JP2018044093A - Nucleating agent for granular polyolefin-based resin having improved flowability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for improving flowability of a nucleating agent for polyolefin-based resin, and to provide a polyolefin-based resin composition which contains a nucleating agent having improved flowability and is excellent in transparency, and a molded body of the same.SOLUTION: There are provided a polyolefin-based resin composition which can easily improve flowability using a nucleating agent for granular polyolefin-based resin granulated by a specific method, and is excellent in transparency using the granular crystal nucleating agent; and a molded body of the same.

Description

  The present invention relates to improvement of fluidity of a crystal nucleating agent for polyolefin resin, and more specifically, a method for improving fluidity by granulation, and a crystal for granular polyolefin resin having improved fluidity including the method. Method for producing nucleating agent, improved flowability of crystalline nucleating agent for granular polyolefin resin obtained by the method, polyolefin resin composition having excellent transparency comprising the crystal nucleating agent and molding thereof About the body.

  Polyolefin 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 resins are crystalline resins, and are often used with the addition of a crystal nucleating agent for the purpose of improving production efficiency and for the purpose of 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, a metal salt of a carboxylic acid or a phosphate ester, and further dissolved in an organic crystal nucleating agent. There are crystal nucleating agents of type and non-dissolving type. In order to improve optical properties such as transparency, a dissolution type organic crystal nucleating agent typified by the diacetal compound is particularly effective and often used.

  One of the characteristics of general-purpose plastics, especially polyolefin-based resins, is that they are inexpensive. For this purpose, it is important to have excellent productivity, and shortening the molding cycle by adding a crystal nucleating agent as described above. Various ideas are made. The feed property of the raw material is one of them, and it is necessary to be excellent in the feed property of each raw material, that is, its fluidity. However, the above-mentioned crystal nucleating agents, especially diacetal-based crystal nucleating agents, have poor fluidity, which is a big problem in productivity.

  For this reason, various studies have been made so far on improving the fluidity of crystal nucleating agents including diacetal compounds. For example, a method of improving fluidity by granulating (Patent Documents 1 to 3), a method of improving fluidity by adding a fluidity improver without granulating (Patent Documents 4 to 7), etc. Proposed and used in practice.

  In recent years, in general-purpose plastics, further improvement in productivity has been demanded, and further improvement in feedability of raw materials, that is, fluidity thereof has been demanded. Further improvement of the fluidity of the crystal nucleating agent was a major issue in improving productivity.

As described above, fluidity improving methods are not limited to crystal nucleating agents, and the following two methods are generally known and widely used.
(1) Method for controlling particle shape such as particle size (2) Method for adding additive effective for improving fluidity, ie, fluidity improver

  As described above, the demand for liquidity has become increasingly severe in recent years, and it has been difficult for the method (2) to sufficiently satisfy the demand. Therefore, the method (1) is often used in applications where stricter fluidity is required.

  In the case of the method (1), generally, the larger the particle size, the better the fluidity. The method of granulating by mixing with the nucleating agent alone or with other additives, or mixing with a resin in advance to form a masterbatch The method to do is used as a general-purpose method.

  However, when granulated, the fluidity is improved, but the dispersibility and solubility in the polyolefin resin tend to deteriorate, and as a result, not only the performance such as the original transparency of the nucleating agent is deteriorated. In addition, there is a concern that appearance problems such as white spots may occur, and in particular, in a field where demands for dispersibility and the like are severe, a method of adding an additive such as a binder is common, and selection thereof is important.

  Various compounds have been studied as the binder, and organic acid monoglycerides widely used as additives for polyolefins as antistatic agents and lubricants are known as easy-to-use binders.

  In addition, the granulating method is also important for fluidity, and various studies have been made so far regarding the method, and at present, the extrusion granulation method and the compression granulation method are widely used. Widely used.

  On the other hand, as a recent trend, in consideration of environmental issues as a whole, and in order to ensure flexibility in formulation, the amount of ingredients other than crystal nucleating agents has been reduced as much as possible. A method of granulating with a binder is desired. Further, depending on the application, there is a case where the blending of the binder may affect the performance of the nucleating agent itself, and reduction of the binder amount has been awaited from that viewpoint. However, in the above-described extrusion granulation method and compression granulation method, granulation is difficult unless a certain amount of binder is included, and there is a limit to the reduction of the binder amount.

  Furthermore, depending on the use, the requirements for dispersibility and solubility in the above-mentioned resin have become more severe, and it has been necessary to add a large amount of a binder having a relatively low melting point such as an organic acid monoglyceride. However, in that case, the occurrence of new problems such as caking caused by the binder has been pointed out, and improvement has been required.

  In particular, in the case of a crystal nucleating agent such as a diacetal compound, there are problems such as secondary agglomeration, and further, it is known that dispersibility and solubility in a molten resin greatly affect the nucleating agent performance. However, it is difficult to sufficiently satisfy all the requirements in the granulation using a conventionally known system, and there is a strong demand for improvement.

WO98 / 33851 JP 2001-81236 A WO02 / 077094 Special table 2009-507982 JP 2013-20962 A Japanese Patent Laying-Open No. 2015-30849 Japanese Patent No. 5920524

  The present invention relates to a method for improving the fluidity of a crystal nucleating agent for polyolefin resins by granulation, a method for producing a crystal nucleating agent for granular polyolefin resin having improved fluidity, including the method, and the method. Another object of the present invention is to provide a crystal nucleating agent for granular polyolefin resin having improved fluidity, a polyolefin resin composition having excellent transparency, and a molded product thereof, which further comprises the crystal nucleating agent.

  In view of the above situation, the present inventors have intensively studied to solve the above problems, and as a result, by blending a specific compound having a binder effect at a specific ratio, and further stirring and mixing under specific conditions. It is possible to produce a crystal nucleating agent for a granular polyolefin resin with a small amount of a specific compound used, and the obtained crystal nucleating agent for a granular polyolefin resin has no problems such as caking, The polyolefin resin composition comprising the crystal nucleating agent and the molded product thereof are also excellent in transparency. The headline and the present invention were completed.

  That is, the present invention was obtained by the following method for improving the fluidity of a crystal nucleating agent for polyolefin resins, a method for producing a crystal nucleating agent for granular polyolefin resins having improved fluidity, and the method. A granular nucleating agent for a granular polyolefin resin having improved flowability, a polyolefin resin composition having excellent transparency, and a molded product thereof, comprising the crystal nucleating agent.

[Item 1] A crystal nucleating agent for polyolefin-based resins, (B) an organic acid monoglyceride, and (C) a crystal nucleating agent for granular polyolefin-based resins comprising an organic compound having a melting point of 100 ° C. or higher.
The proportion of the component (A) in the granular polyolefin resin crystal nucleating agent is 60 to 80% by weight, the proportion of the component (B) is 10 to 30% by weight, and the components (B) and (C ) The total proportion of the components is 20-40% by weight,
The proportion of the component (B) in the total amount of the component (B) and the component (C) is 30 to 80% by weight, and the granular polyolefin resin crystal nucleating agent has a powder temperature of (B A crystal nucleating agent for a granular polyolefin-based resin, which is heated and mixed while being controlled within a temperature range of not less than the melting point of the component) and not more than the melting point of the component (C).

[Item 2] The ratio of the component (A) is 65 to 75% by weight, the ratio of the component (B) is 13 to 25% by weight, and the total ratio of the component (B) and the component (C) is 25 to 35% by weight. The crystal nucleating agent for granular polyolefin resin according to [Item 1].

[Claim 3] The granular polyolefin according to [Claim 1] or [Claim 2], wherein the proportion of the component (B) in the total amount of the component (B) and the component (C) is 35 to 75% by weight. -Based crystal nucleating agent.

[Claim 4] The granular polyolefin resin according to any one of [Claim 1] to [Claim 3], wherein the component (B) is a monoglyceride of a fatty acid that may have at least one hydroxyl group in the molecule. Crystal nucleating agent.

[Claim 5] The crystalline polyolefin resin crystal nucleating agent according to [Claim 4], wherein the fatty acid is a saturated fatty acid having 14 to 22 carbon atoms.

[Item 6] The granular polyolefin resin according to Item 5, wherein the saturated fatty acid is one or more fatty acids selected from the group consisting of 12-hydroxystearic acid, stearic acid, and behenic acid. Crystal nucleating agent.

[Claim 7] The crystal nucleating agent for granular polyolefin resin according to [Claim 6], wherein the saturated fatty acid is stearic acid.

[Item 8] The component (C) is one selected from the group consisting of an alkali or alkaline earth metal salt of a saturated fatty acid having 14 to 22 carbon atoms, a hindered phenol compound, and a phosphite compound. Or the crystal nucleating agent for granular polyolefin resin in any one of [Item 1]-[Item 7] which is a 2 or more types of compound.

[Item 9] The component (C) is pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and / or tris (2,4-di-t-butylphenyl). The crystal nucleating agent for granular polyolefin resin according to [Item 8], which is a phosphite.

[Claim 10] The granular polyolefin resin according to [Claim 9], wherein the component (C) is pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]. Crystal nucleating agent.

[Item 11] The crystal nucleating agent for a granular polyolefin resin according to any one of [Item 1] to [Item 10], wherein the powder temperature during the heating and mixing is 50 to 120 ° C.

[Item 12] The granular polyolefin resin crystal nucleating agent according to any one of [Item 1] to [Item 11] is used as a core, and particles of (D) a polyolefin resin crystal nucleating agent adhere to the core. A crystal nucleating agent for a granular polyolefin-based resin, characterized in that it is in a finished state.

[Claim 13] The granular polyolefin system according to [Claim 12], wherein the adhesion amount of component (D) is 1 to 20 parts by weight with respect to 100 parts by weight of the crystal nucleating agent for granular polyolefin resin in the core part. Crystal nucleating agent for resin.

[Item 14] The granular polyolefin system according to [Item 13], wherein the adhesion amount of the component (D) is 5 to 15 parts by weight with respect to 100 parts by weight of the crystal nucleating agent for the granular polyolefin resin in the core part. Crystal nucleating agent for resin.

[Item 15] The repose angle of the granular polyolefin resin crystal nucleating agent is 40 degrees or less, and the compression ratio obtained from the loose bulk density or the bulk density is 1.2 or less, [Item 1] to [Item 1] Item 14.] A crystal nucleating agent for a granular polyolefin resin according to any one of Items 14].

[Item 16] The crystal nucleating agent for granular polyolefin resin according to [Item 15], wherein the angle of repose is 35 degrees or less, and the compression ratio obtained from the loose bulk density and hence the bulk density is 1.1 or less. .

[Section 17] In a screening test conducted under conditions according to JIS K0069 (1992), the ratio of the residue on the JIS test sieve having an aperture of 600 μm to the total weight is 10% by weight or more. [Claim 16] The crystal nucleating agent for polyolefin resin according to any one of [16].

[Item 18] The granular form according to any one of Items 1 to 17, wherein the component (A) and / or the component (D) is a diacetal compound represented by the following general formula (1). Crystal nucleating agent for polyolefin resin.
[In Formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched carbon. An alkoxy group having 1 to 4 carbon atoms, a linear or branched alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom is shown. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkenyl group having 2 to 4 carbon atoms, or a linear or branched carbon atom. The hydroxyalkyl group of number 1-4 is shown. m and n each represent an integer of 1 to 5. p represents 0 or 1; Two R ¹ may be bonded to each other to form a tetralin ring together with a benzene ring to which they are bonded. Two R ² groups may be bonded to each other to form a tetralin ring together with the benzene ring to which they are bonded. ]

[Item 19] In the general formula (1), R ¹ and R ² are the same or different, and are a methyl group or an ethyl group, R ³ is a hydrogen atom, and m and n are 1 or 2. The crystal nucleating agent for granular polyolefin resin according to [Item 18], which is an integer and p is 1.

[Item 20] In the general formula (1), R ¹ and R ² are the same or different and are a propyl group or a propoxy group, R ³ is a propyl group or a propenyl group, and m and n are 1 The crystal nucleating agent for granular polyolefin resin according to [Item 18], wherein p is 1.

[Item 21] The crystal nucleating agent for granular polyolefin resin according to any one of [Item 1] to [Item 20], wherein the crystal nucleating agent for granular polyolefin resin is a heat-stir granulated product.

[Item 22] A method for producing a crystal nucleating agent for granular polyolefin resin with improved fluidity, comprising:
(I) (A) Crystal nucleating agent for polyolefin resin, (B) organic acid monoglyceride, and (C) organic compound having melting point of 100 ° C. or higher, powder temperature and melting point of component (B) (C) A production method comprising the step of stirring and granulating while controlling the temperature range between the melting points of the components.

[Item 23] The proportion of the component (A) in step (i) is 60 to 80% by weight, the proportion of the component (B) is 10 to 30% by weight, and the sum of the components (B) and (C) [Claim 22], wherein the proportion of the component (B) in the total amount of the component (B) and the component (C) is 30 to 80% by weight. Production method.

[Item 24] The proportion of the component (A) in the step (i) is 65 to 75% by weight, the proportion of the component (B) is 13 to 25% by weight, and the sum of the components (B) and (C) The ratio of the component (B) is 35 to 75% by weight, and the ratio of the component (B) in the total amount of the component (B) and the component (C) is 35 to 75% by weight. Production method.

[Item 25] After the step (i) according to any one of the items [Item 22] to [Item 24], (ii) the crystal nucleating agent for the granular polyolefin resin obtained in the step (i) is further ( D) Production comprising adding a crystal nucleating agent for polyolefin resin and heating and mixing while controlling the powder temperature to a temperature range above the melting point of component (B) and below the powder temperature of step (i) Method.

[Item 26] The amount of component (D) in step (ii) is 1 to 20 parts by weight with respect to 100 parts by weight of the crystalline polyolefin resin crystal nucleating agent obtained in step (i). The production method according to [25].

[Item 27] The blending amount of the component (D) in the step (ii) is 5 to 15 parts by weight with respect to 100 parts by weight of the granular polyolefin resin crystal nucleating agent obtained in the step (i). The production method according to [Item 26].

[Item 28] The production according to any one of items [22] to [27], wherein the powder temperature in the step (i) is in the range of not less than the melting point of the component (B) and not more than the melting point of the component (C). Method.

[Item 29] The powder temperature in the step (ii) is in the range of the melting point of the component (B) to the melting point of the component (B) + 50 ° C. and lower than the powder temperature in the step (i) [item 25]. ] To [Item 28].

[Claim 30] The production method according to any one of [Claim 22] to [Claim 29], wherein the component (A) and / or the component (D) is a diacetal compound represented by the following general formula (1). .
[In Formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched carbon. An alkoxy group having 1 to 4 carbon atoms, a linear or branched alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom is shown. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkenyl group having 2 to 4 carbon atoms, or a linear or branched carbon atom. The hydroxyalkyl group of number 1-4 is shown. m and n each represent an integer of 1 to 5. p represents 0 or 1; Two R ¹ may be bonded to each other to form a tetralin ring together with a benzene ring to which they are bonded. Two R ² groups may be bonded to each other to form a tetralin ring together with the benzene ring to which they are bonded. ]

In [Claim 31] the general formula (1), ^{R 1} and ^{R 2} are the same or different, a methyl group or an ethyl group, and, ^{R 3} is a hydrogen atom, m and n is 1 or 2 The production method according to [30], which is an integer and p is 1.

[Item 32] In the general formula (1), R ¹ and R ² are the same or different, and are a propyl group or a propoxy group, R ³ is a propyl group or a propenyl group, and m and n are 1 And the production method according to [30], wherein p is 1.

[Item 33] The production method according to any one of Items 22 to 32, wherein the component (B) is a monoglyceride of a fatty acid that may have at least one hydroxyl group in the molecule.

[Item 34] The production method according to Item 33, wherein the fatty acid is a saturated fatty acid having 14 to 22 carbon atoms.

[Item 35] The production method according to Item 34, wherein the saturated fatty acid is one or more fatty acids selected from the group consisting of 12-hydroxystearic acid, stearic acid, and behenic acid.

[Item 36] The production method according to Item 35, wherein the saturated fatty acid is stearic acid.

[Item 37] The component (C) is one selected from the group consisting of an alkali or alkaline earth metal salt of a saturated fatty acid having 14 to 22 carbon atoms, a hindered phenol compound, and a phosphite compound. Or the manufacturing method in any one of [Item 22]-[Item 35] which is two or more types of compounds.

[Item 38] The component (C) is pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and / or tris (2,4-di-t-butylphenyl). ) The production method according to Item 37, which is a phosphite.

[Item 39] The production method according to Item 38, wherein the component (C) is pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].

[Item 40] A polyolefin resin composition comprising a polyolefin resin and a crystal nucleating agent for a granular polyolefin resin according to any one of [Item 1] to [Item 21].

[Item 41] The polyolefin resin composition according to [Item 40], wherein the content of the crystal nucleating agent for the granular polyolefin resin is 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyolefin resin. .

[Item 42] The polyolefin resin composition according to Item 41, wherein the content is 0.01 to 5 parts by weight.

[Item 43] A polyolefin-based resin molded article using the polyolefin-based resin composition according to any one of [Item 40] to [Item 42] as a raw material.

[Item 44] (A) Crystal nucleating agent for polyolefin-based resin, (B) organic acid monoglyceride and (C) an organic compound having a melting point of 100 ° C. or higher, powder temperature is higher than melting point of component (B), (C ) A method for improving the fluidity of a crystal nucleating agent for polyolefin resin, which is granulated by stirring and mixing while controlling within a temperature range below the melting point of the component.

[Item 45] The polyolefin resin crystal nucleating agent granulated in the above method and the added (D) polyolefin resin crystal nucleating agent have a powder temperature equal to or higher than the melting point of the component (B), The fluidity improving method according to [Item 44], wherein the mixture is stirred and mixed into a granule while being controlled within a temperature range lower than the powder temperature during the stirring and mixing.

  The crystal nucleating agent for granular polyolefin resin of the present invention is very excellent in fluidity and can greatly contribute to improvement of productivity. Further, the crystal nucleating agent for granular polyolefin resin of the present invention is equivalent to the conventional crystal nucleating agent in terms of dispersibility and solubility in polyolefin resin, which is very important especially for diacetal compounds. It has the above performance and can exhibit very excellent performance as a crystal nucleating agent for polyolefin resin. Therefore, the crystal nucleating agent for granular polyolefin resin of the present invention can be widely used in various applications, and the obtained molded product has very excellent transparency, and has many uses. It is useful in. Furthermore, the crystal nucleating agent for granular polyolefin resin of the present invention produced by the production method comprising the step (ii) is free from problems such as caking caused by a specific compound having a binder effect, and can be used in a wider range of applications. Application to is possible.

<Crystal nucleating agent for granular polyolefin resin>
The crystal nucleating agent of the present invention is granular, and the granular crystal nucleating agent is obtained by adding (A) a predetermined amount of ( B) Add organic acid monoglyceride and (C) an organic compound having a melting point of 100 ° C. or higher, and mix by heating while controlling the powder temperature to a temperature range between the melting point of component (B) and the melting point of component (C). Can be obtained. The heating mixing means mixing the components under heating, and the mixing method is not particularly limited as long as the effects of the present invention can be obtained, but a preferable method is mixing by stirring. The method (stir mixing) is recommended. That is, a method of granulating while mixing by stirring (stirring granulation) is particularly recommended as a method for obtaining the granular form of the present invention. The granular polyolefin resin crystal nucleating agent (heated and agglomerated product) that has been granulated with stirring under heating is particularly advantageous in terms of performance such as fluidity.

  In the present invention, it was difficult to confirm the reason why the above effect was obtained. However, the component (B) completely melted by the preparation under the above conditions is uniform in the aggregated particles of the component (A). It is presumed that the binder effect of the component (B) is adjusted by allowing the component (C), which is not completely melted, to coexist with the component (B). In other words, the component (B) alone has a concern about a decrease in dispersibility due to granulation which is generally known, but by coexisting with the component (C), the binder effect is adjusted and there is a concern about a decrease in dispersibility. Presumed to have disappeared. Further, it is presumed that the concern such as caking is reduced by the coexistence of the component (C) having a high melting point. From the above estimation, it is considered that the mixing condition and the mixing ratio are very important requirements in the present invention.

  Further, depending on the use, problems such as caking caused by the component (B) having a binder effect even under the above conditions may occur.In that case, in the granular crystal nucleating agent of the present invention obtained above, Furthermore, the powder obtained by adding the powder of the crystal nucleating agent for polyolefin resin (D) obtained by the usual production method, and preparing the core part in the first stage with the powder temperature equal to or higher than the melting point of the component (B) By stirring and mixing while controlling the temperature range below the body temperature, it is possible to obtain a granular polyolefin resin crystal nucleating agent in which problems such as caking are solved. Generally, caking in the resin additive composition is considered to be caused by a component having a low melting point, that is, the component (B) in the present invention. Therefore, the most effective method is to reduce the amount of the component, but in that case, sufficient granulation cannot be performed, and the originally intended performance improvement such as fluidity and dispersibility becomes insufficient. It is becoming difficult to meet the strict requirements of the company. Therefore, as a result of various studies on methods for solving the problems such as caking while maintaining the fluidity and dispersibility of the object of the present invention, the present inventors are not clear but the reason is as follows. This led to the conclusion that problems such as caking could be resolved. In this case, the boundary is unclear and difficult to confirm by visual inspection or the like, but it is assumed that most of the added component (D) is in a state of adhering to the surface of the granular crystal nucleating agent, Such a state is considered to be particularly important for suppressing caking.

  The shape of the crystal nucleating agent for polyolefin resin as the component (A) and the component (D) is not particularly limited as long as the effect of the present invention is exhibited, but preferably the average particle diameter obtained by laser diffraction particle size distribution measurement Is preferably in a powder form of 0.01 to 15 μm, more preferably in a powder form of 0.1 to 10 μm. When the average particle size is 0.01 μm or more, granulation tends to be facilitated, and when the average particle size is 15 μm or less, the granular crystal nucleating agent of the present invention is dispersed in the polyolefin resin. There is a tendency to positively affect the properties and solubility.

  It is important that the granular crystal nucleating agent of the present invention is granular from the viewpoint of fluidity, and preferably for a JIS test having a mesh size of 600 μm in a screening test performed under conditions according to JIS K0069 (1992). It is recommended that the ratio of the residue on the sieve to the total weight be 10% by weight or more, more preferably 20% by weight or more. Here, in order to adjust the particle size of the granular crystal nucleating agent with a small amount of component (B) or component (C), the stirring granulation method was most advantageous.

  The granular crystal nucleating agent of the present invention is recommended to have an angle of repose of preferably 40 degrees or less, more preferably 35 degrees or less, from the viewpoint of improving fluidity. If the angle of repose exceeds 40 degrees, sufficient fluidity tends to be difficult to obtain.

  Furthermore, it is recommended that the granular crystal nucleating agent of the present invention has a compression ratio (for example, bulk density / loose bulk density) obtained from the loose bulk density and the bulk density is 1.2 or less. In general, the closer the compression ratio is to 1, the more excellent the fluidity tends to be. In the present invention, the compression ratio is closer to 1 compared to a normal powdery crystal nucleating agent, which is effective for improving the fluidity. Is presumed to have brought

  The laser diffraction particle size distribution measurement can be performed by a general-purpose method and condition using a general-purpose apparatus. For example, using a laser diffraction particle size distribution meter (Malvern Instruments, “Mastersizer 3000”), the sample is placed in an aqueous solution to which a surfactant is added as a dispersant by sufficiently stirring and mixing in a wet measurement cell. Then, while further stirring and circulating the resulting mixture in the apparatus, apply ultrasonic waves to disperse sufficiently uniformly in the apparatus, and then apply the ultrasonic waves to determine the particle size distribution of the sample. Can be measured. From the obtained particle size distribution, an average particle size, that is, a volume-based cumulative 50% particle size (median diameter: d50) can be obtained.

  The screening test can be performed using a general-purpose sieve conforming to the JIS standard according to JIS K0069 (1992). Specifically, a sieving test is performed under the conditions in accordance with 6.1 of JIS K0069 (1992), the weight of the residue on the JIS test sieve having an aperture of 600 μm is measured, and all the samples used in the test are measured. The ratio to the weight was determined.

(A) component; crystal nucleating agent for polyolefin resin, and
Component (D): Crystal nucleating agent for polyolefin resin (A) Component nucleating agent for polyolefin resin and component (D) crystal nucleating agent for polyolefin resin are, for example, diacetal compounds and carboxylic acids. Examples thereof include salt compounds, phosphate ester salt compounds, amide compounds, rosin compounds and the like, which may be the same as or different from the types of component (A) and component (D), preferably component (A) ( D) It is recommended that the components are of the same type. Among these, the effect of the present invention is most remarkable in the diacetal compound. However, the type is not particularly limited as long as the effect of the present invention is exhibited.

Specific examples of the diacetal compound include diacetal compounds represented by the following general formula (1).
[In Formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched carbon. An alkoxy group having 1 to 4 carbon atoms, a linear or branched alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom is shown. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkenyl group having 2 to 4 carbon atoms, or a linear or branched carbon atom. The hydroxyalkyl group of number 1-4 is shown. m and n each represent an integer of 1 to 5. p represents 0 or 1; Two R ¹ may be bonded to each other to form a tetralin ring together with a benzene ring to which they are bonded. Two R ² groups may be bonded to each other to form a tetralin ring together with the benzene ring to which they are bonded. ]

Among the diacetal compounds, more preferable compounds include, for example, R ¹ and R ² in the general formula (1) are the same or different, and are a methyl group or an ethyl group, and R ³ is a hydrogen atom. A compound in which m and n are integers of 1 or 2, and p is 1, or R ¹ and R ² in the general formula (1) are a propyl group or a propyloxy group, and R ³ is Examples thereof include a propyl group or a propenyl group, m and n are 1, and p is 1.

The following compounds can also be exemplified as further preferred compounds; in the general formula (1), R ¹ and R ² are a propyl group or a propyloxy group, and R ³ is a propyl group or a propenyl. A compound wherein m and n are 1 and p is 1.

Specific examples of the diacetal compound include the following compounds. 1,3: 2,4-di-O-benzylidene-D-sorbitol, 1,3: 2,4-bis-O- (methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O -(O-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p- Methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (ethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (o-ethylbenzylidene) -D- Sorbitol, 1,3: 2,4-bis-O- (m-ethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol, 1, 3: 2,4-bis-O- (o-isopropyl Benzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-isopropylbenzylidene) -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- (on-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, -Bis-O- (ot-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (mt-butylbenzylidene) -D-sorbitol, 1,3: 2,4 -Bis-O- (pt-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (dimethylbenzylidene) -D-sorbitol, 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, 1,3 : 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D Sorbitol, 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'-diethylbenzylidene) -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-methoxy) Benzylidene) -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, , 3: 2,4-bis-O- (p-ethoxybenzili ) -D-sorbitol, 1,3: 2,4-bis-O- (o-isopropoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-isopropoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-isopropoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (on-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- Sorbito 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-ethoxycarbonylbenzylidene) -D-sorbitol, , 3: 2,4-bis-O- (o-isopropoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-isopropoxycarbonylbenzylidene) -D-sorbitol, , 3: 2,4-bis-O- (p-isopropoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (on-propoxycarbonyl) Benzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (mn-propoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (pn- 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, -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'-dimethylbenzylidene) -D-sorbitol, 1,3 -O- (3 ', 4'-dimethylbenzylidene) -2,4-O-benzylidene-D-sorbitol, 1,3-O- (p-methylbenzylidene) -2,4-O- (p-ethylbenzylidene) ) -D-sorbitol, 1,3-O- (p-ethylbenzylidene) -2,4-O- (p-methylbenzylidene) -D-sorbitol, 1,3-O- (p-methylbenzylidene) -2 , 4-O- (3 ′, 4′-di Methylbenzylidene) -D-sorbitol, 1,3-O- (3 ′, 4′-dimethylbenzylidene) -2,4-Op-methylbenzylidene-D-sorbitol, 1,3-O- (p-ethyl) Benzylidene) -2,4-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol, 1,3-O- (3 ′, 4′-dimethylbenzylidene) -2,4-Op-ethyl Benzylidene-D-sorbitol, 1,3-O- (p-methylbenzylidene) -2,4-O- (p-chlorobenzylidene) -D-sorbitol, 1,3-O- (p-chlorobenzylidene) -2 , 4-O- (p-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3 ′, 4′-dichlorobenzylidene) -D-sorbitol, 1,3: 2,4 -Bis-O-benzylidene-1 Methylsorbitol, 1,3: 2,4-bis-O- (p-methylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -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′-dimethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O— (2 ′, 5 '-Dimethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2', 6'-dimethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O -(3 ', 4'-dimethylbenzylidene) -1 Methyl sorbitol, 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'-diethylbenzylidene) -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, , 3: 2,4-bis-O- (3′-methyl-4′-me Xylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (3 ′, 4′-dichlorobenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O— ( p-methoxycarbonylbenzylidene) -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-benzylidene-1-ethylsorbitol, 1,3: 2,4-bis -O- (p-methylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O -(Pn-propy Rubenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -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'-dimethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -1-ethylsorbitol, , 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-ethylsorbitol, 1,3: 2,4-bis-O- (2', 5'-diethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4 -Bis-O- (2 ', 6'-diethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3', 4'-diethylbenzylidene) -1-ethylsorbitol, , 3: 2,4-bis-O- (3 ′, 5′-diethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3′-methyl-4′-methoxybenzylidene) ) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3 ′, 4′-dichlorobenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O— (p— Methoxycarbonylbenzylidene) -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-propyl sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-n-propyl sorbitol, 1,3: 2,4-bis-O- (pn- Propylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -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'-dimethylbenzylidene) -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'- Diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3 ′, 5′-diethylbenzylidene) -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- (p-ethoxycarbonylbenzylidene)- 1-n-propyl sorbitol, 1,3 2,4-bis-O- (p-propoxycarbonylbenzylidene) -1-n-propylsorbitol, 1,3-O- (pn-propylbenzylidene) -2,4-O- (p-propoxybenzylidene) -1-n-propylsorbitol, 1,3-O- (p-propoxybenzylidene) -2,4-O- (pn-propylbenzylidene) -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-propyl sorbitol, 1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-propenylsorbitol, 1,3: 2,4-bis-O- (p-ethoxycarbonyl) Nidylidene) -1-propenylsorbitol, 1,3: 2,4-bis-O- (p-propoxycarbonylbenzylidene) -1-propenylsorbitol, 1,3-O- (pn-propylbenzylidene) -2, 4-O- (p-propoxybenzylidene) -1-propenyl sorbitol, 1,3-O- (p-propoxybenzylidene) -2,4-O- (pn-propylbenzylidene) -1-propenyl sorbitol, , 3: 2,4-bis-O-benzylidene-1-allylsorbitol, 1,3: 2,4-bis-O- (p-methylbenzylidene) -1-allylsorbitol, 1,3: 2,4- Bis-O- (p-ethylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-allylso Rubitol, 1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O— (2 ′, 4′-dimethyl) Benzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (2 ′, 5′-dimethylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O— (2 ', 6'-dimethylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -1-allylsorbitol, 1,3: 2,4- Bis-O- (3 ′, 5′-dimethylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O— (2 ′, 3′-diethylbenzylidene) -1-allylsorbitol, 1, 3: 2,4-bis-O- (2 ′, 4′-diethylbenzylidene ) -1-allylsorbitol, 1,3: 2,4-bis-O- (2 ′, 5′-diethylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O— (2 ′) , 6'-diethylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (3 ', 4'-diethylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis -O- (p-ethoxycarbonylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (p-propoxycarbonylbenzylidene) -1-allylsorbitol, 1,3-O- (p- n-propylbenzylidene) -2,4-O- (p-propoxybenzylidene) -1-allylsorbitol, 1,3-O- (p-propoxybenzylidene) -2,4-O- (pn-propylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (3 ′, 5′-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O— (3 '-Methyl-4'-methoxybenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (3 ′, 4′-dichlorobenzylidene) -1-allylsorbitol, 1,3: 2, 4-bis-O- (p-methoxycarbonylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (3′-methyl-4′-fluorobenzylidene) -1-allylsorbitol, , 3: 2,4-bis-O- (3′-bromo-4′-ethylbenzylidene) -1-allylsorbitol and the like.

  Particularly preferred embodiments include 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D. -Sorbitol, 1,3: 2,4-bis-O- (3 ', 4'-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (pn-propylbenzylidene) Examples include -1-propyl sorbitol.

  Moreover, although the diacetal compound of the said specific aspect may be used independently, from a viewpoint of other performance, for example, low temperature workability, it uses it in the aspect which used 2 or more types of diacetal compounds together, or mixed beforehand. Also good.

  When used in the above combination or mixed system, for example, 1,3: 2,4-di-O-benzylidene-D-sorbitol and 1,3: 2,4-bis-O- (p-methylbenzylidene) -D- Combination of sorbitol and 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol and 1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene)- A combination of D-sorbitol, 1,3: 2,4-dibenzylidene-D-sorbitol and 1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol and 1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p- Lorobenzylidene) -D-sorbitol and 1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O— (3 ′ , 4'-dichlorobenzylidene) -D-sorbitol and 1,3: 2,4-bis-O- (3 ', 4'-dimethylbenzylidene) -D-sorbitol, and the like are exemplified. May be used after being finely pulverized.

  The diacetal compound is produced by, for example, a method described in Japanese Patent Publication No. 48-43748, JP-A 53-5165, JP-A 57-185287, JP-A-2-231488, and the like. Etc., and can be easily manufactured. In addition, those currently marketed as crystal nucleating agents for polyolefins, for example, Milad 3988 and Milad NX8000 manufactured by Milliken (USA), Gelall D, Gelall MD, Gelall DXR, etc. from Shin Nippon Rika Co., Ltd. are used as they are. Also good.

Examples of the crystal nucleating agent other than the diacetal compound include sodium benzoate, aluminum pt-butylbenzoate, cyclohexanedicarboxylic acid metal salt represented by the following general formula (3), and general formula (4 ) Carboxylate compounds such as norbornane dicarboxylic acid metal salts, phosphoric ester salt compounds represented by the following general formula (5), amide compounds represented by the following general formula (6), and the following general formula Examples thereof include rosin compounds such as rosin acid represented by (7) or metal salt compounds thereof (for example, alkali metal salts such as lithium, sodium, potassium and magnesium).
[Wherein, M ₁ and M ₂ are both lithium ions, or a single metal selected independently from the group consisting of calcium, strontium, zinc, magnesium and monobasic aluminum. R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and are a hydrogen atom, an alkyl having 1 to 9 carbon atoms. A group (wherein any two vicinal (bonded to adjacent carbon) or geminal (bonded to the same carbon) alkyl groups may together form a hydrocarbon ring having up to 6 carbon atoms). , A hydroxy group, an alkoxy group having 1 to 9 carbon atoms, an alkyleneoxy group having 1 to 9 carbon atoms, an amino group and an alkylamino group having 1 to 9 carbon atoms, a halogen atom (fluorine, chlorine Are each selected from the group consisting of bromine and iodine) and phenyl group. ]
Wherein M ₃ and M ₄ are the same or different and are independently selected from the group consisting of metal cations or organic cations, or the two metal ions are combined into a single metal ion (two Valence, such as calcium), R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, Hydroxy group, C1-C9 alkoxy group, C1-C9 alkyleneoxy group, amino group, and C1-C9 alkylamino group, halogen atom, phenyl group, alkylphenyl group, and up to 9 Each of the metal cations is preferably selected from the group consisting of geminal or vicinal carbocycles having the following carbon atoms: calcium, strontium, barium, magnesium, Miniumu, silver, sodium, lithium, rubidium, is selected from the group consisting of potassium, and the like. ]
[In formula, R < ²⁷ > -R < ³⁰ > is the same or different and represents a hydrogen atom or a C1-C9 alkyl group, R < ³¹ > represents a hydrogen atom or a C1-C3 alkyl group, d is 1 Or an integer of 2, when d is 1, M ₅ represents an alkali metal, and when d is 2, M ₅ represents an alkaline earth metal, zinc or hydroxyaluminum. ]
[Wherein f represents an integer of 2 to 6. R ³² is a C 2-18 saturated or unsaturated aliphatic polycarboxylic acid residue, a C 3-18 alicyclic polycarboxylic acid residue, or a C 6-18 aromatic polycarboxylic acid residue. Represents a group. 2 to 6 R ^{33 s} are the same or different and are each a saturated or unsaturated aliphatic amine residue having 5 to 30 carbon atoms, an alicyclic amine residue having 5 to 30 carbon atoms, or 6 to 6 carbon atoms. Represents 30 aromatic amine residues. ]
[Wherein, R ³⁴ , R ³⁵ and R ³⁶ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different. ]

  The proportion of the component (A) in the granular polyolefin resin crystal nucleating agent or the granular polyolefin resin crystal nucleating agent as the core of the present invention is 60 to 80% by weight, preferably 65 to 75% by weight. % Is recommended.

  The blending amount of component (D) in step (ii) is appropriately selected depending on the use conditions of the crystalline polyolefin resin crystal nucleating agent of the present invention, and is particularly limited as long as the effects of the present invention are exhibited. Although not intended, it is recommended that the amount is preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the crystalline polyolefin resin crystal nucleating agent as a core. (D) If the compounding quantity of a component is the said range, it can adapt to wide use conditions and can eliminate caking.

Component (B): Organic acid monoglyceride (B) The organic acid monoglyceride as the component (B) can be any organic acid monoglyceride having any structure as long as the effects of the present invention are exhibited. It is recommended that it is a monoglyceride of a fatty acid that may have at least one hydroxyl group in the molecule, and more preferably that the fatty acid is a saturated fatty acid having 12 to 24 carbon atoms.

  Specifically, for example, monoglycerides of saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, oleic acid, elaidic acid, gadoleic acid, elca Acids, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, monoglycerides of unsaturated fatty acids such as docosahexaenoic acid, undecylenic acid, isostearic acid, ricinoleic acid, 12- Hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, hydrogenated castor oil fatty acids (fatty acids containing small amounts of stearic acid and palmitic acid in addition to 12-hydroxystearic acid), etc. Glycerides of fatty acids or the like having a 岐鎖 or substituents.

  Among the organic acid monoglycerides, stearic acid monoglyceride, behenic acid monoglyceride, 12-hydroxystearic acid monoglyceride are particularly recommended, and stearic acid monoglyceride is most recommended.

Component (C): Organic compound having a melting point of 100 ° C. or higher The organic compound (C) component having a melting point of 100 ° C. or higher has a melting point of 100 ° C. or higher as long as the effects of the present invention are exhibited. Any organic compound having any structure can be used as long as it is preferable, but preferably an alkali or alkaline earth metal salt or transition metal salt of a saturated fatty acid having 14 to 22 carbon atoms, a hindered phenol compound, and phosphorous acid. It is particularly recommended that the compound be one or more compounds selected from the group consisting of ester compounds.

  Specifically, examples of the alkali or alkaline earth metal salt of a saturated fatty acid having 14 to 22 carbon atoms include saturated fatty acids such as myristic acid, palmitic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, and lignoceric acid. And isostearic acid, ricinoleic acid, 12-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, hydrogenated castor oil fatty acid (fatty acids containing small amounts of stearic acid and palmitic acid in addition to 12-hydroxystearic acid) ) And the like, and alkali metal salts such as lithium, sodium, potassium and cesium of saturated fatty acids having a branched chain and a substituent, alkali metal salts such as calcium, magnesium and barium, and transition metal salts such as zinc. Among these, stearic acid, behenic acid, calcium salt of 12-hydroxystearic acid, magnesium salt, zinc salt and the like are recommended as particularly preferable compounds.

  Specifically, examples of hindered phenol compounds include 2,6-diphenyl-4-octadecyloxyphenol, 4,4′-methylenebis (2,6-di-t-butylphenol), 2- [1. -(2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, triethylene glycol-bis [3- (3-t-butyl-5-methyl) -4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 5] undecane, 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy) Benzyl) mesitylene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3-bis- (3′-t-butyl-) 4′-hydroxyphenyl) butyric acid] ethylene glycol ester, 2,6-bis (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methylphenol, bis [2-tert-butyl-4 -Methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) phenyl] terephthalate, α-tocopherol, β-tocopherol, γ-tocopherol, α- Cotrienol, β-tocotrienol, γ-tocotrienol, dodecyl gallate, hexadecyl gallate, stearyl gallate, octyl 3- (4-hydroxy-3,5-diisopropylphenyl) propionate, 2,4-dimethyl-6- ( 1-methylpentadecyl) -phenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′- Butylidenebis (3-methyl-6-tert-butylphenol), nordihydroguaiaretic acid, 2,2'-methylenebis [4-methyl-6-nonylphenol], 2,2'-methylenebis [6- (1-methylcyclohexyl) ) -4-methylphenol], 2,2 ′-[(2-hydroxy-5-methylbenzene-1, -Diyl) dimethanediyl] bis (4-methyl-6-nonylphenol), 2,2'-thiodiethylbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4 ' -Thiobis (2-t-butyl-5-methylphenol), 2-hydroxy-4-n-octyloxybenzophenone, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) 5- Chlorobenzotriazole, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, N, N ′-(1,6-hexanediyl) bis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1, 3 , 5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-ethylidene Compounds such as bis (4-s-butyl-6-tert-butylphenol), 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, curcumin Is exemplified.

  Among the above compounds, 4,4′-methylenebis (2,6-di-t-butylphenol), 3,9-bis [2- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -Propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane, 1,1,3-tris (2-methyl-5-tert-butyl-4 -Hydroxyphenyl) butane, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl) -4'-hydroxyphenyl) propionate] methane, 2,2'-thiodiethylbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N '-(1,6 -Hexanediyl) bis [3 Recommended compounds such as (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate Among them, 3,9-bis [2- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8 , 10-tetraoxaspiro [5 · 5] undecane, 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane, tetrakis- [methylene-3- (3 ′, 5 '-Di-t-butyl-4'-hydroxyphenyl) propionate] methane, 2,6-bis (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methylphenol, 1,3,5 -Tris Compounds such as (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate are particularly recommended, and tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate] methane is most recommended.

  Examples of phosphite compounds include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, and trilauryl phosphite. , Tris (tridecyl) phosphite, trioleyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, trilauryl trithiophosphite, tetraphenyl dipropylene glycol diphos Phyto, tetraphenyl (tetratridecyl) pentaerythritol tetraphosphite and bis (2-ethylhexyl) phthalate mixture, tetra (C12-C15 alkyl)- , 4'-isopropylidene diphenyl diphosphite, mixture of bis (tridecyl) pentaerythritol diphosphite and bis (nonylphenyl) pentaerythritol diphosphite, bis (decyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol Diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, hydrogenated bisphenol A / pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite Examples thereof include polymers. Among these, tris (2,4-di-t-butylphenyl) phosphite is particularly recommended.

  The proportion of the component (B) in the crystal nucleating agent for the granular polyolefin resin or the core for the granular polyolefin resin of the present invention is 10 to 30% by weight, preferably 13 to 25% by weight. % Is recommended. Similarly, it is recommended that the total ratio of the component (B) and the component (C) is 20 to 40% by weight, preferably 25 to 35% by weight. When the proportion of the component (B) is less than 10% by weight or the total proportion of the component (B) and the component (C) is less than 20% by weight, there is a concern that the granulation becomes insufficient and sufficient fluidity improvement cannot be achieved. is there.

  Further, when the proportion of the component (B) exceeds 30% by weight, the concern about caking increases, and when the total proportion of the component (B) and the component (C) exceeds 40% by weight, the crystal nucleating agent for polyolefin resin. As a result, there is a concern that performance problems may occur.

Production of Granular Polyolefin Resin Crystal Nucleating Agent The production method of the granular polyolefin resin crystal nucleating agent of the present invention will be described in detail with reference to specific examples. However, the present invention is not necessarily limited to the following method as long as the desired performance is obtained.
Step (i): (A) Crystalline nucleating agent for polyolefin resin, (B) organic acid monoglyceride, and (C) an organic compound having a melting point of 100 ° C. or higher, and the powder temperature is higher than the melting point of component (B), (C) The mixture is granulated with stirring while controlling the temperature within the melting point of the component.

Step (ii): (D) Polyolefin resin crystal nucleating agent (core) obtained in step (i) is further added to (D) polyolefin resin crystal nucleating agent, and the powder temperature is adjusted to component (B). The mixture is heated and mixed while the temperature is controlled in the temperature range above the melting point of the step (i) and below the powder temperature.

  The stirring granulation in the said process (i) should just be granulated, stirring, The heatable stirring granulator which has a stirring blade in a general purpose stirring tank can be used. Typical stirring granulators include, for example, a stirring tumbling granulator (such as a high speed mixer), a high speed stirring granulator (such as a Henschel mixer), a vertical granulator, a pharmamatrix, a super mixer, GRAL-Glar, Examples include vertical mixers such as Shugi mixers, high speeders, and new speed kneaders, horizontal mixers such as Redige mixers, Spartan luzers, and pin mixers. Among them, stirring tumbling granulators and high-speed stirring granulators Etc. are particularly recommended.

  The heating and mixing in the step (ii) only needs to be able to mix under heating, and a general-purpose stirring mixer such as a universal mixer can also be used. However, in consideration of productivity, it is used in the step (i). A method using the stirred granulator as it is is efficient and preferable.

  The method for charging each component in step (i) is not particularly limited. For example, a method of stirring and granulating under heating after charging the three components simultaneously, or a method of charging only component (A) in advance and stirring under heating. In the process, the remaining (B) component and (C) component may be added all at once or sequentially, followed by stirring and granulation.

  “Powder temperature” in the claims and specification of the present invention means the actual temperature of a powder which is a powder or a granular mixture at the time of stirring granulation, stirring mixing and heating mixing, for example, It can be easily measured by installing or inserting a thermometer in an apparatus used for stirring granulation, stirring mixing, and heating mixing.

  The powder temperature can be controlled by, for example, heating means of the stirring device, specifically, heating the temperature through a heating medium through a jacket of the stirring device, and then adjusting the actual powder temperature with a thermometer installed in the device. There can be mentioned a method of controlling the powder temperature by adjusting the heating with the above-mentioned heat medium or the heat generated by shearing while adjusting the cooling by the refrigerant when the heat generated by shearing is large.

  The control range of the powder temperature according to the present invention depends on the types of the component (B) and the component (C). Specifically, the powder temperature in the step (i) is preferably (B). It is recommended that the temperature range be between the melting point of the component and the melting point of the component (C), particularly preferably between the melting point of the component (B) + 10 ° C. and the melting point of the component (C) −10 ° C. . The powder temperature in step (ii) is preferably in the range of the melting point of component (B) to the melting point of component (B) + 50 ° C. and less than the heating temperature in step (i). .

<Polyolefin resin composition>
The polyolefin resin composition of the present invention is a dry blend at room temperature with the polyolefin resin crystal nucleating agent and polyolefin resin according to the present invention added, if necessary, with other polyolefin resin additives. Then, it can obtain easily by melt-mixing on predetermined conditions.

  The concentration of the crystal nucleating agent for polyolefin resin according to the present invention in the polyolefin resin is not particularly limited as long as the effect as the crystal nucleating agent for polyolefin resin according to the present invention is obtained, but 100 parts by weight of the polyolefin resin Is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight.

[Polyolefin resin]
The polyolefin resin is not particularly limited as long as the effects of the present invention are exhibited, and conventionally known polyolefin resins can be used. For example, polyethylene resins, polypropylene resins, polybutene resins, polymethylpentenes can be used. Examples thereof include polyresin and polybutadiene resin. More specifically, high density polyethylene, medium density polyethylene, linear polyethylene, ethylene content of 50% by weight or more, preferably 70% by weight or more of ethylene copolymer, propylene homopolymer, propylene of 50% by weight or more, preferably 70% by weight % Propylene copolymer, butene homopolymer, butene content 50% by weight or more, preferably 70% by weight or more butene copolymer, methylpentene homopolymer, methylpentene content 50% by weight or more, preferably 70% by weight methylpentene copolymer And polybutadiene. The copolymer may be a random copolymer or a block copolymer. Furthermore, when these resins have stereoregularity, they may be isotactic or syndiotactic. As the comonomer that can constitute the copolymer, specifically, an α-olefin having 2 to 12 carbon atoms such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, 1,4- Examples include bicyclo type monomers such as endomethylenecyclohexene, (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate, and vinyl acetate.

  As a catalyst applied for producing such a polymer, not only a Ziegler-Natta type catalyst generally used but also a transition metal compound (for example, a titanium halide such as titanium trichloride and titanium tetrachloride) is chlorinated. A catalyst system, a metallocene catalyst, or the like, which is a combination of a catalyst formed on a carrier mainly composed of magnesium halide such as magnesium and an alkylaluminum compound (triethylaluminum, diethylaluminum chloride, etc.) 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 be applied, but is usually about 0.01 to 200 g / 10 minutes. Preferably, about 0.05 to 100 g / 10 min is recommended.

[Other additives]
In addition, as described above, the polyolefin resin composition of the present invention may contain other polyolefin resin additives within a range that does not impair the effects of the present invention, depending on the purpose of use and use thereof. Good.

  Examples of the polyolefin resin additive include various additives described in “Polylist Additives Manual” (January 2002) edited by the Sanitation Council for Polyolefins. Specifically, fluorescent whitening agents (2,5-thiophenediyl (5-t-butyl-1,3-benzoxazole), 4,4′-bis (benzoxazol-2-yl) stilbene, etc.), Antioxidants, stabilizers (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), UV absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants, lubricants (paraffin, wax, etc.) Aliphatic hydrocarbon, higher fatty acid having 8 to 22 carbon atoms, higher fatty acid metal (Al, Ca) salt having 8 to 22 carbon atoms, higher aliphatic alcohol having 8 to 22 carbon atoms, polyglycol, 4 to 22 carbon atoms Esters of higher fatty acids and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives, etc.), fillers (talc, high Lotalcite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agent, foaming aid, polymer additive, plasticizer (dialkyl phthalate, dialkyl hexahydrophthalate, etc.), crosslinking agent, crosslinking accelerator, charging Various additives such as inhibitors, flame retardants, dispersants, organic inorganic pigments (indigo compounds, phthalocyanine compounds, anthraquinone compounds, ultramarine compounds, cobalt aluminate compounds, etc.), processing aids, and other nucleating agents Illustrated.

  When using these additives, the amount used may be used in a range that is usually used as long as the effects of the present invention are not impaired, but for example, preferably 100 parts by weight of 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.

  As said antioxidant, in addition to the above-mentioned phenolic compound or phosphite ester compound, a phenolic antioxidant or a phosphite ester antioxidant may be added, and further a sulfur antioxidant is added. You can also. Specific antioxidants include 2,6-di-t-butylphenol, tetrakis [methylene-3- (3,5-t-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxy. Phenolic antioxidants such as benzophenone, sulfur-based antioxidants such as alkyl disulfides, thiodipropionic esters, benzothiazoles, trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris (2,4 -Di-t-butylphenyl) phosphite, 3,9-bis (2,6-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5 ] Phosphite 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-based antioxidant, 4-di-t-butylphenyl) phosphite, 3,9-bis (2,6-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5 5] Undecane and the like are particularly recommended.

<Polyolefin resin molding>
The polyolefin resin molded product of the present invention can be obtained by molding the polyolefin resin composition of the present invention according to a conventional molding method. 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, rotational molding, or film molding can be employed.

  The polyolefin-based resin molded body thus obtained is excellent in optical properties such as transparency and mechanical properties such as impact resistance. As molded products, sheets, and films, automobile members, electrical members, mechanical parts, daily life It is very useful for various applications such as general goods.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the symbol of the compound in an Example and an application example and the measurement of each characteristic are as follows.

[Properties of crystal nucleating agent]
(1) Measurement of average particle size of raw material crystal nucleating agent (laser diffraction particle size distribution measurement)
Using a laser diffraction particle size distribution meter (“Malvern Instruments,” “Mastersizer 3000”), the measurement was performed by the following method. First, using a wet measurement cell, by sufficiently stirring and mixing, the sample is dispersed in an aqueous solution to which a nonionic surfactant is added as a dispersant, and then the resulting mixture is further stirred in the apparatus. While circulating, ultrasonic waves were applied to sufficiently uniformly disperse in the apparatus. Thereafter, 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 (d50) was determined and used as the average particle size.

(2) Measurement of particle size of nucleating agent for granular polyolefin resin of the present invention (sieving test)
A sieving test was performed under the conditions in accordance with 6.1 of JIS K0069 (1992), and the weight of the residue on the JIS test sieve having an aperture of 600 μm was accurately measured using an analytical balance. From the weight of the obtained sieve having an aperture of 600 μm, the ratio of the sample used in the test to the total weight was determined.

(3) Measurement funnel compression ratio so that the opening on 2cm of the graduated cylinder, and therewith vertically held so that the axis is coincident, the crystal nucleating agent in a measuring cylinder of 100 cm ³ through a funnel 100 cm ³ slowly I put it in. Using a scale, the weight of the crystal nucleating agent in the graduated cylinder was measured to the order of 0.1 g. The loose bulk density was determined from the obtained weight using the following formula (1). Subsequently, an operation (tapping) of dropping the measuring cylinder vertically from a height of 5 cm above the rubber sheet was repeated 50 times. The volume of the crystal nucleating agent in the graduated cylinder was read to the order of 0.1 cm ³ , and the bulk density was determined using the following formula (2). The compression ratio was calculated | required using the following formula (3) from the obtained loose bulk density and the bulk density. Generally, it is said that the closer the compression ratio is to 1, the better the fluidity.
Formula (1);
Loose bulk density (g / cm ³ ) = weight of crystal nucleating agent in graduated cylinder (g) / 100 cm ³
Formula (2);
Bulk density (g / cm ³ ) = weight of crystal nucleating agent in graduated cylinder (g) / volume of crystal nucleating agent after tapping (cm ³ )
Formula (3);
Compression ratio = firm bulk density / loose bulk density

[Evaluation of fluidity]
(4) Measurement of angle of repose Under conditions of 25 ° C. and 60% humidity, 30 g of the crystal nucleating agent was placed on the funnel having a diameter of 9 cm at the opening and a hole diameter of 1 cm from a height of 1 cm to the upper edge of the funnel. And is dropped on a circular platform with a diameter of 9 cm at a position 10 cm from the bottom of the funnel without vibration. The height of the fallen cone-shaped deposit was measured, and the angle between the horizontal plane and the generatrix was obtained by calculation, and the angle of repose (unit: degree) was obtained. The smaller the angle of repose, the better the powder flowability.

(5) Powder flowability test (funnel test)
The crystal nucleating agent is poured from a height of 5 cm to the upper edge of the funnel onto a funnel having an opening diameter of 15 cm and a hole diameter of 1.5 cm, and dropped from the lower funnel without vibration. From the state discharged from the funnel of the crystal nucleating agent, the fluidity of the crystal nucleating agent was determined by a four-step evaluation according to the following criteria.
(Evaluation criteria)
(Double-circle): All the crystal nucleating agents are discharged | emitted from a funnel rapidly, and the deposit | attachment of a funnel inner wall is hardly confirmed.
○: The crystal nucleating agent remains slightly discharged from the funnel, but all the remaining crystal nucleating agent is discharged by a slight impact.
Δ: The crystal nucleating agent remains without being discharged from the funnel, and it is difficult to completely discharge the crystal nucleating agent remaining on the funnel only by a slight impact.
X: The crystal nucleating agent remains in a large amount without being discharged from the funnel, and it is difficult to discharge the crystal nucleating agent remaining on the funnel even when an impact is applied.

[Evaluation of caking properties]
(6) Caking test 10 g of granular crystal nucleating agent was put in a beaker, allowed to stand in an oven set at 50 ° C. for 24 hours, and the properties of the granular crystal nucleating agent in the taken out beaker were confirmed visually. Classification was evaluated in the following four stages.
A: A lump cannot be formed.
○: Almost no lumps are formed, or even if lumps are formed, they are very brittle and soft.
Δ: A lump is formed, but it is easily broken and hardly causes a problem in practical use.
X: It becomes a lump as a whole and needs to be crushed for use.

[Properties of molded product]
(7) Measurement of haze value Using a haze meter manufactured by Toyo Seiki Seisakusho, the haze value was measured by a method according to JIS K7136 (2000). As an evaluation sample, a 1 mm-thickness injection-molded polypropylene resin molded body was used. It shows that it is excellent in transparency, so that the numerical value of the obtained haze value is small.

(8) White spot evaluation The injection-molded polyolefin resin molded body of 50 mm × 50 mm × 1 mm shape was used as an evaluation sample, and the number of white spots in the molded body was counted by visual observation. The obtained results were obtained by taking the average value of 5 samples and setting the number of white points of the samples, and classifying and evaluating from the obtained evaluation results in the following three stages.
A: The number of white spots is less than 3. There is no problem at all on the performance of the molded body.
A: The number of white spots is in the range of 3-15. Although there is no problem in the performance as a nucleating agent, there is a possibility that the influence of undispersed matter may appear on other physical properties.
X: Existence is confirmed when the number of white spots exceeds 15. Obviously, the performance of the nucleating agent is not sufficiently effective, and the undispersed material is likely to cause problems in various physical properties.

Abbreviations of compounds in Examples DMDBS: 1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol PDBN: 1,3: 2,4-bis-O— ( pn-propylbenzylidene) -1-n-propylsorbitol GMS: monoglyceride stearic acid Irg1010: tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (BASF Japan ( Product name “IRGANOX1010”)
CaSt: Calcium stearate

[Example 1]
DMDBS (manufactured by Nippon Nippon Chemical Co., Ltd., Gelol DXR, average particle size 6.2 μm) 1.5 kg, GMS (manufactured by Riken Vitamin Co., Ltd.) , Melting point: 65 ° C.) and 0.5 kg of Irg1010 (melting point: 120 ° C.) were added, and the jacket was stirred at a stirring speed of 300 rpm while steam heating. After the temperature of the powder was raised to 65 ° C., the steam was stopped and the mixture was stirred at a stirring speed of 1500 rpm for 5 minutes to obtain the granular crystal nucleating agent of the present invention. The final powder temperature was 96 ° C. The obtained granular crystal nucleating agent was confirmed from the result of the screening test that the ratio of the residue on the sieve having an opening of 600 μm was 30% by weight with respect to the total weight.
Subsequently, the compression ratio and angle of repose were measured using the obtained granular crystal nucleating agent, and the results are shown in Table 1. Similarly, using the obtained granular crystal nucleating agent, the caking property was evaluated and the powder fluidity was evaluated by a powder fluidity test (funnel test). The results are shown in Table 1.

[Example 2]
A granular crystal nucleating agent was obtained in the same manner as in Example 1 except that the amount of DMDBS was changed to 1.4 kg, the amount of GMS was changed to 0.3 kg, and the amount of Irg1010 was changed to 0.3 kg. The final powder temperature was 94 ° C. The obtained granular crystal nucleating agent shows that the ratio of the residue on the sieve having an aperture of 600 μm is 58% by weight based on the results of the screening test. confirmed.
Subsequently, using the obtained granular crystal nucleating agent, the compression ratio and the angle of repose were measured in the same manner as in Example 1, and the caking property and the powder fluidity were evaluated. The results are summarized in Table 1. It was shown to.

[Example 3]
A granular crystal nucleating agent was obtained in the same manner as in Example 1 except that the amount of DMDBS was changed to 1.4 kg, the amount of GMS was changed to 0.4 kg, and the amount of Irg1010 was changed to 0.2 kg. The final powder temperature was 99 ° C. The obtained granular crystal nucleating agent was confirmed from the result of the screening test that the ratio of the residue on the sieve having an opening of 600 μm was 99% by weight with respect to the total weight.
Subsequently, using the obtained granular crystal nucleating agent, the compression ratio and the angle of repose were measured in the same manner as in Example 1, and the caking property and the powder fluidity were evaluated. The results are summarized in Table 1. It was shown to.

[Example 4]
A 20 L supermixer equipped with a thermometer was charged with 1.4 kg of DMDBS, 0.3 kg of GMS, and 0.3 kg of Irg1010 at room temperature, and stirred at a stirring speed of 300 rpm while steam heating the jacket. After raising the temperature until the powder temperature reached 65 ° C., the steam was stopped and the mixture was stirred at a stirring speed of 1500 rpm for 5 minutes to obtain a granular crystal nucleating agent serving as a core. The powder temperature at this time was 96 ° C. Subsequently, stirring was stopped, and 0.1 kg of DMDBS was additionally charged into the supermixer, and again stirred at a stirring speed of 1500 rpm for 3 minutes. The final powder temperature was 90 ° C. The obtained granular crystal nucleating agent was confirmed from the result of the screening test that the ratio of the residue on the sieve having an opening of 600 μm was 98% by weight with respect to the total weight.
Subsequently, using the obtained granular crystal nucleating agent, the compression ratio and the angle of repose were measured in the same manner as in Example 1, and the caking property and the powder fluidity were evaluated. The results are summarized in Table 1. It was shown to.

[Example 5]
A granular crystal nucleating agent was obtained in the same manner as in Example 4 except that the amount of DMDBS added additionally was changed to 0.2 kg. The final powder temperature was 87 ° C. The obtained granular crystal nucleating agent was confirmed from the results of the screening test that the ratio of the residue on the sieve having an opening of 600 μm was 84% by weight with respect to the total weight.
Subsequently, using the obtained granular crystal nucleating agent, the compression ratio and the angle of repose were measured in the same manner as in Example 1, and the caking property and the powder fluidity were evaluated. The results are summarized in Table 1. It was shown to.

[Example 6]
A granular crystal nucleating agent was obtained in the same manner as in Example 2 except that DMDBS was changed to PDBN (average particle size: 5.9 μm). The final powder temperature was 95 ° C. The obtained granular crystal nucleating agent was confirmed from the result of the screening test that the ratio of the residue on the sieve having an opening of 600 μm was 50% by weight with respect to the total weight.
Subsequently, using the obtained granular crystal nucleating agent, the compression ratio and the angle of repose were measured in the same manner as in Example 1, and the caking property and the powder fluidity were evaluated. The results are summarized in Table 1. It was shown to.

[Example 7]
A granular crystal nucleating agent was obtained in the same manner as in Example 2 except that Irg1010 was changed to CaSt (manufactured by Nitto Kasei Kogyo Co., Ltd., melting point: 148 ° C.). The final powder temperature was 100 ° C. The obtained granular crystal nucleating agent was confirmed from the result of the screening test that the ratio of the residue on the sieve having an opening of 600 μm was 99% by weight with respect to the total weight.
Subsequently, using the obtained granular crystal nucleating agent, the compression ratio and the angle of repose were measured in the same manner as in Example 1, and the caking property and the powder fluidity were evaluated. The results are summarized in Table 1. It was shown to.

[Example 8]
Polypropylene random copolymer (MFR = 7 g / 10 min (load 2160 g, temperature 230 ° C.) as a polyolefin resin, R-720, manufactured by Prime Polymer Co., Ltd.) 100 parts by weight, obtained as Example 1 as a crystal nucleating agent 0.31 parts by weight of a granular crystal nucleating agent and 0.05 parts by weight of calcium stearate (CaSt) as other additives, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ] 0.01 parts by weight of methane (Irg1010) and 0.05 parts by weight of tetrakis (2,4-di-t-butylphenyl) phosphite (BASF Japan, trade name “IRGAFOS168”) were dry blended. The dry blend is melt-mixed using a single screw extruder (VS-20 manufactured by Tanabe Plastics Machine Co., Ltd.) at a barrel temperature of 250 ° C., and then the extruded strand is cooled, cut with a pelletizer, and polyolefin resin. A composition was prepared.

  Then, using the obtained polyolefin resin composition, injection molding temperature (heating temperature) 240 ° C., mold temperature (cooling temperature) 40 ° C. with an injection molding machine (NS40-5A manufactured by Nissei Plastic Industry Co., Ltd.). The polyolefin-based resin molded body having a thickness of 1 mm and a thickness of 2 mm was obtained.

  Using the molded body obtained above as an evaluation sample, the haze value was measured, and the obtained results are shown in Table 2. Then, the white point evaluation in a molded object was performed visually by the said method, and the result was combined and shown in Table 2.

[Example 9]
Except that 0.29 parts by weight of the granular crystal nucleating agent obtained in Example 2 was used as the crystal nucleating agent, the same operation as in Example 8 was carried out to obtain a polyolefin resin composition and a polyolefin resin molded article. Obtained. Using the obtained molded body, the haze value was measured, and the obtained results are shown in Table 2. Then, the white point evaluation in a molded object was performed visually by the said method, and the result was combined and shown in Table 2.

[Example 10]
As the crystal nucleating agent, the same procedure as in Example 8 was carried out except that 0.29 parts by weight of the granular crystal nucleating agent obtained in Example 3 was used and the amount of Irg1010 was changed to 0.02 parts by weight. A polyolefin resin composition and a polyolefin resin molding were obtained. Using the obtained molded body, the haze value was measured, and the obtained results are shown in Table 2. Then, the white point evaluation in a molded object was performed visually by the said method, and the result was combined and shown in Table 2.

[Example 11]
Except that 0.28 parts by weight of the granular crystal nucleating agent obtained in Example 4 was used as the crystal nucleating agent, the same procedure as in Example 8 was carried out to obtain a polyolefin resin composition and a polyolefin resin molded article. Obtained. Using the obtained molded body, the haze value was measured, and the obtained results are shown in Table 2. Then, the white point evaluation in a molded object was performed visually by the said method, and the result was combined and shown in Table 2.

[Example 12]
A polyolefin resin composition and a polyolefin resin molded article were prepared in the same manner as in Example 8 except that 0.28 parts by weight of the granular crystal nucleating agent obtained in Example 5 was used as the crystal nucleating agent. Obtained. Using the obtained molded body, the haze value was measured, and the obtained results are shown in Table 2. Then, the white point evaluation in a molded object was performed visually by the said method, and the result was combined and shown in Table 2.

[Example 13]
The polyolefin-based resin composition and the polyolefin-based resin molded body were obtained in the same manner as in Example 8, except that 0.29 parts by weight of the granular crystal nucleating agent obtained in Example 6 was used as the crystal nucleating agent. Obtained. Using the obtained molded body, the haze value was measured, and the obtained results are shown in Table 2. Then, the white point evaluation in a molded object was performed visually by the said method, and the result was combined and shown in Table 2.

[Example 14]
As the crystal nucleating agent, 0.29 part by weight of the granular crystal nucleating agent obtained in Example 7 was used, except that the amount of Irg1010 was changed to 0.05 part by weight and the amount of calcium stearate was changed to 0.01 part by weight. Were carried out in the same manner as in Example 8 to obtain a polyolefin resin composition and a polyolefin resin molded article. Using the obtained molded body, the haze value was measured, and the obtained results are shown in Table 2. Then, the white point evaluation in a molded object was performed visually by the said method, and the result was combined and shown in Table 2.

  From the results of Table 1 and Table 2, the granular crystal nucleating agent according to the present invention is very excellent in fluidity, and further contributes to improvement in productivity without problems such as caking, and It can be seen that the polyolefin resin molded body containing the granular crystal nucleating agent has no problems such as white spots and has very excellent transparency and is very useful in various applications.

  The crystal nucleating agent for granular polyolefin resin of the present invention has greatly improved fluidity, and can be used in various applications as a crystal nucleating agent having extremely excellent fluidity. In addition, the crystal nucleating agent for granular polyolefin resin of the present invention has the same or better performance than the conventional crystal nucleating agent in terms of dispersibility and solubility in the polyolefin resin. It is also very useful. Therefore, the crystal nucleating agent for granular polyolefin resin of the present invention can greatly contribute to the improvement of productivity in various applications, and the obtained polyolefin resin molded product is an uncrystallized nucleating agent. There are no defects such as white spots due to dispersions and undissolved materials, and it has excellent optical properties such as transparency and mechanical properties such as impact resistance, automobile parts, electrical parts, mechanical parts, daily goods, It can be widely used in various applications such as clothes cases and food containers.

Claims (14)

(A) Crystal nucleating agent for polyolefin resin, (B) Organic acid monoglyceride, (C) Crystal nucleating agent for granular polyolefin resin comprising an organic compound having a melting point of 100 ° C. or higher,
The proportion of the component (A) in the granular polyolefin resin crystal nucleating agent is 60 to 80% by weight, the proportion of the component (B) is 10 to 30% by weight, and the components (B) and (C ) The total proportion of the components is 20-40% by weight,
The proportion of the component (B) in the total amount of the component (B) and the component (C) is 30 to 80% by weight, and the granular polyolefin resin crystal nucleating agent has a powder temperature of (B A crystal nucleating agent for a granular polyolefin-based resin, which is heated and mixed while being controlled within a temperature range of not less than the melting point of the component) and not more than the melting point of the component (C). The crystal nucleating agent for a granular polyolefin resin according to claim 1, wherein the component (B) is a monoglyceride of a fatty acid which may have at least one hydroxyl group in the molecule. The component (C) is one or more selected from the group consisting of alkali or alkaline earth metal salts of saturated fatty acids having 14 to 22 carbon atoms, hindered phenol compounds, and phosphite compounds. The crystal nucleating agent for granular polyolefin resin according to claim 1 or 2, which is a compound of The granular polyolefin resin crystal nucleating agent according to any one of claims 1 to 3 is used as a core, and particles of the (D) polyolefin resin crystal nucleating agent are attached to the core. A crystal nucleating agent for a granular polyolefin resin. The crystal nucleating agent for granular polyolefin resin according to claim 4, wherein the adhesion amount of component (D) is 1 to 20 parts by weight with respect to 100 parts by weight of the crystal nucleating agent for granular polyolefin resin in the core part. . The angle of repose of the crystal nucleating agent for granular polyolefin resin is 40 degrees or less, and the compression ratio calculated from the loose bulk density or the bulk density is 1.2 or less. Crystal nucleating agent for granular polyolefin resin. The crystal nucleating agent for granular polyolefin resin according to any one of claims 1 to 6, wherein the component (A) and / or the component (D) is a diacetal compound represented by the following general formula (1).
[In Formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched carbon. An alkoxy group having 1 to 4 carbon atoms, a linear or branched alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom is shown. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkenyl group having 2 to 4 carbon atoms, or a linear or branched carbon atom. The hydroxyalkyl group of number 1-4 is shown. m and n each represent an integer of 1 to 5. p represents 0 or 1; Two R ¹ may be bonded to each other to form a tetralin ring together with a benzene ring to which they are bonded. Two R ² groups may be bonded to each other to form a tetralin ring together with the benzene ring to which they are bonded. ] The crystal nucleating agent for granular polyolefin resin according to any one of claims 1 to 7, wherein the crystal nucleating agent for granular polyolefin resin is a heated stirring granulated product. A method for producing a crystal nucleating agent for a granular polyolefin resin with improved fluidity, comprising:
(I) (A) Crystal nucleating agent for polyolefin-based resin, (B) organic acid monoglyceride, and (C) an organic compound having a melting point of 100 ° C. or higher, powder temperature is higher than the melting point of component (B), (C ) A production method comprising a step of granulating with stirring while controlling within a temperature range below the melting point of the component. After step (i) according to claim 9, (D) a crystal nucleating agent for polyolefin-based resin obtained in step (i) is further added (D) a crystal nucleating agent for polyolefin-based resin, A production method comprising a step of heating and mixing while controlling a powder temperature to a temperature range not lower than the melting point of component (B) and lower than the powder temperature of step (i). A polyolefin resin composition comprising a polyolefin resin and the crystal nucleating agent for a granular polyolefin resin according to any one of claims 1 to 8. A polyolefin resin molded body using the polyolefin resin composition according to claim 11 as a raw material. (A) Crystal nucleating agent for polyolefin resin, (B) organic acid monoglyceride and (C) organic compound having melting point of 100 ° C. or higher, powder temperature is higher than melting point of component (B), melting point of component (C) A method for improving the fluidity of a crystal nucleating agent for polyolefin resin, which is granulated by stirring and mixing while controlling to a temperature range below. The polyolefin resin crystal nucleating agent granulated in the above method and the further added (D) polyolefin resin crystal nucleating agent have a powder temperature equal to or higher than the melting point of the component (B) and the above-mentioned stirring and mixing. The fluidity improving method according to claim 13, wherein the mixture is heated and mixed while being controlled in a temperature range lower than the powder temperature.