WO2002034827A1

WO2002034827A1 - Dibenzylidenesorbitol nucleating agent, polyolefin resin composition containing the same, and molded object

Info

Publication number: WO2002034827A1
Application number: PCT/JP2001/009366
Authority: WO
Inventors: Masahide Ishikawa; Chiaki Ueoka
Original assignee: New Japan Chemical Co., Ltd.
Priority date: 2000-10-26
Filing date: 2001-10-25
Publication date: 2002-05-02
Also published as: JPWO2002034827A1; AU2002210939A1

Abstract

A nucleating agent comprising 100 parts by weight of a dibenzylidenesorbitol compound and either 0.1 to 50 parts by weight of at least one amino acid and 0.1 to 100 parts by weight of at least one alkali metal salt of a fatty acid having 8 to 32 carbon atoms or 0.1 to 50 parts by weight of at least one alkali metal salt of an amino acid and 0.1 to 100 parts by weight of at least one fatty acid having 8 to 32 carbon atoms; a polyolefin resin composition comprising the nucleating agent and a polyolefin resin; and a molded object obtained by molding the resin composition.

Description

'' Nucleating agent, including it

TECHNICAL FIELD The present invention relates to a dibenzylidene sorbitol nucleating agent, which contains the dibenzylidene sorbitol nucleating agent, is excellent in transparency, and has an odor and taste transfer property during thermoforming and in a final molded product. The present invention relates to a polyolefin-based resin composition in which is significantly suppressed. Further, the present invention also relates to a molded article obtained by molding the polyolefin resin composition. mm

Polyols are compounds useful as nucleating agents for polyolefin-based resins, in particular, homopolymers of ethylene and propylene or copolymers containing these as main components. In particular, it has an excellent effect of improving transparency, and is widely used as a resin additive in the field of molded articles such as various containers requiring transparency.

However, dibenzylidene sorbitols partially decompose during thermoforming, liberating the benzaldehydes constituting the dibenzylidene sorbitol, and generating odor. For this reason, the aldehyde odor may remain in the final molded article, and the taste of the aldehyde may be transferred to foods that come into contact with the molded article, which is not preferred in the field of food containers and the like. There are cases.

Various proposals have been made to improve the above problems. For example, treatment with hydroxylamine or phenylhydrazines (Japanese Patent Application Laid-Open No. 60-32791, Japanese Patent Application Laid-Open No. 60-42585), addition of a non-aromatic organic amine (Japanese Patent Application No. 62-42889), surface treatment with an aliphatic metal salt and a metal lactate (Japanese Patent Application Laid-Open No. Sho 62-505355), blending of an aliphatic amine (Japanese Patent Application Laid-Open No. 2-199) No. 6841), addition of sorbic acid and Z or potassium sorbate (Japanese Patent Application Laid-Open No. 5-22055), A method such as addition of an alkali metal salt of a phosphoric acid (Japanese Patent Application Laid-Open No. 9-2866787) is known.

However, in the above-mentioned conventional technology, the addition of the above-mentioned additives may cause the polyolefin-based resin molded article to develop yellow coloring, and the odor improving effect is insufficient. There are drawbacks, such as limitations, and the current situation is that the above problems have not yet been resolved. DISCLOSURE OF THE INVENTION The present invention suppresses the development of the yellow coloration of the above-mentioned polyolefin-based resin molded article, and solves the above-mentioned problems based on the instability of dibenzylidene sorbitols. An object of the present invention is to provide a novel and useful polyolefin-based resin composition in which the generation amount of odorants is significantly suppressed, and the odor and taste transferability are suppressed.

In view of this situation, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, dibenzylidene sorbitols have at least one type of '(A) amino acid and fatty acid having 8 to 32 carbon atoms. At least one kind of alkali metal salt (hereinafter abbreviated as “additive (A)”), or (B) at least one kind of alkali metal salt of amino acid and at least one kind of fatty acid having 8 to 32 carbon atoms (hereinafter “ Additives (abbreviated as “B”)) significantly reduce the amount of aldehydes generated in pellets and molded products, and have the effect of suppressing the transfer of odor and taste. Came out.

Furthermore, according to the study of the present inventors, it was feared that the addition of the above-mentioned additive (A) or additive (B) would impair the function of dibenzylidene sorbitols as a clarifying agent. However, it was also found that even when the nucleating agent of the present invention was used, the transparency of the molded article was hardly impaired.

The present invention has been completed based on such findings and further studied. That is, the present invention provides the following dibenzylidene sorbitol nucleating agent, polyolefin resin composition and polyolefin resin molded article. Item 1 General formula (1)

[Wherein, R ¹ and R ² are the same or different and each represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen atom. m and n each represent an integer of 0-3. ]

Dibenzylidene sorbitol represented by the following, and per 100 parts by weight of the dibenzylidene sorbitol,

(A) at least one kind of amino acid 0.1 to 50 parts by weight and at least one kind of fatty acid metal salt of fatty acid having 8 to 32 carbon atoms 0.1 to 100 parts by weight, or

(B) at least one kind of an alkali metal salt of an amino acid 0.1 to 50 parts by weight and at least one kind of a fatty acid having 8 to 32 carbon atoms 0.1 to 100 parts by weight

A dibenzylidene sorbitol nucleating agent comprising: Item 2 Amino acid has the general formula (2)

R 3

H ゥ N— C— COOH (2)

R 4

[Wherein, R ³ and R ⁴ are the same or different and are each a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched chain having 2 to 6 carbon atoms, Alkenyl group, an alkyl group having 1 to 2 carbon atoms substituted with a phenyl group which may have one or two hydroxyl groups on a benzene ring, or one or two nitrogen atoms A 5- to 6-membered monocyclic heterocyclic group or a C1-C2 alkyl group substituted with a bicyclic heterocyclic group in which the monocyclic heterocyclic group and a benzene ring are condensed;

The linear or branched alkyl group having 1 to 6 carbon atoms represented by R ³ and R ⁴ is an alkylthio group having 1 to 2 carbon atoms, a hydroxyl group, 1 SH, an amino group, a carboxyl group, a carbamoyl group, It may be substituted with one or two substituents selected from the group consisting of a guanidino group and —S—SCH ₂ CH (NH ₂ ) 1 COOH.

Further, one of R ³ and R ⁴ and the amino group may be bonded to each other to form a pyrrolidine ring which may have a 7K acid group together with the carbon atom to which they are bonded. ]

2. The dibenzylidene sorbitol nucleating agent according to the above item 1, which is an α-amino acid represented by the formula: Item 3 The amino acid is glycine, alanine, phenylalanine, isoleucine, palin, leucine, proline, arginine, aspartic acid, cystine, glutamic acid, serine, histidine, tributofan, lysine, threonine, methionine, cystine, tyrosine, Item 1. The above item 1 which is at least one amino acid selected from the group consisting of asparagine, glutamine, norparin and α-aminobutyric acid.

Item 4 The amino acid is glycine, L-alanine, L-phenylalanine, L-^-soleucine, L-valine, L-mouth isin, L-proline, L-arginine, L-aspartic acid, L-cystine, L-glutamic acid , L-serine, L-histidine, L-tryptophan, L-lysine, L-threonine, L-methionine, DL-methionine, L-cystine, L-tyrosine, L-asparagine, L-Dalmin, L-norvaline and L 2. The dibenzylidene sorbitol nucleating agent according to the above item 1, which is at least one kind of amino acid selected from the group consisting of mono-α-aminobutyric acid. Item 5 Fatty acids having 8 to 32 carbon atoms are octanoic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, oleic acid, linole Acid, linolenic acid, eleostearin 2. The dibenzylidene sorbitol mononucleating agent according to the above item 1, which is at least one member selected from the group consisting of an acid, ricinoleic acid and erlic acid. Item 6 — dibenzylidene sorbitol represented by the general formula (1);

(A) 0.1 to 50 parts by weight of at least one kind of amino acid and at least one kind of 0.1 to 50 parts by weight of fatty acid metal salt of fatty acid having 8 to 32 carbon atoms per 100 parts by weight of sorbitol. Item 2. The dibenzylidene sorbitol nucleating agent according to the above item 1, comprising 100 parts by weight. Item 7. The dibenzylidene sorbitol nucleating agent according to Item 6, wherein the metal salt of the metal salt of a fatty acid having 8 to 32 carbon atoms is sodium or potassium. Item 8 The dibenzylidene sorbitol nucleating agent according to Item 6, wherein the fatty acid alkali metal salt having 8 to 32 carbon atoms is at least one member selected from the group consisting of sodium stearate and potassium stearate. Item 9 The dibenz according to any one of Items 1 to 8 further comprising an antioxidant.

-Nucleating agent. Item 10. The divedylidene sorbitol nucleating agent according to Item 9, wherein the antioxidant is a phenolic antioxidant. Term 1 1 (I) General formula (1)

[Wherein, R ¹ and R ² are the same or different and each represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen atom. m and n each represent an integer of 0-3. ] Per 100 parts by weight,

(B) at least one kind of alkali metal salt of amino acid 0.1 to 50 parts by weight and at least one kind of fatty acid having 8 to 32 carbon atoms 0.1 to 100 parts by weight

A dibenzylidene sorbitol nucleating agent comprising: and

(II) Polyolefin resin

A polyolefin-based resin composition comprising: Item 12. The polyolefin resin composition according to Item 11, which contains the dibenzylidene sorbitol nucleating agent in an amount of 0.05 to 3 parts by weight based on 100 parts by weight of the polyolefin resin. Term 13 amino acids are represented by the general formula

Wherein R ³ and R ⁴ are the same or different,

(a) a hydrogen atom,

(b) a linear or branched alkyl group having 1 to 6 carbon atoms,

(c) a linear or branched alkenyl group having 2 to 6 carbon atoms,

(d) an alkyl group having 1 to 2 carbon atoms substituted with a phenyl group which may have one or two hydroxyl groups on the benzene ring, or (e) a carbon substituted with a 5- to 6-membered monocyclic heterocyclic group containing one or two nitrogen atoms or a bicyclic heterocyclic group obtained by condensing the monocyclic heterocyclic group with a benzene ring; Alkyl group of number 1-2

Represents

The linear or branched alkyl group having 1 to 6 carbon atoms of (b) represented by R ³ and R ⁴ is an alkylthio group having 1 to 2 carbon atoms, a hydroxyl group, —SH, amino group, It may be substituted with one or two substituents selected from the group consisting of a ropoxyl group, a carpamoyl group, a guanidino group and one S_SCH ₂ CH (NH ₂ ) one COOH. Further, one of R ³ and R ⁴ and the amino group may be bonded to each other to form a pyrrolidine ring which may have a hydroxyl group together with the carbon atom to which they are bonded. ]

Item 11. The polyolefin resin composition according to Item 11, which is an α-amino acid represented by the formula: Item 14 The amino acid is glycine, alanine, phenylalanine, isoleucine, palin, leucine, proline, arginine, aspartic acid, cystine, glutamic acid, serine, histidine, tributphan, lysine, threonine, methionine, cystine, tyrosine. 11. The polyolefin-based resin composition according to the above item 11, which is at least one amino acid selected from the group consisting of asparagine, glutamine, norparin and α-aminobutyric acid. Item 15 The amino acid is glycine, L-alanine, L-phenylalanine, L-isoleucine, L-parin, L-leucine, L-proline, L-arginine, L-aspartic acid, L-cystine, L-glutamic acid L-serine, L-histidine, L-tryptophan, L-lysine, L-threonine, L-methionine, DL-methionine, L-cystine, L-tyrosine, L-asparagine, L-glyletamine, L-norvaline and L- Item 11. The polyolefin-based resin composition according to Item 11, which is at least one amino acid selected from the group consisting of hyaminobutyric acid. Item 16 Fatty acids with 8 to 32 carbon atoms are octanoic acid, chlorophyllic acid, lauric acid, At least one selected from the group consisting of myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid and eric acid Item 11. The polyolefin-based resin composition according to Item 11, wherein Item 17—Dibenzylidene sorbitol represented by the general formula (1) and 100 parts by weight of the dibenzylidene sorbitol, (A) 0.1 to 50 parts by weight of at least one kind of amino acid; Item 11. The polyolefin-based resin composition according to item 11, wherein the polyolefin-based resin composition contains 0.1 to 100 parts by weight of at least one metal salt of a fatty acid having 8 to 32 carbon atoms. Item 18. The polyolefin resin composition according to Item 17, wherein the alkali metal of the fatty acid metal salt of a fatty acid having 8 to 32 carbon atoms is sodium or potassium. Item 19 The polyolefin resin composition according to Item 17, wherein the fatty acid metal salt of fatty acid having 8 to 32 carbon atoms is at least one selected from the group consisting of sodium stearate and potassium stearate. . Item 20. The polyolefin resin composition according to Item 11, further comprising an antioxidant. Item 21. The polyolefm-based resin composition according to item 20, wherein the antioxidant is a phenolic antioxidant. Item 22. A polyolefin resin molded article obtainable by molding the polyolefin resin composition according to any one of Items 11 to 21 above. Term 2 3 — General formula

A method for suppressing the transfer of odor and taste from a polyolefin resin composition or a polyolefin resin molded product containing a dibenzylidene sorbitol and a polyolefin resin represented by the following general formula (1): The dibenzylidenesorbyl 1 ^

(A) at least one of amino acids 0.1 to 50 parts by weight and at least one of alkali metal salts of fatty acids having 8 to 32 carbon atoms 0.1 to 100 parts by weight, or

(B) A method comprising adding 0.1 to 50 parts by weight of at least one kind of an alkali metal salt of an amino acid and 0.1 to 100 parts by weight of at least one kind of a fatty acid having 8 to 32 carbon atoms. Term 24—general formula

[Wherein, R ¹ and R ² are the same or different and each represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a genogen atom. m and n each represent an integer of 0 to 3. ]

For suppressing the transfer of odor and taste from a polyolefin-based resin composition or a polyolefin-based resin molded product containing dibenzylidene sorbitols and a polyolefin-based resin represented by the formula:

(A) at least one kind of amino acids 0.1 to 50 parts by weight and at least one kind of alkali metal salts of fatty acids having 8 to 32 carbon atoms 0.1 to 100 parts by weight, or

(B) 0.1 to 50 parts by weight of at least one alkali metal salt of an amino acid and 0.1 to 100 parts by weight of at least one fatty acid having 8 to 32 carbon atoms. Detailed description of the invention

In the dibenzylidene sorbitols represented by the general formula (1) (hereinafter, referred to as “DBSs”), the alkyl group having 1 to 8 carbon atoms represented by R ¹ and R ² may be a straight chain or a branched chain. Such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-amyl, isoamyl, n-hexyl, n-heptyl, n-octyl Examples thereof include an alkyl group having 1 to 3 carbon atoms. Examples of the alkoxy group having 1 to 8 carbon atoms include straight-chain or branched ones such as methoxy, ethoxy, n-propoxy, n-butoxy, and isobutoxy. Particularly, an alkoxy group having 1 to 3 carbon atoms is preferable. Examples of the halogen atom include a chlorine atom and a bromine atom.

Specific examples of the DBSs of the above general formula (1) include 1,3: 2,4 dibenzylidene sorbitol, 1,3: 2,4 di (p-methylbenzylidene) sorbitol, and 1,3: 2 4-di (p-ethylbenzylidene) sorby] 1,3: 2,4 di (p-methoxybenzylidene) sorby] ^ 1, 1,3: 2,4-di (p-chlorobenzylidene) ) Sorbitol, 1,3: 2,4-bis (2,4-dimethyl) Benzylidene) Sorbitol, 1,3: 2,4-bis (3,4-dimethyl benzylidene) Compounds having the same or different substituted or unsubstituted benzylidene groups, such as sorbitol, can be exemplified.

Further, as DBSs that can be used in the present invention, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol! ^ 1; 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol; , 3-benzylidene 2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene 2,4,1-benzylidene sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene Rubitol, 1,3_p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-benzylidene 2,4- (2,4-dimethylbenzylidene) sorby] ^ 1,1,3 — (2,4-dimethylbenzylidene) 1,2,4-benzylidene sorpitol, 1,3-benzylidene—2,4-1 (3,4-dimethylbenzylidene) sorbitol, 1,3-1 (3,4-dimethyl) (Penzilidene) One, two, four—benzy Densorbitol, 1,3-p-methyl-benzylidene 2,4—p-ethylbenzylidene sorbyl! 1,3—p-ethyl-benzylidene sorbet 2,4—p—methyl benzylidene sorby! 1,3-ρ-methyl-benzylidene-2,4-p-chlorobenzylidenesorby] ^ yl, 1,3-p-chloro-benzylidene-2,4-p-methylbenzylidene sorbitol Compounds having a benzylidene group are exemplified.

In the present invention, the DBS represented by the general formula (1) is used alone or in an appropriate combination of two or more.

Among the DBSs represented by the general formula (1), the following compounds are particularly preferable: • a compound represented by the general formula '(1), wherein m and n are 0,

• General formula (1) in which R ¹ and R ² are an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc.), and m and n are 1 or 2 A compound represented by the formula:

The scope of the present invention also includes the benzylidene sorbitol compositions described in Japanese Patent No. 2111253 and Japanese Patent No. 2826152. Amino acids and metal salts thereof

The amino acid used in the present invention broadly refers to a compound having at least one propyloxyl group and at least one amino group in a molecule at the same time, and includes the amino acid (an amino group and an amino group) constituting a protein. Such compounds are generally known to be extremely safe, with the carboxyl group being bonded to the same carbon atom), and are applied singly or in an appropriate combination of two or more. When an asymmetric carbon is present in these amino acids, either the optical isomer alone or a mixture of two or more optical isomers (for example, a racemic mixture) can be used.

Among these amino acids, the following general formula (2)

Wherein R ³ and R ⁴ are the same or different,

(a) a hydrogen atom,

(b) a linear or branched alkyl group having 1 to 6 carbon atoms,

(c) a linear or branched alkenyl group having 2 to 6 carbon atoms,

(d) an alkyl group having 1 to 2 carbon atoms, which is substituted with a phenyl group which may have one or two hydroxyl groups on a benzene ring, or

(e) a carbon substituted with a 5- to 6-membered monocyclic heterocyclic group containing one or two nitrogen atoms or a bicyclic heterocyclic group obtained by condensing the monocyclic heterocyclic group with a benzene ring; Alkyl group of number 1-2

Represents

The linear or branched alkyl group having 1 to 6 carbon atoms of the above (b) represented by R ³ and R ⁴ is an alkylthio group having 1 to 2 carbon atoms, a hydroxyl group, one SH, an amino group, a carboxy group. It may be substituted with one or two substituents selected from the group consisting of a xyl group, a carbamoyl group, a guanidino group and —S—SCH ₂ CH (NH ₂ ) 1 C〇OH.

In addition, one of R ³ and R ⁴ and an amino group (ie, the carbon to which R ³ and R ⁴ are bonded) An amino group bonded to an atom) may be bonded to each other to form a pyrrolidine ring which may have a hydroxyl group together with the carbon atom to which they are bonded. Is recommended.

Examples of the above linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl, η_amyl, isoamyl, η-hexyl and the like. Among these, an alkyl group having 1 to 4 carbon atoms is particularly preferable.

Examples of the linear or branched alkenyl group having 2 to 6 carbon atoms include aryl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-methyl-3-butenyl and the like. An alkenyl group having 3 to 5 carbon atoms is preferred.

Examples of the alkyl group having 1 to 2 carbon atoms substituted with a phenyl group which may have 1 or 2 hydroxyl groups on a benzene ring include a benzyl group having 1 to 2 hydroxyl groups on a benzene ring. And particularly, 4-hydroxybenzyl group and 3,4-dihydroxybenzyl group).

Further, a 5- to 6-membered monocyclic heterocyclic group containing 1 to 2 nitrogen atoms or a carbon number of 1 to 1 substituted with a bicyclic heterocyclic group in which the monocyclic heterocyclic group and a benzene ring are condensed. As the 2 alkyl groups, those in which the alkyl group having 1 to 2 carbon atoms is a methyl group are preferable, and examples thereof include a 4-imidazolylmethyl group and a 3_indolylmethyl group. Examples of the pyrrolidine ring optionally having a hydroxyl group include a pyrrolidine ring optionally having one or two hydroxyl groups.

Among the above-mentioned amino acids, in particular, the above-mentioned general formula (2) wherein R ³ and R ⁴ are the same or different and are each a hydrogen atom, a straight-chain or branched-chain having 1 to 4 carbon atoms. alkyl group, a benzene ring on the base hydroxyl may a have one Njiru group, 4 - represents imidazolylmethyl group or a 3-indolylmethyl group, R ³ and R ⁴ carbon atoms is Ru indicated by 1-4 It represents a linear or branched alkyl group, a methylthio group, hydroxyl group, one SH, amino group, carboxyl group, a force Rubamoiru group, Guanijino group and one S - from SCH _₂ CH (NH ₂₎ one CO OH It may be substituted with one or two substituents selected from the group consisting of: Further, one of R ³ and R ⁴ and the amino group are bonded to each other to form a pyrrolidine which may have one hydroxyl group and a carbon atom to which they are bonded. May form a ring. ] Is more preferable.

Among the above amino acids, glycine, alanine, feniralanine, isoleucine, parin, leucine, proline, arginine, aspartic acid, cystine, glutamic acid, serine, histidine, tributofan, lysine, threonine, methionine, cystine, tyrosine, aspirin Preferably, at least one kind of α-amino acid selected from the group consisting of glutamine, norparin and α-aminobutyric acid is used.

In particular, among the above α-amino acids, (1) glycine, L-alanine, L-phenylalanine, L-isoleucine, L-valine, L-leucine, L-proline, L-arginine, L Aspartic acid, L-cystine, L-glucamic acid, L-serine, L-histidine, L-tributophan, L-lysine, L-threonine, L-methionine, DL-methionine, L-cystine, and L-mouth mouth synth And at least one selected from the group consisting of L-asparagine, L-glutamine, L-norparin, and L-0! -Aminobutyric acid is also preferable. .

'' In the alkali metal salt of an amino acid as described above used in the present invention, examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium, and among them, sodium and potassium are most preferred. No. These alkali metal salts of amino acids can also be used alone or in combination of two or more.

The amino acids and alkali metal salts thereof used in the present invention may be any of known or conventionally used synthetic methods, for example, Kirk-Othmer Encyclopedia of Chem. mical Technology) It can be easily manufactured according to the method described in the 4th edition, volume 2, pages 504 to 570, and the like. Fatty acids and their salts

As the fatty acid having 8 to 32 carbon atoms used in the present invention, either a saturated or unsaturated fatty acid can be used, and a saturated or unsaturated fatty acid having 8 to 22 carbon atoms is particularly preferable. Specifically, octanoic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, etc. which are saturated fatty acids, and oleic acid which is unsaturated fatty acid Examples thereof include acids, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, and erlic acid. These fatty acids are used alone or in an appropriate combination of two or more.

In the alkali metal salt of fatty acid having 8 to 32 carbon atoms used in the present invention, examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium, and among them, sodium and potassium are most preferable. The alkali metal salts of these fatty acids are also used alone or in an appropriate combination of two or more. Additive (A) and additive (B)

In the present invention, as described above, at least one kind of the above-mentioned amino acids and at least one kind of the above-mentioned alkali metal salts of fatty acids having 8 to 32 carbon atoms (additive (A)); Use at least one salt and at least one fatty acid having 8 to 32 carbon atoms (additive (B)). '

With respect to the amount of each component of the additive (A) according to the present invention, 0.1 to 50 parts by weight of at least one amino acid is used with respect to 100 parts by weight of the DBS represented by the general formula (1). Preferably, it is used in a ratio of 0.2 to 30 parts by weight, more preferably 0.3 to 10 parts by weight, and at least one of alkali metal salts of fatty acids having 8 to 32 carbon atoms is used. It is recommended to use preferably 0.2 to 80 parts by weight, more preferably 0.3 to 60 parts by weight.

Similarly, the amount of each component of the additive (B) according to the present invention is such that at least one alkali metal salt of an amino acid is added to 100 parts by weight of the DBS represented by the general formula (1). It is used in an amount of 1 to 50 parts by weight, preferably 0.2 to 30 parts by weight, more preferably 0.3 to 10 parts by weight, and at least one of fatty acids having 8 to 32 carbon atoms is used. It is recommended to use 1 to 100 parts by weight, preferably 0.2 to 80 parts by weight, more preferably 0.3 to 60 parts by weight.

Addition of additive (A) to 100 parts by weight of DBS represented by general formula (1) Or at least one of the metal salts of fatty acids having 8 to 32 carbon atoms, or at least one of the alkali metal salts of amino acids of additive (B) and 8 to carbon atoms. If the amount of at least one of the 32 fatty acids is less than 0.1 part by weight, it is difficult to obtain the desired effect.

On the other hand, based on 100 parts by weight of the DBS represented by the general formula (1), at least one kind of the amino acid of the additive (A) or at least one alkali metal salt of the amino acid of the additive (B) is used. When the amount of the seed exceeds 50 parts by weight, or the amount of at least one of the fatty acid alkali metal salt of the additive (A) or the at least one of the fatty acid of the additive (B) is 100% by weight. If the amount exceeds the limit, it has the effect of suppressing the transfer of taste and odor, but when added to the resin, it tends to cause problems such as bleeding from the molded product and reducing the transparency of the molded product . Antioxidant

Further, by adding an antioxidant to the nucleating agent of the present invention comprising the DBSs and the additive (A) or the additive (B), the storage stability of the nucleating agent of the present invention, especially The storage stability when stored under high temperature conditions is significantly improved. That is, the dibenzylidene sorbitol nucleating agent of the present invention having further improved storage stability is 100 parts by weight of the nucleating agent comprising the additive (A) or the additive (B) of the present invention and DBS. To 0.1 to 5 parts by weight of an antioxidant.

Examples of such an antioxidant include various stabilizers described in “Polylist Additives Handbook” (January 1995) edited by the Polyolefin Hygiene Council, and more specifically. Examples thereof include a phenolic compound, a phosphite compound and a zeolite compound, which are applied alone or in combination of two or more.

Among the antioxidants, phenol-based antioxidants, which are particularly effective as primary antioxidants against heat, 2,6-di-t-butyl-4-methyl phenol, n-octyl decyl 3- (3,, 5 , Tert-butyl-4, -hydroxyphenyl) -pionate, tetrakis [methylene-13- (3,5-di-t-butyl--4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-) Butyl I-4-Hydroxybenzyl) isocyanurate, 4,4, butylidene-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) provione 1-] and 3,9-bis {2— [3- (3-t-butyl-4-hydroxy-1-5-methylphenyl) propionyloxy] —1,1,1-dimethylethyl} -2,4,8,10-tetra Oxaspiro [5,5] undecane and the like are exemplified, and among them, tetrax [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is recommended.

The preferred amount of the acid inhibitor according to the present invention is 0.01 to 4 parts by weight, particularly 100 parts by weight of the nucleating agent comprising the additive (A) or the additive (B) and the DBS. , 0.01 to 3 parts by weight. Dibenzylidene sorpitol nucleating agent of the present invention

The dibenzylidene sorbitol nucleating agent of the present invention is obtained by adding the above-mentioned additive (A) or additive (B) and, if necessary, the above-mentioned antioxidant to the DBS represented by the general formula (1). It is manufactured by doing. .

The method of adding the additive (A), the additive (B), or the antioxidant according to the present invention is not particularly limited, but (a) various methods conventionally used (for example, A method described in JP-A-2-231488), wherein sorbitol and the corresponding benzaldehyde are added in the process of producing the DBS represented by the general formula (1), and (b) the general formula A method of mixing powders with the DBS represented by (1) using a mixer such as a Henschel mixer, a V-Blender, a Ripon blender, or the like; (c) Alcohols having about 1 to 3 carbon atoms such as methanol and ethanol; In a slurry of DBS represented by the general formula (1) using water or the like as a dispersion medium, the above additive (A) or (B) and, if necessary, an antioxidant as they are or as a solvent. Alcohols such as ethanol, ethanol, etc. In the form of a solution in medium, added and mixed the predetermined amount, and thereafter method in which the solvent is distilled off.

Regarding the method (a) above, the addition of the above-mentioned compound after the point at which the DBS represented by the general formula (1) is formed by the diacetylation reaction of sorbitol and benzaldehydes. It is preferable to add the agent (A) or (B) and, if necessary, the antioxidant in the above-mentioned predetermined amounts.

In the method (c), the concentration of the DBS slurry is not particularly limited, but is generally preferably about 10 to 60% by weight. In addition, the temperature of the slurry can be selected from a wide range, but generally, it is preferably 20 to 100 ° C.

The nucleating agent of the present invention comprising the additive (A) or the additive (B) thus obtained, and the DBS containing an antioxidant as required, can be used to remove aldehydes due to heat history when used as a resin additive. It is a new and useful material with extremely low generation and performance degradation. When the nucleating agent of the present invention contains an antioxidant, the storage stability is remarkably improved. Polyolefin resin composition

The polyolefin-based resin composition of the present invention is obtained by blending the stabilized DBS of the present invention with a polyolefin-based resin according to a conventional method.

The amount of the dibenzylidene sorbitol nucleating agent of the present invention relative to the polyolefin resin is not particularly limited as long as a predetermined effect can be obtained, and can be appropriately selected from a wide range. About 0.05 to 3 parts by weight, preferably about 0.07 to 1 part by weight, per 0.0 parts by weight. The effect of the present invention can be sufficiently obtained by blending within these ranges.

As a method for adding the DBS to the polyolefin-based resin, a direct addition method using a commonly used apparatus, for example, a single-screw or twin-screw extruder is preferable, but not limited thereto. Further, for example, an addition method in the form of a single batch of a high concentration master of about 2 to 15% by weight may be employed.

Examples of the polyolefin resin according to the present invention include a polyethylene resin, a polypropylene resin, and a polybutene resin. More specifically, high-density polyethylene, medium-density polyethylene, linear polyethylene, and an ethylene content of 50 wt. % Or more (especially 70% by weight or more) ethylene copolymer, propylene homopolymer, propylene 50% or more (especially 70% by weight or more) propylene copolymer, butene homopolymer, butene content 50% by weight or more ( Especially 70% by weight or more) Examples thereof include limers, methylpentene homopolymers, methylpentene copolymers having a methylpentene content of 50% by weight or more (especially 70% by weight or more), polybutadiene, and the like.

The copolymer may be a random copolymer or a block copolymer. When these resins have stereoregularity, they may be isotactic or syndiotactic.

Examples of the comonomer that can constitute the copolymer include α-olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, pendecene, and dodecene; and 1,4-endmethylenecyclo. Examples thereof include hexyl-type monomers such as hexene, (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, and vinyl acetate.

Examples of the catalyst used for producing such a polymer include transition metal compounds (eg, titanium halides such as titanium trichloride and titanium tetrachloride) as well as commonly used Ziegler-Natta type catalysts. A catalyst composed of a catalyst supported on a carrier mainly composed of magnesium halide such as magnesium chloride and an alkylaluminum compound (triethylaluminum, getylaluminum chloride, etc.), a catalyst system comprising Catalysts can also be used.

The recommended melt edge rate (hereinafter, abbreviated as “MFR”. JISK 7210—19776) of the polyolefin resin according to the present invention is appropriately selected depending on the molding method to be applied. Usually, 0.01 to 200 gZ10 minutes, preferably 0.05 to: L00 gZ10 minutes.

To the polyolefin-based resin composition according to the present invention, conventionally known modifiers for polyolefins can be appropriately added according to the purpose of use and the use within a range that does not impair the effects of the present invention.

Examples of such polyolefin modifiers include various additives described in “Polylist Additives Handbook” (January 1995) edited by the Polyolefin Hygiene Council. Include stabilizers (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), antioxidants (phenol compounds, zinc oxide Acid ester compounds, zeolite compounds, surfactants, lubricants (aliphatic hydrocarbons such as paraffin, box, etc.) and higher fatty acid metals having 8 to 22 carbon atoms (Al, Ca, Mg, Zn) ) Salts, higher aliphatic alcohols with 8 to 22 carbon atoms, polydalicol, esters of higher fatty acids with 4 to 22 carbon atoms and aliphatic monohydric alcohols with 4 to 18 carbon atoms, 8 to 22 carbon atoms Higher fatty acid amides, silicone oils, rosin derivatives, etc.), fillers (talc, hydrated talcite, mai power, zeolite, perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agents, blowing aids, polymer additives Other plasticizers (dialkyl phthalate, dialkylhexahydrophthalate, etc.), crosslinking agents, crosslinking accelerators, antistatic agents, flame retardants, dispersants, organic and inorganic pigments, processing aids, other nucleating agents, etc. Of various additives are exemplified.

The polyolefin-based resin composition according to the present invention thus obtained is a novel and useful resin composition which suppresses the generation of aldehydes during thermoforming and the odor and taste transferability of aldehydes in the final molded product and has excellent properties such as transparency. Polyolefin resin composition. Polyolefin resin molded body

The polyolefin-based resin molded article of the present invention is obtained by molding the polyolefin-based resin composition of the present invention according to a commonly used molding method. In molding the resin composition according to the present invention, any of conventionally known molding methods such as injection molding, extrusion molding, blow molding, pressure molding, rotation molding, and film molding can be employed. As the molding conditions, conventionally employed conditions can be appropriately selected from a wide range. The polyolefin-based resin composition according to the present invention is applied in the same field as a polyolefin-based resin composition obtained by combining DBSs as a nucleating agent, and is used as a molded article.

More specifically, medical instruments such as disposable syringes, blood transfusion sets, blood collection instruments, etc., which are sterilized by heat, radiation, etc .; foods, plants, etc., sterilized by radiation, etc .; clothing cases Cases such as containers for storing food and clothing; cups for hot-filling food; packaging containers for retort food; containers for microwave ovens; cans for drinks such as juice and tea, cosmetics, pharmaceuticals, and shampoos Containers and caps for seasonings such as miso and soy sauce; Cases for food such as water, rice, bread, pickles, etc. Suitable as materials for containers; miscellaneous goods such as refrigerator cases; stationery; electric and mechanical parts;

Compared with a molded article molded from a conventional resin composition containing DBS, the polyolefin-based resin molded article of the present invention suppresses the generation of aldehydes at the time of thermoforming. Odor is sometimes low.

In the molded article of the present invention, since the amount of aldehydes is significantly reduced, the odor and taste transferability due to the aldehydes are reduced. Moreover, the polyolefin resin molded article of the present invention is excellent in transparency.

Therefore, the polyolefin resin molded article of the present invention can be advantageously used in the fields of food packaging materials, food containers, cosmetic containers and the like. Examples _ Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

Example A .: Production of dibenzylidene sorbitol nucleating agent of the present invention

While stirring and dispersing 1,3: 2,4-di (p-methylbenzylidene) sorbitol (hereinafter abbreviated as “Me-DBS”) in methanol (6 times the weight of Me-DBS), Example 1 The amino acid and fatty acid metal salts described in Examples 1 to 9 are mixed with deionized water (4 times the weight of Me-DBS) in the amount described in Examples 1 to 9 in Table 1. Was added.

The resulting dispersion was heated and stirred for 1 hour under reflux conditions to obtain a white paste-like mixture. Next, methanol and deionized water were removed under reduced pressure, and the sample was dried for 2 hours under a condition of a pressure of 1333 Pa and a temperature of 80 ° C using a vacuum drier as a drying device to obtain a powdery sample.

Examples 1 to 9

An isotactic random polypropylene resin having an ethylene content of 3.0% by weight (MFR = 20 gZl 0 minutes, hereinafter abbreviated as “r-PP”). 0.2 parts by weight of nucleating agent consisting of alkali metal salt of amino acid and fatty acid and Me-DBS, tetrakis [methylene-3- (3,5-di — T-butyl-1-hydroxyphenyl) propionate] methane (trade name “Ilganox 1010”, manufactured by Ciba 'Specialty-I' Chemicals) 0.05 parts by weight 0.05 parts by weight of calcium stearate After mixing with a Henschel mixer, the mixture was melt-kneaded with a single screw extruder having a resin temperature of 240 ° C and a diameter of 25 mm to form pellets.

The resulting pellets were evaluated for odor by the following dry method. Table 1 shows the obtained results.

After sealing 60 g of the pellet in a 225 ml glass bottle, it was left in a constant temperature bath at 80 ° C for 2 hours, and the odor intensity was judged by 10 panelists. The evaluation criteria for panelists were: 0 points = no smell, 1 point = slight smell, 2 points clear smell, 3 points = strong smell, and the evaluation was made based on a total of 10 points.

Next, the pellets obtained above were injection molded under the conditions of a resin temperature of 240 ° C and a mold temperature of 40 ° C to prepare test pieces. Using the obtained injection molded product, the crystallization temperature (Tc) and the haze value were measured by the following methods. Table 1 shows the obtained results.

The measurement was carried out using a differential scanning calorimeter (trade name “DSC7”, manufactured by Perkin-Elmer Co., Ltd.) according to JIS K7121. The higher the Tc, the faster the crystallization speed and the shorter the molding cycle.

Using a haze meter manufactured by Toyo Seiki Seisaku-sho, the measurement was performed according to JIS K6714 and JIS K6717. The smaller the value obtained, the better the transparency. Next, the obtained injection molded product was evaluated for odor by the following dry method and wet method. Table 1 shows the obtained results.

Odor Evaluation of Injection Molded Products by the Dry Dry Method>

After sealing 20 g of the test piece in a 225 ml glass bottle, the test piece was left in a constant temperature bath of 80 for 2 hours, and the intensity of odor was judged by 10 panelists. The criteria for panelists are: 0 points = no smell, 1 point = slightly smell, 2 points G = Smell clearly, 3 points = Smell violently.

After sealing 20 g of the test piece and 140 g of deionized water in a 225 ml glass bottle, it was allowed to stand in a constant temperature bath at 80 ° C for 2 hours. After cooling, the odor intensity was judged by 10 panelists. The evaluation criteria for panelists were: 0 points: No smell, 1 point: Slightly smell, 2 points: Clearly deep, 3 points: Strong smell.

Comparative Example 1

Evaluation was performed in the same manner as in Example 1 except that the amino acid and the fatty acid alkali metal salt were not added. Table 1 shows the obtained results.

Example 10

Evaluation was performed in the same manner as in Example 5 except that 1,3: 2,4-dibenzylidenesorby! ^ 1 (hereinafter abbreviated as “DBS”) was used as DBSs. Table 1 shows the obtained results.

Comparative Example 2

The evaluation was performed in the same manner as in Example 10 except that no amino acid and a fatty acid alkali metal salt were added. Table 1 shows the obtained results.

Example 11

Evaluation was performed in the same manner as in Example 1 except that 1,3: 2,4-di (p-ethylbenzylidene) sorbitol (hereinafter abbreviated as “Et-DBS”) was used as DBSs. Was. Table 1 shows the obtained results.

Comparative Example 3

Evaluation was carried out in the same manner as in Example 11 except that no amino acid or fatty acid alkali metal salt was added. Table 1 shows the obtained results.

Example 12

Example 7 was repeated except that 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol (hereinafter abbreviated as “3,4-1 DMBS”) was used as DBSs. Evaluation was performed in the same manner. Table 1 shows the obtained results. Comparative Example 4

Evaluation was performed in the same manner as in Example 12, except that no metal salt of an amino acid or a fatty acid was added. Table 1 shows the obtained results.

Comparative Example 5

Evaluation was performed in the same manner as in Example 1 except that DBSs, amino acids and fatty acid alkali metal salts were not blended. Table 1 shows the obtained results.

Example 13

The evaluation was performed in the same manner as in Example 1 except that an isokinetic homopolypropylene resin (MFR = 30 g / 10 min, hereinafter abbreviated as “h-PP”) was used as the resin. Table 1 shows the obtained results.

Comparative Example 6

Evaluation was performed in the same manner as in Example 13 except that the amino acid and the alkali metal salt of the fatty acid were not added. Table 1 shows the obtained results.

Comparative Example 7

Evaluation was performed in the same manner as in Example 13 except that DBSs, amino acids, and fatty acid metal salts were not added. Table 1 shows the obtained results.

Example 14

A dibenzylidene sorbitol nucleating agent of the present invention was prepared in the same manner as in Example A, except that the amino acid, fatty acid metal salt of fatty acid and Me-DBS shown in Table 1 were used in the proportions shown in Table 1, respectively.

0.2 parts by weight of the obtained dibenzylidene sorbitol nucleating agent of the present invention is abbreviated as “LLDPE” in a linear low-density polyethylene resin (density = 0.926 Q / c MFR = 20 g / 10 min, hereinafter). ) 100 parts by weight, mixed with a Henschel mixer, melt-kneaded with a single screw extruder with a diameter of 25 mm set at 200 ° C, and pelletized. The odor of the obtained pellets was evaluated by the following dry method. Table 1 shows the obtained results.

Odor evaluation of pellets by dry method>

After sealing 60 g of the pellet in a 225 ml glass bottle, it was left in a constant temperature bath at 40 ° C for 2 hours, and the odor intensity was judged by a panel of 10 persons. For panelists The evaluation criteria were as follows: 0 points = no smell, 1 point = slight smell, 2 points = clear smell, 3 points = strong smell, and evaluation was made based on a total of 10 points.

Next, the obtained pellets were injection molded under the conditions of a resin temperature of 200 ° C and a mold temperature of 30 ° C to prepare test pieces. Using the obtained injection molded product, the crystallization temperature (Tc) and the haze value were measured by the methods employed in Examples 1 to 9. Table 1 shows the obtained results.

Next, the odor evaluation of the obtained injection molded article was evaluated by the following dry method. Table 1 shows the obtained results. ·

After 20 g of the test piece was sealed in a 225 ml glass bottle, it was left in a constant temperature bath at 40 ° C for 2 hours, and the odor intensity was judged by 10 panelists. The judgment criteria for panelists were: 0 points = no smell, 1 point = slightly smell, 2 points = clear smell, 3 points = strong smell, and the evaluation was made based on the total value of 10 points.

Comparative Example 8

The evaluation was performed in the same manner as in Example 14 except that the amino acid and the fatty acid metal salt were not added. Table 1 shows the obtained results.

Comparative Example 9

Evaluation was performed in the same manner as in Example 14 except that DBSs, amino acids and fatty acid alkali metal salts were not blended. Table 1 shows the obtained results.

Example 15

Evaluation was performed in the same manner as in Example 14 except that a high-density polyethylene resin (density = 0.967 g / cm MFR = 67 g / 10 min, hereinafter abbreviated as “HDPE”) was used as the resin. . Table 1 shows the obtained results.

Comparative Example 10

Evaluation was performed in the same manner as in Example 15 except that the amino acid and the alkali metal salt of the fatty acid were not added. Table 1 shows the obtained results.

Comparative Example 1 1 Evaluation was performed in the same manner as in Example 15 except that DBSs, amino acids and fatty acid alkali metal salts were not blended. Table 1 shows the obtained results.

table 1

Extractor 5l Evaluation Resin Π R ^ $ 1 Anostearic acid

Injection J Reno Crystallization Head Injection Molded product Addition amount

\ l \ J u (parts by weight) Addition amount mm. CO Dry wet Risato cu (Heavy halo) Ri a

1 _r _ pp

Γ r IVI c UD L M / N 6.4 2 1.8 1 28 1 2 5 4 4 o

M ™ Γ r Me-D DOL-Knoreta: ^ noic acid 6.8 14.3 3 15.0 1 27 1 3 6 5 6

Β Γ Γ M β-D D L-Cryretanoic acid 5.9 1 2.4 1 28 1 1 7 6 6

4 r-Γ Γ Ivl e-D B S L-Cryretanoic acid 6.8 28.4 4 1 2 7 1 3 6 5 5 c J

o r-r r M e -L b -f \

Klinno 6.7 2 7.5 1 27 1 2 5 3 3

D Γ r— D r P r M β U D Kurinno 2. 2.8.9 1 28 1 0 7 7 7

7

Γ ~ Dr Dr M 6 U D o L HIANNO 5.9 1 1-8 1 2 7 1 1 5 2 3 o

o r Γ— D r D r M 6 U D O L-Sanno 0.5 0.5 1. 0 1 28 1 0 7 6 6

Q

Γ r Γ m c L D 1— k

L 1 "

Noton 5. 7. 8. 6 1 28 I ID 3 4

1 0 _r _ pp π ς 11>

Nono 6. 7 2 7. 5 1 1 8 4> <

3 4 r-p `` p 1 1 7 7 6.4 2 1.8 1 26 I c

D 4 4

1 Eighth z No 5.9 1 1.8 1 2 7 1

I z 4 3 3

1 3 — P P, \ -a-6.4 2 1-8 1 3 3 1 D 5 6

1 4 * + 1 L 1 Π P F 1

/ No 6.4 2 1.8 1 1 2 c 5

1 1 c i n P P M Π R 1

Ivl β l D L MA, NO, 6.4 2 1.8 1 1 7 4 3 Tote protection 11 Γ r r Ivl 6 U 1 28 1 0 1 6 1 7

2 _r -pp DBS 1 1 9 1

1 tJ; 1 4 1 4

3 r-P P E t-D B S 1 2 7 1 7 1 6 1 6 1 6

4 r-P P 3,4-DM B S 1 28 1 1 1 1 5 1 4 1 4

5 r-P P 1 05 70 4 2 2

6 h-P P M e-D B S 1 3 3 20 1 9 1 7 1 9

7 h-P P 1 1 4 75 3 3 2

8 L L D P E e-D B S 1 1 2 29 1 8 1 6

9 L L D P E 1 04 54 4 3

1 0 H D P E M e-D B S 1 1 9 1 6 1 5

1 1 HDPE 1 1 2 2 2

Examples 16 to 24

(MFR = 20 gZl 0 min, “r_PP”) The same procedure as in Example A was conducted except that predetermined amounts of Me-DBS, amino acids and sodium stearate shown in Table 2 were used for 100 parts by weight. An inventive nucleating agent was obtained.

The obtained nucleating agent of the present invention was added in parts by weight shown in Table 2 (the amount of Me-DBS was 0.2 parts by weight based on 100 parts by weight of r-PP resin), and tetrakis [ Methylene-1- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name “Ilganox 1010”, Ciba's Specialty Chemicals Co., Ltd.) 0.05 parts by weight and calcium stearate 0.05 parts by weight were blended and mixed with a Henschel mixer until uniform, then melt-kneaded with a single-screw extruder having a diameter of 25 mm set at 240 ° C and pelletized.

Next, the obtained pellets were injection molded under the conditions of a resin temperature of 240 ° C and a mold temperature of 40 to prepare test pieces.

After sealing 20 g of the obtained test piece and 140 g of deionized water in a 225 ml glass bottle, leave it in a constant temperature bath at 80 ° C for 2 hours, and use the cooled aqueous solution as a sample for evaluation. The aldehyde generation was measured and the taste was evaluated. Table 2 shows the results.

The aldehyde content of the evaluation sample was quantified using high performance liquid chromatography. The amount of aldehyde is expressed in g / PPg, that is, the number of microdams per gram of the test piece.

10 ml of the evaluation sample was placed in a glass cup, and taste evaluation was performed by 10 panelists. Judgment criteria are: 0 points = No difference, 1 point = Slightly different, 2 points = Clearly different, compared to the taste of the taste sample prepared by the following method. It was expressed by.

Example 16 except that DBSs, amino acids and alkali metal salts of fatty acids were not added. By the same operation as described above, the obtained aqueous solution was used as a comparative sample for taste evaluation. · Comparative Example 12

Evaluation was performed in the same manner as in Example 16 except that the amino acid and the alkali metal salt of the fatty acid were not added. Table 2 shows the obtained results.

Comparative Example 13

Evaluation was performed in the same manner as in Example 21 except that no amino acid was added. Table 2 shows the obtained results.

Example 25

Evaluation was performed in the same manner as in Example 19 except that DBS was used as DBS. Table 2 shows the obtained results.

Comparative Example 14

Evaluation was performed in the same manner as in Example 25, except that no amino acid or fatty acid alkali metal salt was added. Table 2 shows the obtained results.

Example 26

Evaluation was performed in the same manner as in Example 16 except that Et-DBS was used as DBS. Table 2 shows the obtained results.

Comparative Example 15

Evaluation was performed in the same manner as in Example 26, except that no amino acid or a fatty acid alkali metal salt was added. Table 2 shows the obtained results.

Example 27

Evaluation was performed in the same manner as in Example 18 except that 3,4-DMBS was used as DBSs. Table 2 shows the obtained results.

Example 28

Evaluation was performed in the same manner as in Example 21 except that 3,4-DMBS was used as DBSs. Table 2 shows the obtained results.

Comparative Example 16

Evaluation was performed in the same manner as in Example 27, except that no amino acid or a fatty acid alkali metal salt was added. Table 2 shows the obtained results.

Example 29. Evaluation was performed in the same manner as in Example 16 except that h-PP (MFR = 30 gZl 0 min) was used as the resin. Table 2 shows the obtained results.

Comparative Example 17

Evaluation was performed in the same manner as in Example 29, except that no amino acid or a fatty acid alkali metal salt was added. Table 2 shows the obtained results.

Table 2

Nuclear agent

Tree m D B S amino acids Stealine Aldehyde of nucleating agent Taste evaluation Addition amount Acid generation amount

(100 (parts by weight) sodium, parts by weight) (g / PPg)

Parts by weight)

(Weight part)

Example 16 r r P P e-D B S L-alanine 6.4 2 1.8 .0 2 .6 1.6 .5

1 ί r-one P P M e -D B S L-glutamic acid 6.8 2 8.4 0 .2 7 2. 0 7

1 o r ― P P e-D B S L -Glutamic acid 5.9 1 2.40.24 2.17

1 9 r 1 P P M e-D B S Glycine 6. 7 2 7. 5 0.2 7 1. 7 5

2 0 r 1 P P e-D B S Glycine 2.2.8.9 0.2 2 2.26

2 I r-PP eD BSL-histidine 5.9.1 1 .8 0 .24 1.33 and άr 1 Pr M eD BS shi-histidine 1.6 .3 0 .2 1 1 .7 4 r ― PPM e-UBL-Hisnanno 1.0 2.10.2 1 1.8 4 yi P (P) M eD BSL-Histidine 0.5.1.0 0.0.2 1 2.3 1

2 5 ― P P D B S Glycine 6. 7 2 7. 5 0. 2 7 2. 2 4

26 r-P P E t -D B S L-alanine 6.4 2 1.8 .26 1.1.8 4

2 7 r-P P 3,4-DMB S L-Glutamic acid 5.9 1 2.4 0.24 1.0.93

28 r- P P 3,4-D B S shi-histidine 5.9.1 1 .8 0 .24 1 .3 1

2 9 h- P P e-D B S L-alanine 6.4 2 1.8 .2 0 2 .6 2 2 7 Comparative example 1 2 r-P P M e-D B S 0.2 0 4.8.20

1 3 r-P P M e-D B S 1 1.8 0 2 2 4. 6 1 8

1 4 r ― P P D B S 0.2 0 5.0 0 1 6

1 5 r 1 P P E t-D B S 0.2 0 4. 8 1 8

1 6 r-1 P P 3,4-DM B S 0.20 4.4.3 15

1 7 h- PP eD BS 0.2 0 5.2 2 2 0

Example 30

While stirring and dispersing 5 g of Me-DBS and 0.45 g of stearic acid in 30 g of methanol, a solution of 0.1 g of sodium glycine dissolved in 2 Om1 of deionized water was added. The resulting dispersion was heated and stirred for 1 hour under reflux conditions, and dried to obtain a sample.

Using the obtained sample, the crystallization temperature, haze value and odor were evaluated in the same manner as in Example 1, and the amount of aldehyde generated and the taste were evaluated in the same manner as in Example 16. Result, crystallization temperature: 128 ° C, haze value: 10%, odor evaluation: pellets (dry method) = 7 points, injection molded products (dry method) = 6 points, injection molded products (wet method) = 6 Points, aldehyde generation: 2.1 ig / PPg, taste evaluation: 6 points.

Example 31

(a) A solution of 0.25 g of tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, a phenolic antioxidant, dissolved in 30 g of methanol A solution of 0.08 g of L-histidine and 0.185 g of sodium stearate in 2 Oml of deionized water was added to 5 g of DBS and, with stirring, dispersed. The resulting dispersion was heated, stirred for 1 hour under reflux conditions, and dried to obtain a sample.

After sealing the obtained sample in a glass bottle, it was left in a 5 O constant temperature bath for 1 week or 2 weeks to perform a storage stability test. Subsequently, the yellowness of the samples before and after the storage stability test was measured by the following method. Table 3 shows the obtained results.

(b) The evaluation was performed in the same manner as in (a) except that no antioxidant was added. Table 3 shows the obtained results.

6 g of cyclohexane was added to 4 g of the sample to form a paste, and the measurement was performed using a spectrophotometer (trade name “CM-3500 d” manufactured by Minolta Co., Ltd.). The smaller the obtained value, the less yellowish coloring and the better the storage stability.

Table 3

Note) Antioxidant: Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane

Example 32

(i) A dibenzylidenesorbitol nucleating agent of the present invention was obtained in the same manner as in Example A except that 1 part by weight of L-histidine and 2 parts by weight of sodium stearate were used per 100 parts by weight of Me-DBS.

(ii) The dibenzylidene sorbitol nucleating agent of the present invention obtained at the above ω with respect to 100 parts by weight of r_PP (MF R = 20 g_10 minutes) having an ethylene content of 3.0% by weight.

2 parts by weight, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name “Ilganox 1010”, manufactured by Ciba Specialty Chemicals) 0.05 weight After mixing 0.05 parts by weight of calcium stearate with a Henschel mixer and mixing until uniform, then melt kneading with a single screw extruder with a diameter of 25 mm at a resin temperature of 240 ° C to form pellets did.

Next, the obtained pellets were injection-molded under the conditions of a resin temperature of 240 ° C and a mold temperature of 4 ° to prepare a test piece having a thickness of 2 mm.

(iii) The degree of yellow coloring of the test piece obtained in (ii) and the degree of yellow coloring of the comparative sample described below were visually observed, and no difference was observed between the two.

A test piece prepared by injection molding in the same manner as in the above (ii) except that Me-DBS is used instead of the dibenzylidenesorbitol nucleating agent of the present invention obtained in the above (i) (sample for comparison) I got

Example 33

(1) Example A was repeated except that 100 parts by weight of Me-DBS were replaced by 1 part by weight of sodium L-histidine and 1.8 parts by weight of stearic acid instead of using an amino acid and an alkali metal salt of a fatty acid. Similarly, a dibenzylidene sorbitol nucleating agent of the present invention was obtained.

(2) A test piece was prepared in the same manner as in Example 32 (ii) except that the dibenzylidene sorbitol nucleating agent of the present invention obtained in the above (1) was used.

(3) The degree of yellow coloration of the test piece obtained in (2) above and the degree of yellow coloration of the comparative sample described in (iii) of Example 32 were visually observed. Difference I was not able to admit.

Comparative Example 1 8

(a) Comparative dibenzylidene sorbitol in the same manner as in Example A except that 1 part by weight of sodium L-histidine was used for 100 parts by weight of Me-DBS instead of using an alkali metal salt of an amino acid and a fatty acid. A nucleating agent was obtained.

(b) A test piece was prepared in the same manner as in Example 32 (ii) except that the comparative dibenzylidene sorbitol nucleating agent obtained in (a) was used.

(c) The degree of yellow coloring of the test piece obtained in (b) above and the degree of yellow coloring of the comparative sample described in (iii) of Example 32 were visually observed. There was a clear difference. INDUSTRIAL APPLICABILITY According to the present invention, DBSs represented by the general formula (1) may include (A) at least one amino acid and at least one fatty acid alkali metal salt having 8 to 32 carbon atoms, or (B) the dibenzylidene sorbitol nucleating agent of the present invention obtained by adding at least one alkali metal salt of an amino acid and at least one fatty acid having 8 to 32 carbon atoms in the above-described specific amount, Polyolefin resin composition which suppresses the generation of aldehydes during thermoforming and in the final molded product when used in combination with a resin, significantly reduces odor and taste transferability, and is excellent in transparency. Pellets) and compacts are obtained.

Furthermore, by using an antioxidant in combination with the nucleating agent of the present invention, the storage stability of the nucleating agent of the present invention is improved.

According to the present invention, the use of the resin composition and the molded article can be used without restriction in the food packaging field where the use was sometimes restricted due to odor or yellow coloring.

Claims

Claims General formula (1)

Dibenzylidene sorbitol represented by the following formula: and per 100 parts by weight of the dibenzylidene sorbitol

(A) 0.1 to 50 parts by weight of at least one kind of amino acid and 0.1 to 100 parts by weight of at least one kind of alkali metal salt of fatty acid having 8 to 32 carbon atoms, or

A dibenzylidene sorbitol nucleating agent comprising:

2 amino acids have the general formula (2)

Wherein R ³ and R ⁴ are the same or different, (a) a hydrogen atom,

(b) a linear or branched alkyl group having 1 to 6 carbon atoms,

(c) a linear or branched alkenyl group having 2 to 6 carbon atoms,

(d) an alkyl group having 1 to 2 carbon atoms substituted with a phenyl group which may have one or two hydroxyl groups on the benzene ring, or

Represents

The linear or branched alkyl group having 1 to 6 carbon atoms of the above (b) represented by R ³ and R ⁴ is an alkylthio group having 1 to 2 carbon atoms, a hydroxyl group, one SH, an amino group, It may be substituted with one or two substituents selected from the group consisting of a xyl group, a carbamoyl group, a guanidino group and —S—SCH ₂ CH (NH ₂ ) —CO OH. Further, one of R ³ and R ⁴ and the amino group may be bonded to each other to form a pyrrolidine ring which may have a hydroxyl group together with the carbon atom to which they are bonded. ]

The dibenzylidene sorbitol nucleating agent according to claim 1, which is an α-amino acid represented by the formula:

3 amino acids are glycine, alanine, feniralanine, isoleucine, valine, leucine, proline, arginine, aspartic acid, cystine, daltamic acid, serine, histidine, tributofan, lysine, threonine, methionine, cystine, tyrosine, aspirin 2. The di-amino acid according to claim 1, which is at least one amino acid selected from the group consisting of glutamine, noparin and α-aminobutyric acid.

-Nucleating agent.

4 Amino acids are glycine, L-alanine, L-phenylalanine, L-isoleucine, L-valine, L-mouth isine, L-proline, L-arginine, L-sparaginate, L-cystine, L-glutamic acid, L -Serine, L-histidine, L-tryptophan, L-lysine, L-threonine, L-methionine, DL-me 2. The dibenzylidene sorbitol nucleating agent according to claim 1, which is at least one amino acid selected from the group consisting of thionine, L-cysteine, L-tyrosine, L-asparagine, L-glutamine, L-norvaline and L-α-aminobutyric acid. .

5 Fatty acids with 8 to 32 carbon atoms are octanoic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, oleic acid, linole 2. The dibenzylidene sorbitol nucleating agent according to claim 1, wherein the nucleating agent is at least one member selected from the group consisting of an acid, linolenic acid, eleostearic acid, ricinoleic acid, and erlic acid.

6 With respect to the dibenzylidene sorbitol represented by the general formula (1) and 100 parts by weight of the dibenzylidene sorbitol, (Α) at least one kind of amino acid 0.1 to 50 parts by weight and carbon number 8 2. The dibenzylidene sorbitol nucleating agent according to claim 1, comprising 0.1 to 100 parts by weight of at least one kind of metal salts of fatty acids.

7. The dibenzylidene sorbitol nucleating agent according to claim 6, wherein the alkali metal of the fatty acid alkali metal salt having 8 to 32 carbon atoms is sodium or potassium. 8. The dibenzylidene sorbitol nucleating agent according to claim 6, wherein the fatty acid alkali metal salt having 8 to 32 carbon atoms is at least one selected from the group consisting of sodium stearate and potassium stearate.

9 Claim 1 further containing an antioxidant ⁽

Nucleating agent.

10. The divedylidene sorbitol nucleating agent according to claim 9, wherein the antioxidant is a phenolic antioxidant. (I) General formula (1)

Per 100 parts by weight of dibenzylidene sorbitol represented by

(A) at least one kind of amino acid 0.1 to 50 parts by weight and at least one kind of alkali metal salt of fatty acid having 8 to 32 carbon atoms 0.1 to 100 parts by weight, or

A dibenzylidene sorbitol nucleating agent containing:

(II) Polyolefin resin

A polyolefin-based resin composition comprising:

12. The polyolefin-based resin composition according to claim 11, wherein the polyolefin-based resin composition contains 0.05 to 3 parts by weight of a dibenzylidenesorbitol nucleating agent based on 100 parts by weight of the polyolefin-based resin.

3 amino acids have the general formula (2)

Wherein R ³ and R ⁴ are the same or different,

(a) a hydrogen atom,

(b) a linear or branched alkyl group having 1 to 6 carbon atoms,

(c) a linear or branched alkenyl group having 2 to 6 carbon atoms,

(e) a carbon substituted with a 5- to 6-membered monocyclic heterocyclic group containing 1% or 2 nitrogen atoms or a bicyclic heterocyclic group obtained by condensing the monocyclic heterocyclic group with a benzene ring; Alkyl group of number 1-2

Represents

The linear or branched alkyl group having 1 to 6 carbon atoms in the above (b) represented by R ³ and R ⁴ is an alkylthio group having 1 to 2 carbon atoms, a hydroxyl group, one SH, an amino group, a carboxy group. It may be substituted with one or two substituents selected from the group consisting of a xyl group, a carbamoyl group, a guanidino group and —S—SCH ₂ CH (NH ₂ ) —COOH. Further, one of R ³ and R ⁴ and the amino group may be bonded to each other to form a pyrrolidine ring which may have a 7-acid group together with the carbon atom to which they are bonded. ]

12. The polyolefin resin composition according to claim 11, which is an amino acid represented by the formula:

14 The amino acids are glycine, alanine, fenylalanine, isoleucine, valine, leucine, proline, arginine, aspartic acid, cystine, dalminic acid, serine, histidine, tributphan, lysine, threonine, methionine, cystine, tyrosine. , Asparagine, glutamine, norparin and α-α 12. The polyolefin resin composition according to claim 11, which is at least one amino acid selected from the group consisting of minobutyric acid.

15 amino acids are glycine, L-alanine, L-phenylalanine, L-isoleucine, L-valine, L-leucine, L-proline, L-arginine, L-aspartic acid, L-cystine, L-glutamic acid , L-serine, L-histidine, L-tryptophan, L-lysine, L-threonine, L-methionine, DL-methionine, L-cystine, L-tyrosine, L-asparagine, L-Dalmin, L-norvaline and L -The polyolefin resin composition according to claim 11, which is at least one amino acid selected from the group consisting of monoaminobutyric acid.

16 Fatty acids with 8 to 32 carbon atoms are octanoic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, oleic acid, linole The polyolefin resin composition according to claim 11, which is at least one selected from the group consisting of acids, linolenic acid, eleostearic acid, ricinoleic acid, and erlic acid.

17—Dibenzylidene sorbitol represented by the general formula (1) and 100 parts by weight of the dibenzylidene sorbitol, (A) 0.1 to 50 parts by weight of at least one kind of amino acid (A) The polyolefin-based resin composition according to claim 11, comprising at least 0.1 to 100 parts by weight of a metal salt of a fatty acid having 8 to 32 carbon atoms.

18. The polyolefin resin composition according to claim 17, wherein the alkali metal of the fatty acid alkali metal salt having 18 to 32 carbon atoms is sodium or potassium.

19. The polyolefin resin composition according to claim 17, wherein the metal salt of a fatty acid having 8 to 32 carbon atoms is at least one selected from the group consisting of sodium stearate and potassium stearate. 21. The polyolefin-based resin composition according to claim 11, wherein the 20 nucleating agent composition further contains an antioxidant. 21. The polyolefin resin composition according to claim 20, wherein the 21 antioxidant is a phenolic antioxidant.

22. A polyolefin resin molded article obtainable by forming the polyolefin resin composition according to any one of claims 11 to 21.

2 3 General formula

[Wherein 1 ^ and 1 ^ ² are the same or different and each represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen atom. m and n each represent an integer of 0-3. ]

A method for suppressing the transfer of odor and taste from a polyolefin-based resin composition or a polyolefin-based resin molded product containing a dibenzylidene sorbitol and a polyolefin-based resin represented by the following general formula (1): In the dibenzylidene sorbitol represented,

(A) 0.1 to 50 parts by weight of at least one kind of amino acid and 0.1 to 100 parts by weight of at least one kind of alkali metal salt of a fatty acid having 8 to 32 carbon atoms, or

(B) 0.1 to 50 parts by weight of at least one alkali metal salt of an amino acid and charcoal A method characterized by adding at least one part by weight of 0.008 parts by weight of a fatty acid having a prime number of 8 to 32.

2 4 — general formula

(B) Use of 0.1 to 50 parts by weight of at least one kind of an alkali metal salt of an amino acid and 0.1 to 100 parts by weight of at least one kind of a fatty acid having 8 to 32 carbon atoms.