further, various synthetic rubbers (for example, amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene 3) are added to the above-mentioned crystalline polyolefin.
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, etc. or thermoplastic synthetic resin (for example, amorphous ethylene-cyclic alkene copolymer (for example, amorphous ethylene-tetracyclododecene copolymer) Polymer), polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate,
Polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyvinyl chloride, fluororesin, petroleum resin (for example, C ₅ petroleum resin, hydrogenated C ₅ petroleum resin, C ₉ petroleum resin, hydrogenated C)
₉ petroleum resin, C ₅ -C ₉ copolymer petroleum resin, hydrogenated C ₅ -C ₉ copolymer petroleum resin, and an acid-modified C ₉ petroleum resin), DCPD
Resin (for example, cyclopentadiene-based petroleum resin, hydrogenated cyclopentadiene-based petroleum resin, cyclopentadiene-C ₅
Copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymerized petroleum resin, cyclopentadiene-C ₉ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₉ copolymerized petroleum resin, cyclopentadiene-C ₅ -C ₉ copolymerized petroleum Resin, hydrogenated cyclopentadiene-C ₅ -C ₉ copolymer petroleum resin, etc.
CPD resin) and the like) may be mixed and used.

A crystalline propylene homopolymer, a crystalline propylene copolymer containing 70% by weight or more of a propylene component, which is a crystalline ethylene-propylene random copolymer, a crystalline propylene-butene-1 random copolymer. , 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 regardless 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-63-37
148, 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-63-260943 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-2-251548, It can also be suitably used for a crystalline propylene-based polymer as described in JP-A-2-279746 and JP-A-3-195751.

Further, as the crystalline polyolefin used in the present invention, a high activity catalyst composition containing a titanium halide catalyst component supported on magnesium halide and an organoaluminum catalyst component, particularly the electron donor catalyst component in the high activity catalyst composition. The use of a crystalline propylene-based polymer (preferably a deashing-free process) obtained by polymerization in the presence of a highly active and highly stereoregular catalyst composition further combining It is preferable because the property is further improved.

[0018] 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 (as the alkyl group, 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. In addition, among the hydrogen or the metal atoms of Group II to Group IV of the periodic table represented by M, as the metal atom, magnesium, calcium, strontium, barium, zinc, aluminum, gallium, germanium, tin, titanium, Examples thereof include zirconium and hafnium, and aluminum is particularly preferable.

Therefore, as the compound A, 2,2'-methylene-bis (4,6-di-t-butylphenyl) acid phosphate, 2,2'-methylene-bis (4-methyl-6-t) is used. -Butylphenyl) acid phosphate, 2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) acid phosphate, 2,2'-methylene-bis (4,6-dimethylphenyl) acid phosphate Fate, 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-propyi) -6-t-Butylphenyl) acid phosphate, 2,2'-butylidene-bis (4,6-dimethylphenyl) acid phosphate, 2,2'-butylidene-bis (4,6-di-t-butyl) Phenyl) 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-bis (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 dihydrooxy-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 and aluminum hydroxy-
Examples include 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, and especially 2,2'-methylene-bis (4,6-di-t-butylphenyl) acid phosphate. Fate, 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 is preferred.

Among the compounds A, in the general formula (1),
The compound A in which the atom represented by M is hydrogen is described in the above-mentioned JP-A-3.
It can be obtained by the production method described in JP-A-81368. That is, it can be easily produced by a method in which phosphorus oxychloride and 2,2′-alkylidene bisphenol are reacted and then hydrolyzed. In addition, the general formula
In (1), the atom represented by M is group II to group II of the periodic table.
Compound A, which is a group IV metal atom, is disclosed in the above-mentioned JP-A-5-140466.
It can be obtained by the manufacturing method described in JP-A No. 5-156078. That is, after reacting phosphorus oxychloride with 2,2′-alkylidene bisphenol and then reacting with an oxide or hydroxide of a polyvalent metal, or after forming an alkali metal salt, halogen of the polyvalent metal Or by reacting an alkali metal salt of an acidic cyclic organic phosphoric acid ester with a polyvalent metal halide or an oxidized polyvalent metal halide, and then hydrolyzing as necessary, an acidic cyclic organic compound. It can be easily produced by a method in which a phosphoric acid ester is reacted with a polyvalent metal alkoxide, and then hydrolysis is carried out if necessary. The particle size of the compound A is not particularly limited, and, for example, the average particle size is 0.
The particles having an average particle diameter of 10 μm or less, particularly 3 μm or less, are preferably crushed and used in order to achieve uniform dispersion. The compound A may be used alone or in combination of two or more kinds. The compounding ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the crystalline polyolefin. If the amount is less than 0.01 part by weight, the effect of improving transparency is not sufficiently exerted, and if it exceeds 1 part by weight, further improvement effect of transparency cannot be expected and it is not practical. It is uneconomical.

The compound B used in the present invention has a stoichiometrically almost constant composition as shown above. Examples of the inorganic or organic anion of the compound B include carbonic acid, sulfuric acid, chlorine oxyacid (for example, perchloric acid), phosphorus oxyacid (for example, phosphoric acid, phosphorous acid, metaphosphoric acid, phosphonic acid, phosphonic acid). , Phosphinic acid, phosphinic acid) or a combination of two or more of them is preferable, but acetic acid, propionic acid, adipic acid, benzoic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid,
Examples thereof include succinic acid, p-oxybenzoic acid, salicylic acid and picric acid. Carbonic acid is particularly preferable as the anion. The carbonate type compound B is described in the above-mentioned JP-A-5-1790.
It can be obtained by the production method described in JP-A-52.
That is, it can be obtained by reacting a water-soluble lithium salt or lithium hydroxide with a water-soluble aluminum salt in the presence of a water-soluble carbonate and an alkali. Examples of the water-soluble lithium salt include lithium chloride, lithium nitrate, lithium sulfate, lithium carbonate and the like. Examples of the water-soluble aluminum salt include aluminum chloride, aluminum nitrate, aluminum sulfate and the like. Further, sodium carbonate is generally used as the water-soluble carbonate, and sodium hydroxide is generally used as the alkali. Of course, when lithium hydroxide is used, the addition of sodium hydroxide may be omitted. Good. Each of these components is preferably used so that the atomic ratio of Al / Li is about 2 and the molar ratio of CO ₃ / Li is 0.5 or more. These compounds B may be used alone or in combination of two or more kinds. The compounding ratio of the compound B is 10
0.01 to 1 part by weight, preferably 0.05 to 0.5, relative to 0 part by weight
Parts by weight. If the amount is less than 0.01 part by weight, the effect of improving transparency is not sufficiently exerted, and if it exceeds 1 part by weight, further improvement effect of transparency cannot be expected and it is not practical. It is uneconomical.

In the composition of the present invention, various additives which are usually added to crystalline polyolefins such as antioxidants of phenol type, thioether type and phosphorus type, light stabilizers and 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) Benzylidene) sorbitol and other clarifying agents, sodium-bis (4-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, etc. Nucleating agents (excluding compound A), lubricants, antistatic agents, antifogging agents, antiblocking agents, non-dripping agents, radical generators such as organic peroxides, flame retardants, flame retardant aids, pigments, halogens. Scavenger (excluding compound B), metal soaps Dispersant or neutralizing agent, organic or inorganic antibacterial agent, inorganic filler (for example, 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.), the above-mentioned inorganic surface-treated with a surface treatment agent such as a coupling agent (eg, silane-based, titanate-based, boron-based, aluminate-based, zirco-aluminate-based) Fillers or organic fillers (for example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) can be used together within the range not impairing the object of the present invention.

The composition of the present invention comprises a crystalline polyolefin, a compound A and a compound B, and a predetermined amount of each of the various additives usually added to the crystalline polyolefin, in a conventional mixing device such as a Henschel mixer (trade name). ), A super mixer, a ribbon blender, a Banbury mixer, and the like, and a melt kneading temperature of 150 ° C. to 300 ° C., preferably 180 ° C., using an ordinary single-screw extruder, twin-screw extruder, Brabender or roll. It can be obtained by melt-kneading and pelletizing at 270 ° C. The obtained composition is used for producing a desired molded article by various molding methods such as an injection molding method, an extrusion molding method and a blow molding method.

Further, the composition of the present invention is used for various post-treatments, for example, for medical or food packaging applications where radiation is used for sterilization or for surface properties such as paintability and printability. In order to improve the above, it can be used for applications such as low temperature plasma treatment and corona discharge treatment after molding.

[0025]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. Transparency: length 50mm, width 25mm using the obtained pellets,
A test piece with a thickness of 1 mm is prepared by an injection molding method, and the haze is measured using the test piece (in accordance with ASTM D-1003-61).
It evaluated by doing. A highly transparent material has a small haze value.

Examples 1 to 9 and Comparative Examples 1 to 10 As crystalline polyolefin, MFR 6.0 g / 10 min 100 parts by weight of powdered crystalline propylene homopolymer which is not stabilized, and compound A is 2,2 '. -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 or titanium dihydrooxy
-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, basic aluminum lithium hydroxycarbonate hydrate or basic aluminum lithium hydroxysulfate as compound B A predetermined amount of each of the hydrate and other additives was put in a Henschel mixer (trade name) at a blending ratio shown in Table 1 below, and the mixture was stirred and mixed for 3 minutes, and then a caliber of 30
The mixture was melt-kneaded at 200 ° C. in a twin screw extruder of mm to pelletize. Further, as Comparative Examples 1 to 10, unstabilized powdery crystalline propylene homopolymer having an MFR of 6.0 g / 10 min.
Predetermined amounts of the additives shown in Table 1 below were added to 100 parts by weight, and melt-kneaded according to Examples 1 to 9 to obtain pellets. A test piece used for evaluation of transparency was prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. Using the obtained test piece, the transparency was evaluated by the above test method. These results are shown in Table 1.
It was shown to.

Examples 10-18, Comparative Examples 11-20 MFR 7.0 g / 10 min as crystalline polyolefin, an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 4.0% by weight) 100 In parts by weight,
As compound A, 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) acid phosphate, zinc-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate Fate, aluminum-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, tindihydroxy-2,
2'-methylene-bis (4,6-di-t-butylphenyl) phosphate or zirconiumoxy-2,2'-methylene-
Of bis (4,6-di-t-butylphenyl) phosphate, basic aluminum lithium hydroxycarbonate hydrate or basic aluminum lithium hydroxyhydroxysulfate hydrate as compound B and other additives Table 2 below for each predetermined amount
The mixture was placed in a Henschel mixer (trade name) at the blending ratio described in 3), stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. in a twin-screw extruder having a diameter of 30 mm to form pellets. Further, as Comparative Examples 11 to 20, 100 parts by weight of powdered crystalline ethylene-propylene random copolymer (ethylene content 4.0% by weight) in which the MFR was 7.0 g / 10 min was not stabilized, and Table 2 described below was used.
A predetermined amount of each of the additives described in Example 10-
Melt-kneading was performed according to 18, to obtain pellets. The test piece used for the evaluation of transparency was obtained by using the obtained pellets at the resin temperature.
It was prepared by injection molding at 250 ° C and a mold temperature of 50 ° C. Using the obtained test piece, the transparency was evaluated by the above test method. The results are shown in Table 2.

Examples 19 to 27, Comparative Examples 21 to 30 MFR 6.0 g / 10 min as crystalline polyolefin, unstabilized powdery crystalline propylene homopolymer 15% by weight, MFR 7.0 g / 10 min stable 80% by weight of powdery crystalline ethylene-propylene-butene-1 terpolymer (ethylene content 4.0% by weight, butene-1 content 4.5% by weight) and MI (load at 190 ° C 2.16 kg) Discharge of molten resin for 10 minutes when added) 5.0g / 10min unstabilized powdered Ziegler-Natta high density ethylene
-Propylene copolymer (density 0.950 g / cm ³ , methyl branch 3.
0 pieces / 1000 carbons) 5% by weight to a total of 100 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 or aluminum hydroxy-2,2'-ethylidene-bis (4,6- Di-t-butylphenyl)
Phosphate, basic aluminum as compound B
Lithium hydroxy carbonate hydrate or basic aluminum lithium lithium hydroxy sulphate hydrate and other additives were added to the Henschel mixer (trade name) at the prescribed amounts shown in Table 3 below. 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. Further, as Comparative Examples 21 to 30, the MFR is 6.0 g / 10
Unstabilized powdery crystalline propylene homopolymer 15% by weight, MFR 7.0 g / 10 min unstabilized powdery crystalline ethylene-propylene-butene-1 terpolymer (ethylene Content 4.0% by weight, butene-1 content 4.5
80% by weight and unstabilized powdered Ziegler-Natta high density ethylene with an MI of 5.0 g / 10 min-
Propylene copolymer (density 0.950 g / cm ³ , methyl branch 3.0
(/ 1000 carbons) 5% by weight, and 100 parts by weight in total of each of the additives described in Table 3 below are mixed in a predetermined amount, and melt-kneaded according to Examples 19 to 27 to obtain pellets. It was A test piece used for evaluation of transparency was prepared by injection molding the obtained pellets at a resin temperature of 250 ° C and a mold temperature of 50 ° C. Using the obtained test piece, the transparency was evaluated by the above test method. The results are shown in Table 3.

The compounds and additives relating 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 dihydrooxy-2,2'-methylene
-Bis (4,6-di-t-butylphenyl) phosphate Compound A [12]: tindihydrooxy-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 [14] 15]: Aluminum hydroxy-2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate Compound B [1]: Basic aluminum lithium hydroxycarbonate hydrate (Al ₄ Li ₂ (OH)
₁₂ CO ₃ · 1.6H ₂ O) Compound B [2]: Basic aluminum lithium lithium hydroxysulfate hydrate (Al ₄ Li ₂ (OH)
₁₂ SO ₄ / 1.2H ₂ O)

Phenol type antioxidant 1: tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane Phenol type 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-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 Clarifying agent 1: 1 ・3,2 ・ 4-Dibenzylidene sorbitol Clarifying agent 2: 1 ・ 3,2 ・ 4-bis (4-methylbenzylidene) sorbitol Clarifying agent 3: 1 ・ 3,2 ・ 4-bis (3,4-dimethyl) Benzylidene) 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 · 3.5H ₂ O) [manufactured by Kyowa Chemical Industry Co., Ltd.
DHT-4A]

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

The examples and comparative examples shown in Table 1 are the cases where a crystalline propylene homopolymer was used as the crystalline polyolefin. As can be seen from Table 1, Examples 1 to 1
No. 9 is a mixture of the compound A and the compound B according to the present invention, and comparing Examples 1 to 9 and Comparative Example 1 (no compound of the compound A and the compound B), Examples 1 to 9 are shown. Shows that the transparency is remarkably excellent.
In addition, Comparative Examples 2 and 3 and Example 1 in which only Compound A was blended
As compared with Comparative Example 1, the effect of improving transparency in Comparative Examples 2 to 3 is recognized to some extent as compared with Examples 1 to 9, but is significantly inferior to Examples 1 to 9. Similarly, Comparative Example 4 containing only Compound B and Examples 1 to 9
In comparison with Comparative Example 4, it can be seen that the transparency improving effect of Comparative Example 4 is almost negligible. Further, comparing Comparative Examples 5 to 6 in which Compound B was replaced with Hydrotalcite in Examples 1 to 9 and Examples 1 to 9, the effect of improving transparency in Comparative Examples 5 to 6 was found to be Comparative Example 2 to 6. It is about the same as 3 and it can be seen that even if the compound A is used in combination with hydrotalcite, almost no transparency improving effect is observed. Furthermore, in Comparative Example 3, Comparative Example 7 to 8 and Example 1 in which the compound A was replaced with the acyclic organic phosphoric acid ester metal salt or the acyclic organic phosphoric acid ester basic polyvalent metal salt, that is, the nucleating agent 2 to 3. ~ 9
In comparison with Comparative Examples 7 to 8, the effect of improving transparency is slightly superior to Comparative Example 3, but significantly inferior to Examples 1 to 9. And the comparative examples 9-10 and the examples 1-9 which replaced the compound A with the nucleating agent 2-3 in the examples 1-9.
In comparison with Comparative Examples 9 to 10, the effect of improving transparency in Comparative Examples 9 to 10 is similar to that of Comparative Examples 7 to 8 even though Compound B is used in combination. It can be seen that even if the nucleating agent 2 to 3 which is a metal salt or an acyclic organic phosphate ester basic polyvalent metal salt is used in combination, the effect of improving transparency is hardly recognized. Therefore, it is apparent that the comparative examples that do not simultaneously satisfy the combination of the two components of the compound A and the compound B according to the present invention do 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 the compound A and the compound B are blended with the crystalline polyolefin. Tables 2 and 3 show crystalline ethylene-propylene random copolymer, crystalline propylene homopolymer, crystalline ethylene-as crystalline polyolefin, respectively.
A mixture of a propylene-butene-1 terpolymer and a high-density ethylene-propylene copolymer,
The effects similar to those described above were also confirmed for these.

[0035]

EFFECT OF THE INVENTION The crystalline polyolefin composition of the present invention has a greatly improved transparency, and thus can be suitably used for the production of molded articles requiring transparency.

Claims (1)

[Claims] 1. Crystallinity obtained by blending 0.01 to 1 part by weight of a phosphate compound represented by the following chemical formula 1 and a lithium aluminum complex hydroxide salt shown below with 100 parts by weight of a crystalline polyolefin. Polyolefin composition. [Chemical 1] [Al ₂ Li (OH) ₆ ] _h A · kH ₂ O (wherein R represents an alkylidene group having 1 to 4 carbon atoms,
Ar ₁ and Ar _{2 each} represent an arylene group or an alkylarylene group, M represents hydrogen or a metal atom of Group II to Group IV of the periodic table, and when M represents hydrogen, m represents
Represents 1 and n represents 0, and when M represents a metal atom of Group II of the periodic table, m represents 2 and n represents 0, and M represents a metal of Group III of the periodic table. When an atom is shown, m is 3, n is 0, or m is 2.
, N is 1, X is —OH, and M is a metal atom of Group IV of the periodic table, m is 2 and n is 1
And X represents ═O or (OH) ₂ . A is an inorganic or organic anion, and h is an anion A.
, K is a positive number of 3 or less or 0, respectively. )