JP6761165B2 - A polyolefin-based resin masterbatch, a method for producing the same, and a polyolefin-based resin molded product using the masterbatch. - Google Patents

Description

The present invention relates to a polyolefin-based resin masterbatch, a method for producing the same, and a polyolefin-based resin molded body formed by using the masterbatch. Specifically, the present invention relates to the polyolefin-based resin of the crystal nucleating agent contained in the masterbatch. There is no residual undispersed or undissolved material of the crystal nucleating agent obtained by using the polyolefin-based resin masterbatch with excellent dispersibility and solubility, and as a result, white spots and fish eyes. The present invention relates to a polyolefin-based resin molded body having excellent transparency and mechanical properties without any drawbacks such as.

Polyolefin-based resins such as polyethylene and polypropylene have inexpensive and well-balanced performance, and are used in various applications as general-purpose plastics. In general, polyolefin-based resins are crystalline resins, and are often used with a crystal nucleating agent added for the purpose of improving production efficiency and for improving mechanical properties, thermal properties, and optical properties. .. In particular, the addition of a crystal nucleating agent is indispensable for improving transparency, which is an optical property.

The crystal nucleating agent includes an inorganic crystal nucleating agent such as talc and an organic crystal nucleating agent such as a diacetal compound and a phosphate metal salt, and further, the organic crystal nucleating agent is a dissolved type and insoluble. There are types of crystal nucleating agents. A dissolution-type organic crystal nucleating agent typified by the diacetal compound is particularly effective for improving optical properties such as transparency, and is often used.

In general, any of the crystal nucleating agents has poor miscibility with the polyolefin-based resin, and it is difficult to uniformly disperse or dissolve them in the polyolefin-based resin. In particular, the dissolution type diacetal compound can maximize its effect only when it is uniformly dissolved in the resin, but the compound itself has high cohesiveness and is undispersed in the polyolefin resin. Aggregates of compounds tend to remain, and the aggregates do not dissolve even in the molding process and remain as undissolved substances, which not only does not provide sufficient effects, but also has drawbacks such as fish eyes, resulting in impact strength and tensile properties. There was a problem that it would decrease.

In order to solve the above problems, various improvements have been attempted so far. For example, a method for refining the particle size of diacetal (Patent Document 1), an organic acid acting as a melting point lowering agent for diacetal, and a derivative thereof are used in combination. A method (Patent Document 2) and the like are known. However, the method of refining the particle size raises concerns such as dust explosion, and further improvement in performance has been desired even in a combined system of organic acids.

On the other hand, as a method for improving the dispersibility of additives having poor miscibility with resins such as colorants and fillers, a masterbatch method, that is, for dilution with a high-concentration composition uniformly premixed with a resin. The method of melting and mixing the base resin of the above is often used. Further, in that case, it is generally said that it is preferable that the resin used for the masterbatch is the same resin as the base resin for dilution because there is little change in physical properties and the like.

In the case of the diacetal compound as well, an attempt has been made to improve the dispersibility by the masterbatch method, and in some applications, a method of actually blending the diacetal compound into the resin has been attempted. Specifically, (1) a method for producing a masterbatch at a concentration and heating temperature at which the diacetal compound is completely dissolved in the resin, and (2) the filling without completely dissolving the diacetal compound in the resin at a low temperature. There is a method of uniformly dispersing in the resin in a state of being sheared like an agent or the like. However, as described above, the diacetal compound has poor dispersibility and solubility in the polyolefin resin, and in the case of the method (1), the heating temperature must be raised in order to increase the concentration, and the resin deteriorates. Further, even when the method (2) is used, if the concentration is high, the dispersion and dissolution at the time of molding become insufficient, sufficient performance cannot be obtained, and there is a concern that white spots and the like occur. .. Therefore, it is difficult to prepare a high-concentration masterbatch using the same polyolefin resin as the base resin for dilution, and when the concentration of the masterbatch is lowered or increased, a resin different from the base resin is used. The current situation is that it has to be used (Patent Document 3).

However, if the concentration is low, the productivity will be inferior and it will cause an increase in cost, and if different resins are used, there is a concern that the physical properties will change, so any method can only be used for specific purposes. It could not be used and was a big problem in terms of versatility.

Japanese Unexamined Patent Publication No. 06-145431 WO99 / 018108 JP-A-2009-62417

An object of the present invention is to improve the dispersibility and solubility of a diacetal compound-based crystal nucleating agent in a polyolefin-based resin, and to provide a polyolefin-based resin masterbatch containing the crystal nucleating agent suitable for that purpose. The purpose is.

In view of the above situation, the present inventors have diligently studied to solve the above problems, and as a result, by using a diacetal compound having a specific structure in a specific combination, dispersibility and solubility in a polyolefin resin As a result, it is possible to increase the concentration of the masterbatch, and it is possible to obtain a polyolefin-based resin molded product that is efficient under highly productive conditions, has no defects such as white spots, and has excellent transparency and rigidity. This has led to the completion of the present invention.

That is, the present invention relates to a polyolefin-based resin masterbatch shown below, a method for producing a polyolefin-based resin molded product using the masterbatch as a raw material, and a polyolefin-based resin molded product obtained by the method.

[Item 1] A polyolefin-based resin masterbatch containing a crystal nucleating agent for a polyolefin-based resin, wherein the crystal nucleating agent is a mixture of two or more diacetal compounds represented by the following general formula (1). A polyolefin-based resin masterbatch characterized by this.
[In formula (1), R ¹ and R ² are the same or different, hydrogen atom, linear or branched alkyl group having 1 to 4 carbon atoms, linear or branched carbon, respectively. It indicates an alkoxy group having the number 1 to 4, a linear or branched-chain alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom.
R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ]

[Item 2] The mixture is a mixture containing the component (A) and the component (B) as main components, and the component (A) is 1,3: 2,4-bis-O- (dimethylbenzylidene) -D. -In the case of sorbitol (hereinafter abbreviated as "DMDBS"), the component (B) is 1,3: 2,4-bis-O- (ethylbenzylidene) -D-sorbitol (hereinafter abbreviated as "EDBS"). ) And / or 1,3: 2,4-bis-O- (methylbenzylidene) -D-sorbitol (hereinafter abbreviated as "MDBS"), and the component (A) is 1,3: 2,4-. In the case of bis-O- (methylbenzylidene) -D-sorbitol (MDBS), the component (B) is 1,3: 2,4-bis-O- (ethylbenzylidene) -D-sorbitol (EDBS) [ Item 1] The polyolefin-based resin master batch according to Item 1.

[Item 3] The component (A) is 1,3: 2,4-bis-O- (dimethylbenzylidene) -D-sorbitol (DMDBS), and the component (B) is 1,3: 2,4-bis-. Item 2. The polyolefin-based resin masterbatch according to [Item 2], which is O- (ethylbenzylidene) -D-sorbitol (EDBS).

[Item 4] The 1,3: 2,4-bis-O- (dimethylbenzylidene) -D-sorbitol is replaced with 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene)-. The polyolefin-based resin masterbatch according to [Item 2] or [Item 3], which is D-sorbitol (hereinafter abbreviated as "34DMDBS").

[Item 5] The 1,3: 2,4-bis-O- (ethylbenzylidene) -D-sorbitol is replaced with 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol (. The polyolefin-based resin masterbatch according to any one of [Item 2] to [Item 4], which is hereinafter abbreviated as "pEDBS").

[Item 6] The 1,3: 2,4-bis-O- (methylbenzylidene) -D-sorbitol is replaced with 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol (. The polyolefin-based resin masterbatch according to any one of [Item 2], [Item 4] or [Item 5], which is hereinafter abbreviated as "pMDBS").

[Item 7] The polyolefin-based resin according to any one of [Item 2] to [Item 6], wherein the ratio (weight ratio) of the component (A) to the component (B) is in the range of 60/40 to 10/90. Master Badge.

[Item 8] The polyolefin-based resin masterbatch according to [Item 7], wherein the ratio is 50/50 to 20/80.

[Item 9] The polyolefin-based resin masterbatch according to [Item 8], wherein the ratio is 50/50 to 30/70.

[Item 10] The polyolefin-based product according to any one of [Item 1] to [Item 9], wherein the concentration of the crystal nucleating agent for the polyolefin-based resin is 10% by weight or more based on the total weight of the polyolefin-based resin masterbatch. Resin masterbatch.

[Item 11] The polyolefin-based resin masterbatch according to any one of [Item 1] to [Item 9], wherein the concentration of the crystal nucleating agent for the polyolefin-based resin is 12 to 30% by weight.

[Item 12] The polyolefin-based resin masterbatch according to any one of [Item 1] to [Item 11], which further contains an antioxidant.

[Item 13] The polyolefin-based resin masterbatch according to any one of [Item 1] to [Item 12], which further contains a stabilizer and / or a higher fatty acid metal salt having 8 to 22 carbon atoms.

[Item 14] The antioxidant is 2,6-di-tert-butylphenol, tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-. Methoxybenzophenone, trisnonylphenyl phosphite, diphenylisodecylphosphite, triphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, 3,9-bis (2,6-tert-butyl-) 4-Methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] One or more selected from the group consisting of undecane, [Item 12] or [Item 12] or [Item 12]. 13] The polyolefin-based resin master batch according to.

[Item 15] Antioxidants are tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, tris (2,4-di-tert-butylphenyl) phosphite, 3 , 9-Bis (2,6-tert-butyl-4-methylphenoxy) -2,4,8,10-Tetraoxa-3,9-diphosphaspiro [5,5] One selected from the group consisting of undecane or Item 2. The polyolefin-based resin masterbatch according to [Item 12] or [Item 13], which is two or more kinds.

[Item 16] The method for producing a polyolefin-based resin masterbatch according to any one of [Item 1] to [Item 15], wherein a single-screw extruder or a twin-screw extruder is used and the barrel temperature of the extruder is adjusted. A method for producing a polyolefin-based resin masterbatch, which comprises melting and mixing a crystal nucleating agent and a polyolefin-based resin at a temperature equal to or higher than the dissolution temperature of the crystal nucleating agent in a polyolefin-based resin, and then cooling the mixture.

[Item 17] The manufacturing method according to [Item 16], wherein the barrel temperature of the extruder is 240 ° C. or higher.

[Item 18] The manufacturing method according to [Item 16], wherein the barrel temperature of the extruder is 250 ° C. or higher.

[Item 19] The method for producing a polyolefin-based resin masterbatch according to any one of [Item 1] to [Item 15], wherein a twin-screw extruder is used and the barrel temperature of the extruder is 160 to 210 ° C. A method for producing a polyolefin-based resin masterbatch, which comprises melting and mixing a crystal nucleating agent and a polyolefin-based resin in the above range, and then cooling the mixture.

[Item 20] The manufacturing method according to [Item 19], wherein the barrel temperature of the twin-screw extruder is in the range of 180 to 210 ° C.

[Item 21] The manufacturing method according to [Item 19], wherein the barrel temperature of the twin-screw extruder is in the range of 180 to 200 ° C.

[Item 22] The production method according to any one of [Item 16] to [Item 21], wherein the average particle size of the crystal nucleating agent used is 30 μm or less.

[Item 23] The production method according to any one of [Item 16] to [Item 21], wherein the average particle size of the crystal nucleating agent is in the range of 0.1 to 25 μm.

[Item 24] The production method according to any one of [Item 16] to [Item 21], wherein the average particle size of the crystal nucleating agent is in the range of 0.5 to 15 μm.

[Item 25] A polyolefin-based resin according to any one of [Item 1] to [Item 15], which comprises mixing or melt-mixing the polyolefin-based resin masterbatch and the polyolefin-based resin which is the base resin for dilution. A method for producing a resin composition.

[Item 26] A polyolefin-based resin molded product, wherein the raw material of the crystal nucleating agent component is the polyolefin-based resin masterbatch according to any one of [Item 1] to [Item 15].

[Item 27] A polyolefin-based resin molded product composed of the polyolefin-based resin masterbatch according to any one of [Item 1] to [Item 15] and a polyolefin-based resin as a base resin for dilution.

[Item 28] A method for producing a polyolefin-based resin molded product, which comprises using the polyolefin-based resin masterbatch according to any one of [Item 1] to [Item 15] and a polyolefin-based resin as a base resin for dilution. ..

[Item 29] The production method according to [Item 28], wherein the molding temperature in the production of the molded product is equal to or higher than the temperature at which the entire amount of the crystal nucleating agent after dilution is dissolved in the polyolefin resin.

[Item 30] The production method according to [Item 28], wherein the molding temperature is + 10 ° C. or higher at which the total amount of the crystal nucleating agent after dilution is dissolved in the polyolefin resin.

[Item 31] The production method according to [Item 28], wherein the molding temperature is 220 ° C. or higher.

[Item 32] The production method according to [Item 28], wherein the molding temperature is 240 ° C. or higher.

By using the polyolefin-based resin masterbatch of the present invention, a polyolefin-based resin molded product having excellent transparency and mechanical properties can be obtained as an undispersed or undissolved crystal nucleating agent that causes white spots and fish eyes. It can be easily obtained without leaving a substance substantially.

<Polyolefin resin masterbatch>
The polyolefin-based resin masterbatch of the present invention contains a crystal nucleating agent for a polyolefin-based resin and a polyolefin-based resin as a base resin for dilution, or a polyolefin-based resin having properties similar to the base resin, if necessary. It can be obtained by adding a resin additive and melt-mixing under predetermined conditions.

[Crystal nucleating agent for polyolefin resins]
The crystal nucleating agent for a polyolefin-based resin of the present invention is a mixture of two or more kinds of diacetal compounds represented by the following general formula (1).
[In formula (1), R ¹ and R ² are the same or different, hydrogen atom, linear or branched alkyl group having 1 to 4 carbon atoms, linear or branched carbon, respectively. It indicates an alkoxy group having the number 1 to 4, a linear or branched-chain alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded, and the two R ² groups may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. You may be. ]

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and s. -Butyl group, isobutyl group, t-butyl group and the like can be mentioned. In the present specification, "n-" means normal, "s-" means secondary (sec-), and "t-" means tertiary (tert-).

Similarly, examples of the linear or branched alkoxy group having 1 to 4 carbon atoms represented by R ¹ and R ² include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and n-. Examples thereof include a butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group and the like. Examples of the linear or branched alkoxycarbonyl group having 1 to 4 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and an s-butoxy. Examples thereof include a carbonyl group, an isobutoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an s-butyl group. , Isobutyl group, t-butyl group and the like.

Similarly, the linear or branched alkenyl group having 2 to 4 carbon atoms represented by R ^3, for example, ethenyl group, propenyl group, butenyl group. Examples of the linear or branched hydroxyalkyl group having 1 to 4 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a 1-hydroxypropyl group.

In the general formula (1), m and n are integers of 1 to 5, respectively. Further, p in the general formula (1) is 0 or 1, preferably 1. In the general formula (1), the substitution position of the substituent represented by R1 and R2 is not particularly limited, but when m and n are 1, it is the o-, m- or p-position. , M and n are 2, examples of 2,3-position, 2,4-position, 2,5-position, 3,4-position, 3,5-position, etc., and m and n are 3 In this case, 2,4,5-position, 3,4,5-position, etc. can be exemplified.

All of these diacetals represented by the general formula (1) are known, or Japanese Patent Application Laid-Open No. 48-43748, Japanese Patent Application Laid-Open No. 53-5165, Japanese Patent Application Laid-Open No. 57-185287, It can be easily produced according to a known method such as Kaihei 2-231488.

The following can be exemplified as a typical example of the diacetal represented by the general formula (1). 1,3: 2,4-bis-O-benzylidene-D-sorbitol, MDBS, 1,3: 2,4-bis-O- (o-methylbenzylidene) -D-sorbitol, 1,3: 2,4 -Bis-O- (m-methylbenzylidene) -D-sorbitol, pMDBS, EDBS, 1,3: 2,4-bis-O- (o-ethylbenzylidene) -D-sorbitol, 1,3: 2,4 -Bis-O- (m-ethylbenzylidene) -D-sorbitol, pEDBS, 1,3: 2,4-bis-O- (o-isopropylbenzylidene) -D-sorbitol, 1,3: 2,4-bis -O- (m-isopropylbenzylylene) -D-sorbitol, 1,3: 2,4-bis-O- (p-isopropylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- ( on-propylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (mn-propylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- ( pn-propylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (one-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- ( mn-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (pn-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O-( o-tert-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-tert-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O-( p-tert-butylbenzylidene) -D-sorbitol, DMDBS, 1,3: 2,4-bis-O- (2', 3'-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis -O- (2', 4'-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2', 5'-dimethylbenzylidene) -D-sorbitol, 1,3: 2 , 4-bis-O- (2', 6'-dimethylbenzylidene) -D-sorbitol, 34DMDBS, 1,3: 2,4-bis-O- (3', 5'-dimethylbenzylidene) -D-sorbitol , 1,3: 2,4-bis-O- (2', 3'-diethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2', 4'-diethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2', 5'-diethylbenzylidene) -D -Sorbitol, 1,3: 2,4-bis-O- (2', 6'-diethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3', 4'-diethyl) Benzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3', 5'-diethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2', 4', 5'-trimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3', 4', 5'-trimethylbenzylidene) -D-sorbitol, 1,3: 2, 4-bis-O- (2', 4', 5'-triethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3', 4', 5'-triethylbenzylidene)- D-sorbitol, 1,3: 2,4-bis-O- (o-methoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-methoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-methoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (o-ethoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-ethoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-ethoxybenzylidene) -D-sorbitol, 1,3: 2,4- Bis-O- (o-isopropoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-isopropoxybenzylylene) -D-sorbitol, 1,3: 2,4-bis- O- (p-isopropoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (one-propoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O -(Mn-propoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (pn-propoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O -(O-methoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-methoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O-( p-methoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (o-ethoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-) Ethoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-d) Toxicarbonylbenzylylene) -D-sorbitol, 1,3: 2,4-bis-O- (o-isopropoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-iso) Propoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-isopropoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (one) -Propoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (mn-propoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p) -N-propoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (o-fluorobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-) Fluorobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-fluorobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (o-chlorobenzylidene)- D-sorbitol, 1,3: 2,4-bis-O- (m-chlorobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (o-bromobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-bromobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-bromobenzylidene) -D-sorbitol, 1,3-O-benzylidene-2,4-O- (p-methylbenzylidene) -D-sorbitol, 1,3-O- (P-Methylbenzylidene) -2,4-O-benzylidene-D-sorbitol, 1,3-O-benzylidene-2,4-O- (p-ethylbenzylidene) -D-sorbitol, 1,3-O- (P-Ethylbenzylidene) -2,4-O-benzylidene-D-sorbitol, 1,3-O-benzylidene-2,4-O- (p-chlorobenzylidene) -D-sorbitol, 1,3-O- (P-chloroBenzylidene) -2,4-O-benzylidene-D-sorbitol, 1,3-O-benzylidene-2,4-O- (2', 4'-dimethylbenzylidene) -D-sorbitol, 1, 3-O- (2', 4'-dimethylbenzylidene) -2,4-O-benzylidene-D-sorbitol, 1,3-O-benzylidene-2,4-O- (3', 4'-dimethylben) Gilliden) -D-sorbitol, 1,3-O- (3', 4'-dimethylbenzylidene) -2,4-O-benziliden-D-sorbitol, 1,3-O- (p-methylbenziliden) -2 , 4-O- (p-ethylbenzylidene) -D-sorbitol, 1,3-O- (p-ethylbendylidene) -2,4-O- (p-methylbenziliden) -D-sorbitol, 1,3- O- (p-methylbenzylene) -2,4-O- (3', 4'-dimethylbenziliden) -D-sorbitol, 1,3-O- (3', 4'-dimethylbenzylene) -2,4 -O-p-Methylbenzylidene-D-Sorbitol, 1,3-O- (p-ethylbendilidene) -2,4-O- (3', 4'-Dimethylbenzylidene) -D-Sorbitol, 1,3- O- (3', 4'-dimethylbenzylidene) -2,4-O-p-ethylbendylidene-D-sorbitol, 1,3-O- (p-methylbendylidene) -2,4-O- (p-) Chlorobenzylidene) -D-sorbitol, 1,3-O- (p-chlorobenzylidene) -2,4-O- (p-methylbendylidene) -D-sorbitol, 1,3: 2,4-bis-O- Benziliden-1-methylsorbitol, 1,3: 2,4-bis-O- (p-methylbenziliden) -1-methylsorbitol, 1,3: 2,4-bis-O- (p-ethylbenziliden)- 1-Methylsorbitol, 1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2', 3'- Dimethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2', 4'-dimethylbenziliden) -1-methylsorbitol, 1,3: 2,4-bis-O-( 2', 5'-dimethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2', 6'-dimethylbenziliden) -1-methylsorbitol, 1,3: 2,4 -Bis-O- (3', 4'-dimethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (3', 5'-dimethylbenzylidene) -1-methylsorbitol, 1 , 3: 2,4-bis-O- (2', 3'-diethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2', 4'-diethylbenzylidene)- 1-Methylsorbitol, 1,3: 2,4-bis-O- (2', 5'-diethylben Dilidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2', 6'-diethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (3) ', 4'-diethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (3', 5'-diethylbenzylidene) -1-methylsorbitol, 1,3: 2,4- Bis-O- (3'-methyl-4'-methoxybenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dichlorobenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (p-methoxycarbonylbenzylene) -1-methylsorbitol, 1,3: 2,4-bis-O- (3'-methyl-4'-fluorobenzylidene)- 1-Methylsorbitol, 1,3: 2,4-bis-O- (3'-bromo-4'-ethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O-benzylene-1 -Ethyl sorbitol, 1,3: 2,4-bis-O- (p-methylbenzylidene) -1-ethyl sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-ethyl Sorbitol, 1,3: 2,4-bis-O- (pn-propylbenzylene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (2', 3'-dimethylbenzylene) -1-Ethylsorbitol, 1,3: 2,4-bis-O- (2', 4'-dimethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (2', 5'-Dimethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (2', 6'-dimethylbenziliden) -1-ethylsorbitol, 1,3: 2,4-bis- O- (3', 4'-dimethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3', 5'-dimethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-Bis-O- (2', 3'-diethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (2', 4'-diethylbenzylidene) -1-ethyl Sorbitol, 1,3: 2,4-bis-O- (2', 5'-diethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (2', 6'-diethyl) Benzilidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3', 4'-diethylben) Dilidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3', 5'-diethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3) '-Methyl-4'-methoxybenzylene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dichlorobenzylidene) -1-ethylsorbitol, 1,3: 2, 4-Bis-O- (p-methoxycarbonylbenzylene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3'-methyl-4'-fluorobenzylidene) -1-ethylsorbitol, 1 , 3: 2,4-bis-O- (3'-bromo-4'-ethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O-benzylidene-1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-methylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-n-propyl Sorbitol, 1,3: 2,4-bis-O- (pn-propylbenzylene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 3'-dimethyl) Benzilidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 4'-dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis- O- (2', 5'-dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 6'-dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3', 5'-dimethyl) Benzilidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 3'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis- O- (2', 4'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 5'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 6'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3', 4'-diethyl) Benzilidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3', 5'-diethylbe Ndilidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3'-methyl-4'-methoxybenzylidene) -1-n-propylsorbitol, 1,3: 2,4- Bis-O- (3', 4'-dichlorobenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-methoxycarbonylbenzylidene) -1-n-propylsorbitol, 1 , 3: 2,4-bis-O- (3'-methyl-4'-fluorobenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3'-bromo-4) '-Ethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O-benzylidene-1-allylsorbitol, 1,3: 2,4-bis-O- (p-methylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 3'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 4'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 5'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis- O- (2', 6'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3', 5'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 3'-diethylbenzylidene) -1-allyl Sorbitol, 1,3: 2,4-bis-O- (2', 4'-diethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 5'-diethyl) Benzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 6'-diethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3) ', 4'-diethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3', 5'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2, 4-Bis-O- (3'-methyl-4'-methoxybenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3', 4'-dichlorobenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (p-methoxycarbonylbenzylidene) -1- Allyl sorbitol, 1,3: 2,4-bis-O- (3'-methyl-4'-fluorobenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3'-bromo) -4'-ethylbenzylidene) -1-allylsorbitol and the like are exemplified.

Among the above diacetal compounds, a polyolefin-based resin composed of a mixture containing two or more diacetal compounds selected from the group consisting of MDBS (preferably pMDBS), EDBS (preferably pEDBS), and DMDBS (preferably 34DMDBS). The obtained crystal nucleating agent was obtained because the obtained polyolefin-based resin molded product was excellent in performance and also had excellent dispersibility and solubility in the resin, which is the effect of the present invention. It is particularly effective and recommended for improving defects such as white spots on the molded product. In the present invention, the main component is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, in the mixture of two or more diacetal compounds selected from the above group. Particularly preferably, it means that it is 80% by weight or more.

As a more specific example of the combination of the diacetal compound which is the main component of the mixture, for example, when DMDBS is selected as the component (A), the component (B) to be combined is EDBS and / or MDBS. Is mentioned as a preferable combination. Similarly, for example, when MDBS is selected as the component (A), it is preferable to combine EDBS as the component (B) as a preferable example.

The ratio (weight ratio) of the component (A) to the component (B) is not particularly limited as long as the effect of the present invention is obtained, but a preferable range is component (A) / component (B) = 60/40. The range of 10/90 is recommended, more preferably the range of 50/50 to 20/80, and even more preferably the range of 50/50 to 30/70.

Even if the concentration of the crystal nucleating agent in the polyolefin resin masterbatch of the present invention is less than 10% by weight, there is no problem in performance, but considering the cost advantage of using the masterbatch, it is 10% by weight or more. It is recommended that there be.

Further, the upper limit of the concentration of the crystal nucleating agent is not particularly limited as long as the effect of the present invention is obtained, but from the viewpoint of the dilution ratio (about 20 to 200 times) at the time of normal molding, further for the purpose of the present invention. From the viewpoint of dispersibility and solubility of the crystal nucleating agent in a certain molded product, it is desirable that the concentration is about 30% by weight or less.

More specifically, it is recommended that the concentration range of the crystal nucleating agent is preferably 10% by weight or more, more preferably about 12 to 30% by weight.

[Polyolefin-based resin]
As described above, the polyolefin-based resin used in the master batch of the present invention is a polyolefin-based resin having the same or similar properties as the polyolefin-based resin which is the base resin for dilution. For example, polyethylene-based resin, polypropylene-based resin, and polybutene. Examples thereof include based resins, polymethylpentene resins, and polybutadiene resins. Specifically, high-density polyethylene, medium-density polyethylene, linear polyethylene, ethylene copolymer having an ethylene content of 50% by weight or more, preferably 70% by weight or more, propylene homopolymer, propylene by 50% by weight or more, preferably 70% by weight. The above propylene copolymer, butene homopolymer, butene copolymer having a butene content of 50% by weight or more, preferably 70% by weight or more, methylpentene homopolymer, methylpentene copolymer having a methylpentene content of 50% by weight or more, preferably 70% by weight or more. Examples thereof include polybutadiene. Further, the above-mentioned copolymer may be a random copolymer or a block copolymer. Further, if these resins have stereoregularity, they may be isotactic or syndiotactic. Specific examples of the comonomer that can constitute the above copolymer include α-olefins having 2 to 12 carbon atoms such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene, 1,4-. Examples thereof include bicyclo-type monomers such as endomethylenecyclohexene, (meth) acrylate esters such as methyl (meth) acrylate and ethyl (meth) acrylate, and vinyl acetate.

As the catalyst applied to produce such a polymer, not only a commonly used Ziegler-Natta type catalyst but also a transition metal compound (for example, a halide of titanium such as titanium trichloride and titanium tetrachloride) is chlorided. A catalyst system in which a catalyst supported on a carrier containing magnesium halide such as magnesium as a main component and an alkylaluminum compound (triethylaluminum, diethylaluminum chloride, etc.) is combined, a metallocene catalyst and the like can also be used.

The melt flow rate of the polyolefin resin according to the present invention (hereinafter abbreviated as "MFR"; JIS K 7210-1999) is appropriately selected depending on the molding method to which it is applied, but is usually about 0.01 to 200 g / 10 minutes. , Preferably about 0.05 to 100 g / 10 minutes.

[Other additives]
Further, as described above, the masterbatch for a polyolefin resin of the present invention contains other additives for a polyolefin resin according to the purpose of use and the use thereof, as long as the effects of the present invention are not impaired. May be good.

Examples of the additives for polyolefin resins include various additives described in "Handbook of Additives on the Positive List" (January 2002) edited by the Polyolefin Hygiene Council. Specifically, fluorescent whitening agents (2,5-thiophendiyl (5-tert-butyl-1,3-benzoxazole), 4,4'-bis (benzoxazole-2-yl) stelvene, etc.), Antioxidants, stabilizers (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants, lubricants (paraffin, wax, etc.) Aliphatic hydrocarbons, higher fatty acids with 8 to 22 carbon atoms, higher fatty acid metal (Al, Ca) salts with 8 to 22 carbon atoms, higher aliphatic alcohols with 8 to 22 carbon atoms, polyglycols, 4 to 22 carbon atoms Esters of higher fatty acids with aliphatic monovalent alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives, etc., fillers (talc, hydrotalcite, mica, zeolite, pearlite, etc.) , Silica, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agent, foaming aid, polymer additive, plastic agent (dialkylphthalate, dialkylhexahydrophthalate, etc.), cross-linking agent, cross-linking accelerator, antistatic agent, flame retardant, dispersion Examples thereof include agents, organic-inorganic pigments (indigo compounds, phthalocyanine compounds, anthraquinone compounds, ultramarine compounds, cobalt aluminate compounds, etc.), processing aids, and various additives such as other nucleating agents.
When these additives are used, the amount used may be within the range normally used as long as the effects of the present invention are not impaired, but the concentration after dilution is based on 100 parts by weight of the polyolefin resin. It is generally used in an amount of about 0.0001 to 100 parts by weight, more preferably about 0.001 to 50 parts by weight.

In particular, the antioxidant also has an effect of suppressing deterioration such as coloring in the manufacturing process of the polyolefin resin masterbatch of the present invention. When an antioxidant is used from the above viewpoint, the amount used is preferably about 0.01 to 5 parts by weight, more preferably about 0.03 to 3 parts by weight, based on 100 parts by weight of the polyolefin resin masterbatch. It is recommended that there be.

Examples of the antioxidant include phenol-based antioxidants, phosphite ester-based antioxidants, sulfur-based antioxidants, and the like, and specific antioxidants include 2,6-di-tert-butylphenol. , Phenolic antioxidants such as tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxybenzophenone, alkyl disulfides, thiodipropionic acid esters, Sulfur-based antioxidants such as benzothiazole, trisnonylphenyl phosphite, diphenylisodecylphosphite, triphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, 3,9-bis (2) , 6-tert-Butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] Subphosphate ester-based antioxidants such as undecane are exemplified. Among them, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, which is a phenolic antioxidant, and tris (2,) which is a phosphite ester-based antioxidant. 4-Di-tert-butylphenyl) phosphite, 3,9-bis (2,6-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5, 5] Undecan is especially recommended.

[Manufacturing method of polyolefin resin masterbatch]
The method for producing a masterbatch for a polyolefin resin of the present invention is not particularly limited as long as the obtained masterbatch exerts the effect of the present invention, and is a general-purpose melt-mixer, for example, a single-screw extruder, a twin-screw extruder, or the like. Examples thereof include a method of melting and mixing using the above, cooling and solidifying, and cutting into a shape such as a pellet for use.

Further, in order to exhibit the effect of the present invention, the crystal nucleating agent in the masterbatch needs to be present in a more uniform state. As a specific method of melting and mixing for that purpose, for example, the following two methods are exemplified.
(A) Method of dissolving the crystal nucleating agent in the resin (b) Method of uniformly finely dispersing the crystal nucleating agent in the resin in a solid state

The method (a) is, for example, by heating the crystal nucleating agent to a temperature at which the entire amount of the crystal nucleating agent contained under a certain shearing state is completely dissolved in the polyolefin resin, that is, a temperature at which the crystal nucleating agent is dissolved in the polyolefin resin. Can be achieved.

The melting temperature depends on the concentration of the crystal nucleating agent, but in the case of the present invention, by applying a certain shear, for example, the barrel temperature of an extruder such as a single-screw extruder or a twin-screw extruder is about 240 ° C. It is possible to dissolve the crystal nucleating agent in the polyolefin resin. Further, by preferably setting the barrel temperature to 250 ° C. or higher, more preferably 260 ° C. or higher, the crystals can be crystallized more stably without being affected by the particle size of the raw material crystal nucleating agent and the degree of shearing depending on the apparatus. The nucleating agent can be dissolved in the resin.

In the case of the method (b), it can usually be uniformly dispersed by applying shearing as much as possible. In that case, it is generally known that the lower the temperature, the higher the viscosity of the resin and the easier it is for shearing.

In the case of a dissolution type crystal nucleating agent as in the present invention, there is a concern about secondary aggregation due to the dissolved crystal nucleating agent, so it is possible to disperse the crystal nucleating agent in the resin as it is in a powder state without dissolving it as much as possible. , It is important to disperse more evenly. Therefore, the heating temperature in the method (b) is preferably set as low as possible, and specifically, for example, the barrel temperature is preferably set as low as possible within the range where melt mixing is possible. More specifically, in the case of the present invention, the barrel temperature is preferably set to about 160 to 210 ° C, more preferably about 180 to 210 ° C, and particularly preferably about 180 to 200 ° C. It is recommended because it can be produced stably without dependence.

Further, in the case of the method (b), since the particles of the added crystal nucleating agent remain as they are, it is desirable to make them into a certain particle shape in advance in order to finely disperse them. Specifically, it is recommended that the average particle size of the crystal nucleating agent is preferably 30 μm or less, more preferably 0.1 to 25 μm, and particularly preferably 0.5 to 15 μm. As long as the average particle size is within the range, the crystal nucleating agent can be dissolved in the polyolefin resin in a shorter time even when the method (a) is used, which is preferable.
As will be described later, the average particle size is a "volume-based cumulative 50% particle size" obtained by using a laser diffraction type particle size distribution meter (wet method).

<Polyolefin resin molded product>
The polyolefin-based resin molded product of the present invention is conventionally used by adding the above-mentioned polyolefin-based resin masterbatch of the present invention and the polyolefin-based resin which is the base resin for dilution, and adding other additives for the polyolefin-based resin as necessary. It is obtained by molding according to the molding method used. The molding method is not particularly limited as long as the effects of the present invention are exhibited, and any conventionally known molding method such as injection molding, extrusion molding, blow molding, pressure molding, rotary molding, or film molding can be adopted.

Further, there is also a method in which the masterbatch and the polyolefin resin and other additives are mixed or melt-mixed in advance before the molding to obtain a polyolefin resin composition, and then the composition is subjected to the molding, which is the object of the present invention. This is an effective method for eliminating the residual undissolved crystal nucleating agent.

[Base resin for dilution]
The base resin for dilution in the present invention is appropriately selected depending on its intended use, purpose, etc., but is basically a polyolefin-based resin, and is the same as or the same as the resin used in the above masterbatch. It is a polyolefin resin having similar properties. Specifically, the same polyolefin resin in the above-mentioned masterbatch is exemplified.

[Other additives]
Examples of the other additives for polyolefin resins include the same additives as in the above-mentioned masterbatch, and the additives may be added alone or as a masterbatch like the crystal nucleating agent.

[Molding method of molded body]
As described above, there are no restrictions on the molding method, and the molding conditions can be appropriately selected from a wide range of conditions conventionally adopted. However, in order to utilize the features of the present invention, the molding temperature is set after dilution. It is preferable that the temperature is equal to or higher than the temperature at which the crystal nucleating agent is completely dissolved in the polyolefin resin, that is, the melting temperature of the crystal nucleating agent or higher, preferably "the melting temperature of the crystal nucleating agent + 10 ° C. or higher".

More specifically, the range of the molding temperature at the time of molding is determined by the concentration of the crystal nucleating agent after dilution, but in the case of the concentration range of the crystal nucleating agent normally used, the temperature is 220 ° C. or higher. If there is, it is possible to obtain a polyolefin-based resin molded product having the effect of the present invention without any problem. Further, preferably, by setting the temperature to 240 ° C. or higher, the polyolefin-based resin molded product of the present invention can be obtained more stably without being affected by the apparatus or the like.

The polyolefin-based resin molded product thus obtained is excellent in optical properties such as transparency and mechanical properties such as impact resistance, and can be used as molded products, sheets, films, automobile parts, electric parts, mechanical parts, and daily life. It is very useful for various purposes such as miscellaneous goods.

Examples will be shown below and the present invention will be described in more detail, but the present invention is not limited to these examples. The abbreviations of the compounds in the examples and application examples, and the measurement of each property are as follows.

[Characteristics of crystal nucleating agent]
(1) Average Particle Size of Crystal Nucleating Agent The average particle size of the crystal nucleating agent was determined by the following method using a laser diffraction type particle size distribution meter (“Mastersizer 3000” manufactured by Malvern Instruments). First, the sample is dispersed in an aqueous solution to which a nonionic surfactant is added as a dispersant by sufficiently stirring and mixing using a wet measurement cell, and then the obtained mixture is further stirred in the apparatus. While circulating, ultrasonic waves were applied to disperse the mixture sufficiently uniformly in the apparatus. Then, the particle size distribution of the sample was measured while applying ultrasonic waves. From the obtained particle size distribution, a volume-based cumulative 50% particle size was determined and used as the average particle size.

[Characteristics of molded product]
Mechanical characteristics (2) Impact resistance: DuPont impact strength The DuPont impact value was measured using a DuPont type impact tester (manufactured by Yasuda Seiki Co., Ltd.) by a method according to JIS K 5400 (1990). A polypropylene resin molded product with a thickness of 2 mm was used as the evaluation sample, and it was carried out 20 times under the conditions of a falling weight of 300 g and a striking core tip size of 1/4 inch, and the average value thereof was calculated as the DuPont impact value ( J). The larger the value, the better the impact resistance.

Optical characteristics / appearance (3) Haze value The haze value was measured by a method according to JIS K7136 (2000) using a haze meter manufactured by Toyo Seiki Seisakusho. As the evaluation sample, a polypropylene-based resin molded product having a thickness of 1 mm was used. The smaller the obtained haze value, the better the transparency.

(4) Evaluation of white spots An injection-molded polypropylene-based resin molded product having a shape of 50 mm × 50 mm × 1 mm was used as an evaluation sample, and the number of white spots in the molded product was counted by visual observation. The obtained results were obtained by taking the average value of five samples and using the number of white spots on the samples, and based on the obtained evaluation results, the results were classified and evaluated in the following three stages.
⊚: The number of white spots is less than 3. There is no problem in the performance of the molded product.
◯: The number of white dots is in the range of 3 to 15. There is no problem in terms of performance as a nuclear agent, but there is a possibility that undispersed substances will affect other physical properties.
X: The number of white spots exceeds 15 and the existence is confirmed. Obviously, the effect is not sufficiently exhibited in terms of the performance of the nuclear agent, and there is a high possibility that the undispersed substance causes problems in various physical properties.

[Example 1]
Preparation of polyolefin-based resin masterbatch 85 parts by weight of polypropylene pellets (R-720; manufactured by Prime Polymer Co., Ltd .; MFR 7 g / 10 minutes (230 ° C.)) as polyolefin-based resin, and 34DMDBS (new) as a crystal nucleating agent component for polyolefin-based resin. 15 parts by weight of a crystal nucleating agent (average particle size 10 μm) in which gelol DXR (manufactured by Nippon Rika Co., Ltd.) (component (A)) and pEDBS (component (B)) are mixed at a ratio (weight ratio) of 60/40 is blended. , A uniaxial extruder (VS-20 manufactured by Tanabe Plastics Machinery Co., Ltd.) was used to melt and mix at a barrel temperature of 250 ° C. The extruded strands were cooled and cut with a pelletizer to obtain a pellet-shaped polyolefin resin masterbatch containing the crystal nucleating agent of the present invention.

Preparation of Polyolefin Resin Mold 1 part by weight of the polyolefin resin master batch obtained above and polypropylene pellets (R-720; manufactured by Prime Polymer Co., Ltd .; MFR 7 g / 10 minutes (230 ° C.)) 74 as a base resin for dilution The parts by weight are dry-blended and molded with an injection molding machine (NS40-5A manufactured by Nissei Resin Industry Co., Ltd.) under the conditions of injection molding temperature (heating temperature) 240 ° C. and mold temperature (cooling temperature) 40 ° C. Polypropylene resin molded articles having a thickness of 1 mm and a thickness of 2 mm were obtained.

Using the molded product obtained above as an evaluation sample, the DuPont impact strength and haze value were measured by the above method, and the obtained results are shown in Table 1. Subsequently, the white spots in the molded product were visually evaluated by the above method, and the results are also shown in Table 1.

[Example 2]
Preparation of a polyolefin-based resin masterbatch using a crystal nucleating agent (average particle size 10 μm) mixed in the same manner as in Example 1 except that the ratio of the component (A) to the component (B) was changed to 40/60. A polyolefin-based resin molded product was prepared, and the obtained molded product was used as a test piece to measure the Dupont impact strength and haze value, and the white spots in the molded product were visually evaluated, and the obtained results were summarized. It is shown in Table 1.

[Example 3]
Preparation of a polyolefin-based resin masterbatch using a crystal nucleating agent (average particle size 10 μm) mixed in the same manner as in Example 1 except that the ratio of the component (A) to the component (B) was changed to 30/70. A polyolefin-based resin molded product was prepared, and the obtained molded product was used as a test piece to measure the Dupont impact strength and haze value, and the white spots in the molded product were visually evaluated, and the obtained results were summarized. It is shown in Table 1.

[Example 4]
Preparation of a polyolefin-based resin masterbatch using a crystal nucleating agent (average particle size 10 μm) mixed in the same manner as in Example 1 except that the ratio of the component (A) to the component (B) was changed to 20/80. A polyolefin-based resin molded product was prepared, and the obtained molded product was used as a test piece to measure the Dupont impact strength and haze value, and the white spots in the molded product were visually evaluated, and the obtained results were summarized. It is shown in Table 1.

[Example 5]
Except that the extruder used at the time of masterbatch preparation was changed to a twin-screw extruder (KZW15TW-45MG-NH manufactured by Technobel Co., Ltd.), the same procedure as in Example 4 was carried out to prepare a polyolefin resin masterbatch and a polyolefin resin. A resin molded product was prepared, and the obtained molded product was used as a test piece to measure the Dupont impact strength and haze value, and the white spots in the molded product were visually evaluated. The obtained results are summarized in Table 1. It was shown to.

[Example 6]
The process was carried out in the same manner as in Example 2 except that the extruder used for masterbatch preparation was a twin-screw extruder and the barrel temperature of the extruder was changed to 180 ° C. to prepare a polyolefin-based resin masterbatch and polyolefin-based resin. The molded product was prepared, the obtained molded product was used as a test piece, the Dupont impact strength and haze value were measured, and the white spots in the molded product were visually evaluated. The results obtained are summarized in Table 1. Indicated.

[Example 7]
A polyolefin-based resin masterbatch was prepared and a polyolefin-based resin molded product was prepared in the same manner as in Example 6 except that the barrel temperature of the extruder at the time of masterbatch preparation was changed to 210 ° C. Using the molded product as a test piece, the Dupont impact strength and haze value were measured, and the white spots in the molded product were visually evaluated. The results obtained are summarized in Table 1.

[Example 8]
A crystal nucleating agent (average particle size 10 μm) mixed in the same manner as in Example 2 was used except that 34DMDBS was used as the component (A) and pMDBS (Gelall MD manufactured by New Japan Chemical Co., Ltd.) was used as the component (B). , Prepare a polyolefin-based resin masterbatch, prepare a polyolefin-based resin molded product, measure the DuPont impact strength and haze value using the obtained molded product as a test piece, and visually evaluate the white spots in the molded product. The results obtained were summarized in Table 2.

[Example 9]
The process was carried out in the same manner as in Example 8 except that the extruder used for masterbatch preparation was a twin-screw extruder and the barrel temperature of the extruder was changed to 210 ° C., and the polyolefin-based resin masterbatch was prepared and the polyolefin-based resin was prepared. The molded product was prepared, the obtained molded product was used as a test piece, the Dupont impact strength and haze value were measured, and the white spots in the molded product were visually evaluated. The results obtained are summarized in Table 2. Indicated.

[Example 10]
Preparation of a polyolefin-based resin masterbatch and polyolefin using a crystal nucleating agent (average particle size 10 μm) mixed in the same manner as in Example 2 except that pMDBS was used as the component (A) and pEDBS was used as the component (B). Prepare a based resin molded product, measure the Dupont impact strength and haze value using the obtained molded product as a test piece, and visually evaluate the white spots in the molded product, and the obtained results are summarized in the table. Shown in 2.

[Example 11]
The process was carried out in the same manner as in Example 10 except that the extruder used for masterbatch preparation was a twin-screw extruder and the barrel temperature of the extruder was changed to 210 ° C., and the polyolefin-based resin masterbatch was prepared and the polyolefin-based resin was prepared. The molded product was prepared, the obtained molded product was used as a test piece, the Dupont impact strength and haze value were measured, and the white spots in the molded product were visually evaluated. The results obtained are summarized in Table 2. Indicated.

[Comparative Example 1]
The same procedure as in Example 5 was carried out except that 34DMDBS was used alone as the crystal nucleating agent to prepare a polyolefin-based resin masterbatch and a polyolefin-based resin molded product, and the obtained molded product was used as a test piece. As a result, the impact strength and haze value of Dupont were measured, and the white spots in the molded product were visually evaluated, and the obtained results are summarized in Table 2.

[Comparative Example 2]
A polyolefin-based resin masterbatch was prepared and a polyolefin-based resin molded product was prepared by carrying out the same procedure as in Comparative Example 1 except that the barrel temperature of the extruder at the time of masterbatch preparation was changed to 180 ° C. Using the molded product as a test piece, the impact strength and haze value of Dupont were measured, and the white spots in the molded product were visually evaluated. The results obtained are summarized in Table 3.

[Comparative Example 3]
The same procedure as in Example 5 was carried out except that pMDBS was used alone as the crystal nucleating agent to prepare a polyolefin-based resin masterbatch and a polyolefin-based resin molded product, and the obtained molded product was used as a test piece. As a result, the impact strength and haze value of Dupont were measured, and the white spots in the molded product were visually evaluated, and the obtained results are summarized in Table 3.

Comparing the results of the examples in Tables 1 and 2 with the results of the comparative examples in Table 3, it is derived from the undispersed or undissolved crystal nucleating agent in the molded product by using the polyolefin resin masterbatch of the present invention. The problem of white spots is solved, and as a result, the crystal nucleating agent is uniformly dissolved in the resin in the molding process, and is uniformly and finely dispersed in the obtained molded product. Optical characteristics (haze value), machine It can be seen that the improvement effect inherent in the crystal nucleating agent on the performance such as the target property (impact resistance) is more exhibited.

The polyolefin-based resin masterbatch according to the present invention is very effective in improving the dispersibility and solubility of the crystal nucleating agent for polyolefin-based resin in the polyolefin-based resin, and the polyolefin-based resin masterbatch of the present invention is used. The produced polyolefin-based resin molded product has no defects such as white spots due to undispersed or undissolved material of the crystal nucleating agent, and is excellent in optical properties such as transparency and mechanical properties such as impact resistance. It is used for various purposes such as automobile parts, electrical parts, mechanical parts, daily miscellaneous goods, cases for clothes, and containers for foods.

Claims (13)

A polyolefin-based resin masterbatch containing a crystal nucleating agent for polyolefin-based resins.
The crystal nucleating agent is a mixture containing the component (A) and the component (B) as main components.
The component (A) is 1,3: 2,4-bis-O- (dimethylbenzylidene) -D-sorbitol, or 1,3: 2,4-bis-O- (methylbenzylidene) -D-sorbitol.
When component (A) is 1,3: 2,4-bis-O- (dimethylbenzylidene) -D-sorbitol, component (B) is 1,3: 2,4-bis-O- (ethylbenzylidene). -D-sorbitol and / or 1,3: 2,4-bis-O- (methylbenzylidene) -D-sorbitol, or
When the component (A) is 1,3: 2,4-bis-O- (methylbenzylidene) -D-sorbitol, the component (B) is 1,3: 2,4-bis-O- (ethylbenzylidene). A polyolefin-based resin masterbatch that is −D-sorbitol and has a ratio (weight ratio) of component (A) to component (B) of 50/50 to 20/80 . The component (A) is 1,3: 2,4-bis-O- (dimethylbenzylidene) -D-sorbitol, and the component (B) is 1,3: 2,4-bis-O- (ethylbenzylidene)-. The polyolefin-based resin masterbatch according to claim 1 , which is D-sorbitol. The polyolefin-based resin masterbatch according to claim 1 or 2 , wherein the concentration of the crystal nucleating agent for the polyolefin-based resin is 10% by weight or more based on the total weight of the polyolefin-based resin masterbatch. The polyolefin-based resin masterbatch according to claim 3 , wherein the concentration of the crystal nucleating agent for the polyolefin-based resin is 12 to 30% by weight. The method for producing a polyolefin-based resin masterbatch according to any one of claims 1 to 4 , wherein a uniaxial extruder or a twin-screw extruder is used, and the barrel temperature of the extruder is changed to the polyolefin resin of the crystal nucleating agent. A method for producing a polyolefin-based resin masterbatch, which comprises melting and mixing a crystal nucleating agent and a polyolefin-based resin at a temperature equal to or higher than that of the above, and then cooling the mixture. The manufacturing method according to claim 5 , wherein the barrel temperature of the extruder is 240 ° C. or higher. The method for producing a polyolefin-based resin masterbatch according to any one of claims 1 to 4 , wherein a twin-screw extruder is used, and the barrel temperature of the extruder is in the range of 160 to 210 ° C. A method for producing a polyolefin-based resin masterbatch, which comprises melting and mixing a polyolefin-based resin and then cooling the mixture. The production method according to claim 7 , wherein the average particle size of the crystal nucleating agent used is 30 μm or less. A method for producing a polyolefin-based resin composition, which comprises mixing or melt-mixing the polyolefin-based resin masterbatch according to any one of claims 1 to 4 and a polyolefin-based resin as a base resin for dilution. A polyolefin-based resin molded product according to any one of claims 1 to 4 , wherein the raw material of the crystal nucleating agent component is the polyolefin-based resin masterbatch according to any one of claims 1 to 4 . A polyolefin-based resin molded product comprising the polyolefin-based resin masterbatch according to any one of claims 1 to 4 and a polyolefin-based resin as a base resin for dilution. A method for producing a polyolefin-based resin molded product, which comprises using the polyolefin-based resin masterbatch according to any one of claims 1 to 4 and a polyolefin-based resin as a base resin for dilution. The production method according to claim 12 , wherein the molding temperature in the production of the molded product is equal to or higher than the temperature at which the entire amount of the crystal nucleating agent after dilution is dissolved in the polyolefin resin.