JP6679450B2 - Crystal nucleating agent for granular polyolefin resin with improved fluidity - Google Patents

Description

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

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

  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 phosphoric acid ester, and further dissolved in an organic crystal nucleating agent. There are two types of crystal nucleating agents: non-dissolving type and crystal type. Soluble organic crystal nucleating agents represented by the diacetal compounds are particularly effective and widely used for improving optical properties such as transparency.

  One of the characteristics of general-purpose plastics, especially polyolefin-based resins, is that they are inexpensive, and for that reason it is important to have excellent productivity. As described above, the addition of a crystal nucleating agent shortens the molding cycle. Etc. are variously devised. The feedability of the raw materials is one of them, and it is necessary that the feedability of each raw material, that is, its fluidity is excellent. However, the above crystal nucleating agents, especially diacetal type crystal nucleating agents, have poor fluidity, which has been a serious problem in productivity.

  Therefore, various studies have been made so far regarding the improvement of 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), and the like. Proposed and in use.

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

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

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

  In the case of the method (1), in general, the larger the particle size, the better the fluidity, and the method of granulating the nucleating agent alone or by mixing with other additives, or by mixing with the 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-based resin tend to deteriorate, and as a result, not only the performance such as the transparency inherent to the nucleating agent is deteriorated but also However, there is a concern that appearance problems such as white spots may occur, and particularly 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.

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

  Further, the method of granulating is also important for fluidity, and various studies have been made so far regarding that method as well, and at present, the extrusion granulation method and the compression granulation method are general, Widely used.

  On the other hand, as a recent trend, in consideration of environmental issues etc. in general, and in order to ensure the flexibility of the compounding formulation, the amount of components other than the crystal nucleating agent is being reduced as much as possible. There is a demand for a method of granulating with the above binder. In addition, depending on the application, there are cases in which the performance of the nucleating agent itself may be affected by the blending of the binder, and the reduction of the binder amount has been desired from that viewpoint. However, in the above extrusion granulation method and compression granulation method, granulation is difficult unless the binder is contained in a certain amount or more, and there is a limit to the reduction of the binder amount.

  Further, depending on the use, the demands on the dispersibility and solubility in the above-mentioned resin are more severe, and it is necessary to add a large amount of a binder having a relatively low melting point such as organic acid monoglyceride. However, in that case, it has been pointed out that a new problem such as caking due to the binder has occurred, and improvement thereof has been required.

  In particular, in the case of a crystal nucleating agent such as a diacetal compound, there are problems such as secondary cohesiveness, and it is known that dispersibility and solubility in a molten resin greatly affect the performance of the nucleating agent. At present, it is difficult to sufficiently satisfy all the requirements by granulation using a conventionally known system, and improvement thereof is strongly desired.

WO98 / 33851 JP 2001-81236 A WO02 / 077094 Japanese Patent Publication No. 2009-507982 JP, 2013-209662, A JP, 2015-30849, A Japanese Patent No. 5920524

  The present invention provides a method for improving the fluidity of a crystal nucleating agent for a polyolefin resin by granulation, a method for producing a crystal nucleating agent for a granular polyolefin resin having improved fluidity including the method, and a method for obtaining the same. Another object of the present invention is to provide a crystal nucleating agent for a granular polyolefin resin having improved fluidity, a polyolefin resin composition excellent in transparency and containing the crystal nucleating agent, and a molded article thereof.

  In view of the above situation, the present inventors have made intensive studies to solve the above problems, and as a result, blend a specific compound having a binder effect in a specific ratio, and further stir and mix under specific conditions. It is possible to produce a crystal nucleating agent for granular polyolefin-based resins with a small amount of a specific compound used, and the obtained crystal nucleating agent for granular polyolefin-based resins has no problems such as caking and It has excellent dispersibility and solubility in, and shows significantly improved fluidity, and that the polyolefin resin composition and its molded product containing the crystal nucleating agent are also very excellent in transparency. Heading out, the present invention has been completed.

  That is, the present invention was obtained by the following method for improving the fluidity of a crystal nucleating agent for a polyolefin resin, a method for producing a granular nucleating agent for a polyolefin resin having improved fluidity including the method, and the method. The present invention provides a crystal nucleating agent for a granular polyolefin resin having improved fluidity, a polyolefin resin composition excellent in transparency and containing the crystal nucleating agent, and a molded product thereof.

[Item 1] A crystal nucleating agent for a polyolefin resin, comprising (B) an organic acid monoglyceride, and (C) an organic compound having a melting point of 100 ° C. or higher.
The proportion of the component (A) in the crystal nucleating agent for a granular polyolefin resin 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 to 40% by weight, and
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 crystal nucleating agent for the granular polyolefin resin has a powder temperature of (B A crystalline nucleating agent for a granular polyolefin resin, which is heated and mixed while being controlled in a temperature range from the melting point of the component) to 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 components (B) and (C) is 25 to 35% by weight. The crystal nucleating agent for granular polyolefin resin according to [1], which is

[Item 3] The granular polyolefin according to [Item 1] or [Item 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. Crystal nucleating agent for resin.

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

[Item 5] The crystal nucleating agent for granular polyolefin resin according to [Item 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.

[Item 7] The crystal nucleating agent for granular polyolefin resin according to [Item 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. Alternatively, the crystal nucleating agent for the granular polyolefin resin according to any one of [Item 1] to [Item 7], which is a compound of two or more kinds.

[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 [8], which is a phosphite.

[Item 10] The granular polyolefin-based resin according to item 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 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 nucleating agent for polyolefin resin as defined in any one of [Item 1] to [Item 11] is used as a core, and (D) particles of the crystalline nucleating agent for polyolefin resin are attached to the core. A crystalline nucleating agent for a granular polyolefin resin, characterized in that

[Item 13] The amount of the component (D) attached is 1 to 20 parts by weight with respect to 100 parts by weight of the crystal nucleating agent for the granular polyolefin resin in the core portion, and the granular polyolefin system according to [item 12]. Crystal nucleating agent for resins.

[Item 14] The granular polyolefin-based material according to [Item 13], wherein the amount of the component (D) attached is 5 to 15 parts by weight based on 100 parts by weight of the crystal nucleating agent for the granular polyolefin-based resin in the core portion. Crystal nucleating agent for resins.

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

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

[Item 17] In the sieving test conducted under the conditions based on JIS K0069 (1992), the ratio of the residue on the JIS test sieve having an opening of 600 μm to the total weight is 10% by weight or more, [Item 1] to The crystal nucleating agent for polyolefin resin according to any one of [Item 16].

[Item 18] The granular form according to any one of [Item 1] to [Item 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 the 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, a linear or branched carbon atom, respectively. It represents 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. 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 groups of the numbers 1 to 4 are shown. m and n each represent an integer of 1 to 5. p represents 0 or 1. Two R ^1's may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. The 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 each is 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 each is 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 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 a granular polyolefin resin, which has improved fluidity,
(I) (A) a crystal nucleating agent for polyolefin resin, (B) an organic acid monoglyceride, and (C) an organic compound having a melting point of 100 ° C. or higher, and the powder temperature is set to the melting point of the (B) component and (C). A manufacturing method comprising a 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 the step (i) is 60 to 80% by weight, the proportion of the component (B) is 10 to 30% by weight, and the total of the components (B) and (C) is Is 20 to 40% by weight, and the proportion of the component (B) in the total amount of the components (B) and (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 total of the components (B) and (C) is Is 25 to 35% by weight, and the proportion of the component (B) in the total amount of the components (B) and (C) is 35 to 75% by weight. Production method.

[Item 25] After the step (i) according to any one of [Item 22] to [Item 24], (ii) the granular crystal nucleating agent for a polyolefin-based resin obtained in step (i), and further ( D) Production comprising a step of adding a crystal nucleating agent for polyolefin resin and heating and mixing while controlling the powder temperature in a temperature range not lower than the melting point of the component (B) and lower than the powder temperature in the step (i) Method.

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

[Item 28] The production according to any one of [Item 22] to [Item 27], wherein the powder temperature in the step (i) is in the range from the melting point of the component (B) to 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 is lower than the powder temperature of the step (i). ] The manufacturing method in any one of [item 28].

[Item 30] The production method according to any one of [Item 22] to [Item 29], wherein the component (A) and / or the component (D) is a diacetal compound represented by the following general formula (1). .
[In the 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, a linear or branched carbon atom, respectively. It represents 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. 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 groups of the numbers 1 to 4 are shown. m and n each represent an integer of 1 to 5. p represents 0 or 1. Two R ^1's may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. The 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 31] In the general formula (1), R ¹ and R ² are the same or different and each is a methyl group or an ethyl group, R ³ is a hydrogen atom, and m and n are 1 or 2. The production method according to [Item 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 each is 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 manufacturing method is as set forth in [claim 30], wherein p is 1.

[Item 33] The production method according to any one of [Item 22] to [Item 32], wherein the component (B) is a monoglyceride of a fatty acid which 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. Alternatively, the production method according to any one of [Item 22] to [Item 35], which is two or more 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 the crystal nucleating agent for 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 granular polyolefin resin is 0.001 to 10 parts by weight relative to 100 parts by weight of the polyolefin resin. .

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

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

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

[Item 45] The crystal nucleating agent for a polyolefin resin, which has been granulated in the above method, and the crystal nucleating agent for a polyolefin resin (D), which are further added, have a powder temperature of not less than the melting point of the component (B), The method for improving fluidity according to [Item 44], wherein granules are formed by stirring and mixing while controlling the temperature range to be lower than the powder temperature during the stirring and mixing.

  The crystal nucleating agent for a granular polyolefin resin of the present invention has extremely excellent fluidity and can greatly contribute to the improvement of productivity. Further, the crystal nucleating agent for the granular polyolefin-based resin of the present invention has the same or similar dispersibility and solubility as the conventional crystal nucleating agent in the polyolefin-based resin which is very important particularly in the diacetal compound and the like. It has the above-mentioned properties and can exhibit extremely excellent properties 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 article has very excellent transparency and has many applications. Useful in. Furthermore, the crystal nucleating agent for a granular polyolefin resin of the present invention produced by the production method comprising the step (ii) eliminates problems such as caking caused by a specific compound having a binder effect, and has a wider range of applications. Can be applied to.

<Crystal Nucleating Agent for Granular Polyolefin Resin>
The crystal nucleating agent of the present invention is characterized in that it is in the form of granules, and the granular crystal nucleating agent is (A) a powder of the crystal nucleating agent for a polyolefin resin obtained by an ordinary production method, in a predetermined amount ( B) Mixing with an organic acid monoglyceride and (C) an organic compound having a melting point of 100 ° C. or higher, while controlling the powder temperature within a temperature range of the melting point of the (B) component or higher and the melting point of the (C) component or lower, and mixing by heating. It can be obtained by The heating and mixing means mixing the components under heating, and the mixing method is not particularly limited as long as the effect of the present invention can be obtained, but a preferable method is mixing by stirring. Method (stirring mixing) is recommended. That is, a method of granulating while mixing by stirring (stir granulation) is particularly recommended as a method of forming a granule for the purpose of the present invention. The crystal nucleating agent for a granular polyolefin-based resin (heat-stir-granulated material) that is agitated and granulated under heating is particularly superior in terms of performance such as fluidity.

  In the present invention, it was difficult to confirm the reason why the above effects were obtained, but by preparing under the above conditions, the completely melted component (B) was homogeneous in the aggregated particles of the component (A). It is presumed that the binder effect of the component (B) is adjusted by making the component (C) coexist with the component (C) which does not completely melt, by coexisting with the component (C). That is, the component (B) alone had a concern that the dispersibility may be reduced due to the generally known granulation, but the coexistence of the component (C) may adjust the binder effect and may cause a decrease in the dispersibility. It is supposed to have disappeared. Moreover, it is presumed that coexistence of the component (C) having a high melting point reduces concerns such as caking. From the above speculation, it is considered that the mixing condition and mixing ratio are very important requirements in the present invention.

  In addition, depending on the application, there may be a problem such as caking due to the component (B) having a binder effect even under the above conditions. In that case, the granular crystal nucleating agent of the present invention obtained above, Further, (D) a powder of a crystal nucleating agent for a polyolefin resin obtained by a usual production method is added, and a powder temperature is 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 crystal nucleating agent for a granular polyolefin resin in which the problems such as the caking are solved. Generally, caking in a resin additive composition is considered to be caused by a component having a low melting point, that is, 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 achieved, and the originally desired performance improvement such as fluidity and dispersibility becomes insufficient, and in recent years It is becoming difficult to meet the strict demands of. Therefore, the present inventors have studied various methods of solving the problems such as caking while maintaining the fluidity and dispersibility of the object of the present invention, the reason for which is not clear, but as described above. It was concluded that by doing so, problems such as caking can be solved. In this case, the boundary is unclear and it is difficult to visually confirm, but it is presumed that most of the added component (D) is attached to the surface of the granular crystal nucleating agent, It is considered that such a state would be particularly important for suppressing caking.

  The shape of the crystal nucleating agent for the polyolefin-based resin, which is the component (A) and the component (D), is not particularly limited as long as the effects of the present invention are exhibited, but preferably the average particle diameter determined by laser diffraction particle size distribution measurement. Is particularly preferably 0.01 to 15 μm, more preferably 0.1 to 10 μm. When the average particle size is 0.01 μm or more, granulation tends to be easy, and when the average particle size is 15 μm or less, the granular crystal nucleating agent of the present invention is dispersed in a polyolefin resin. There is a tendency that it positively affects the solubility and solubility.

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

  The angle of repose of the granular crystal nucleating agent of the present invention is 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.

  Further, the granular crystal nucleating agent of the present invention is recommended to have a compression ratio (hard bulk density / loose bulk density) of 1.2 or less, which is obtained from the loose bulk density and the firm bulk density. Generally, the closer the compression ratio is to 1, the more excellent the fluidity is, and in the present invention, the compression ratio is closer to 1 as compared with the usual powdery crystal nucleating agent, which is effective in improving the fluidity. It is presumed that it has brought about.

  The laser diffraction particle size distribution measurement can be carried out by a general-purpose method and conditions using a general-purpose device. For example, by using a laser diffraction type particle size distribution meter ("Mastersizer 3000" manufactured by Malvern Instruments, Inc.), the sample is placed in an aqueous solution containing a surfactant as a dispersant by thoroughly stirring and mixing in a wet measurement cell. Then, while further agitating and circulating the obtained mixture in the device, ultrasonic waves are applied to disperse the mixture evenly in the device, and then the particle size distribution of the sample is changed by applying ultrasonic waves. Can be measured. From the obtained particle size distribution, the average particle size, that is, the volume-based cumulative 50% particle size (median size: d50) can be determined.

  In addition, the sieving test can be measured using a general-purpose sieve that conforms to the JIS standard according to JIS K0069 (1992). Specifically, a sieving test is performed under the conditions according to JIS K0069 (1992) 6.1, and the weight of the residue on the JIS test sieve having an opening of 600 μm is measured, and all the samples used for the test are measured. The ratio to the weight was calculated.

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

Specific examples of the diacetal compound include diacetal compounds represented by the following general formula (1).
[In the 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, a linear or branched carbon atom, respectively. It represents 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. 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 groups of the numbers 1 to 4 are shown. m and n each represent an integer of 1 to 5. p represents 0 or 1. Two R ^1's may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. The 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 above diacetal compounds, more preferable compounds include, for example, R ¹ and R ² in the general formula (1), which are the same or different, are a methyl group or an ethyl group, and R ³ is a hydrogen atom. And 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 propyl groups or propyloxy groups, and R ³ is Examples thereof include a propyl group or a propenyl group, m and n are 1, and p is 1.

Further, the following compounds can be exemplified as more preferable compounds; in the above general formula (1), R ¹ and R ² are propyl groups or propyloxy groups, and R ³ is a propyl group or 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-isopropylate 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- (o-t-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-t-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, 1 , 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, 1 , 3: 2,4-bis-O- (o-isopropoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-isopropoxycarbonylbenzylidene) -D-sorbitol, 1 , 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- (m-n-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)- Two 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 Methylsorbitol, 1,3: 2,4-bis-O- (3 ', 5'-dimethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2', 3'- Diethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2 ′, 4′-diethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- ( 2 ', 5'-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, 1 , 3: 2,4-bis-O- (3'-methyl-4'-me Xybenzylidene) -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, 1 , 3: 2,4-bis-O- (3 ', 5'-dimethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (2', 3'-diethylbenzylidene)- 1-ethylsorbitol, 1,3: 2,4-bis-O- 2 ', 4'-Diethylbenzylidene) -1-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, 1 , 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-propyl sorbitol, 1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -1-n-propyl sorbitol, 1,3: 2,4-bis -O- (2 ', 4'-dimethylbenzylidene)- 1-n-propyl sorbitol, 1,3: 2,4-bis-O- (2 ', 5'-dimethylbenzylidene) -1-n-propyl sorbitol, 1,3: 2,4-bis-O- ( 2 ', 6'-Dimethylbenzylidene) -1-n-propyl sorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -1-n-propyl sorbitol, 1,3 : 2,4-bis-O- (3 ', 5'-dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 3'-diethylbenzylidene)- 1-n-propyl sorbitol, 1,3: 2,4-bis-O- (2 ', 4'-diethylbenzylidene) -1-n-propyl sorbitol, 1,3: 2,4-bis-O- ( 2 ', 5'-diethylbenzylidene) -1-n-propyl sorbitol , 1,3: 2,4-bis-O- (2 ′, 6′-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3 ′, 4′- Diethylbenzylidene) -1-n-propyl sorbitol, 1,3: 2,4-bis-O- (3 ′, 5′-diethylbenzylidene) -1-n-propyl sorbitol, 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-propenyl sorbitol, 1,3: 2,4-bis-O- (p-ethoxycarbonyl) Benzylidene) -1-propenylsorbitol, 1,3: 2,4-bis-O- (p-propoxycarbonylbenzylidene) -1-propenylsorbitol, 1,3-O- (pn-propylbenzylidene) -2, 4-O- (p-propoxybenzylidene) -1-propenylsorbitol, 1,3-O- (p-propoxybenzylidene) -2,4-O- (pn-propylbenzylidene) -1-propenylsorbitol, 1 , 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-allyl sorbitol, 1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-allylso Rubitol, 1,3: 2,4-bis-O- (2 ', 3'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 4'-dimethyl Benzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2 ', 5'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2 ', 6'-Dimethylbenzylidene) -1-allylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -1-allylsorbitol, 1,3: 2,4- Bis-O- (3 ', 5'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 3'-diethylbenzylidene) -1-allyl sorbitol, 1, 3: 2,4-bis-O- (2 ', 4'-diethylbenzylidene ) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2 ′, 5′-diethylbenzylidene) -1-allyl sorbitol, 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-allyl sorbitol, 1,3: 2,4-bis-O- (3 ', 5'-diethylbenzylidene) -1-n-propyl sorbitol, 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, 1 , 3: 2,4-bis-O- (3′-bromo-4′-ethylbenzylidene) -1-allylsorbitol and the like.

  In a particularly preferred embodiment, 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 and the like.

  Further, the diacetal compound of the specific embodiment may be used alone, but from the viewpoint of other performances such as low temperature processability, two or more kinds of diacetal compounds are used in combination or are used in a premixed manner. 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- A combination of sorbitol, 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, a combination of 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- Lolobenzylidene) -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 are exemplified, and only one of them is exemplified. May be finely pulverized before use.

  The diacetal compounds are described in, for example, Japanese Patent Publication No. 48-43748, Japanese Patent Laid-Open No. 53-5165, Japanese Patent Laid-Open No. 57-185287, Japanese Patent Laid-Open No. 2-231488, and the like. It can be easily manufactured by using Also, what is currently marketed as a crystal nucleating agent for polyolefins, for example, Millad 3988, Millad NX8000 of Milliken (USA), Gelol D, Gelol MD, Gelol DXR of New Japan Rika Co., Ltd. are used as they are. Good.

Examples of the crystal nucleating agent other than the diacetal compound include sodium benzoate, aluminum p-t-butylbenzoate salt, metal salt of cyclohexanedicarboxylic acid represented by the following general formula (3), and general formula (4) below. ) Carboxylic acid salt-based compounds such as norbornanedicarboxylic acid metal salts represented by the formula (1), phosphoric acid ester salt-based compounds represented by the following general formula (5), amide compounds represented by the following general formula (6), and the following general formula Examples include rosin compounds such as rosin acid represented by (7) or a metal salt compound thereof (for example, alkali metal salts such as lithium, sodium, potassium, and magnesium).
[Wherein, M ₁ and M ₂ are both lithium ions, or jointly a single metal selected independently from the group consisting of calcium, strontium, zinc, magnesium and monobasic aluminum] A cation, 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 each is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. Groups (wherein any two vicinal (bonded to adjacent carbons) 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 Valency, 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 Individually selected from the group consisting of geminal or vicinal carbocycles having 5 carbon atoms, preferably the metal cation is 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, and 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. ]
[In formula, f represents the integer of 2-6. R ³² is a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 18 carbon atoms, an alicyclic polycarboxylic acid residue having 3 to 18 carbon atoms, or an aromatic polycarboxylic acid residue having 6 to 18 carbon atoms. Represents a group. 2 to 6 R ^{33 s} are the same or different and each is 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. ]
[In the formula, 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 ratio of the component (A) in the crystal nucleating agent for granular polyolefin resin of the present invention or the crystal nucleating agent for granular polyolefin resin to be the core is 60 to 80% by weight, and preferably 65 to 75% by weight. % Is recommended.

  The blending amount of the component (D) in the step (ii) is appropriately selected depending on the use conditions of the crystal nucleating agent for a granular polyolefin resin of the present invention, and is not particularly limited as long as the effects of the present invention are exhibited. Although not limited, 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 crystal nucleating agent for the granular polyolefin resin serving as the core. When the compounding amount of the component (D) is within the above range, caking can be eliminated by adapting to a wide range of use conditions.

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

  Specifically, for example, lauric acid, myristic acid, palmitic acid, stearic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, monoglycerides of saturated fatty acids such as lignoceric acid and palmitoleic acid, oleic acid, elaidic acid, gadoleic acid, erucic acid. Monoglycerides of unsaturated fatty acids such as acids, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, undecylenic acid, and further isostearic acid, ricinoleic acid, 12- Hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, hydrogenated castor oil fatty acid (fatty acid containing a small amount 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 above-mentioned organic acid monoglycerides, stearic acid monoglyceride, behenic acid monoglyceride and 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 An organic compound having a melting point of 100 ° C. or higher, which is the component (C), has a melting point of 100 ° C. or higher as long as the effects of the present invention are exhibited. Although any organic compound having any structure can be used, 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 is one or more compounds selected from the group consisting of ester compounds.

  Specifically, examples of alkali or alkaline earth metal salts of saturated fatty acids 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 acid containing a small amount of stearic acid and palmitic acid in addition to 12-hydroxystearic acid ) And the like, saturated metal salts of saturated fatty acids having a branched chain or a substituent such as lithium, sodium, potassium and cesium, alkali metal salts such as calcium, magnesium and barium, and transition metal salts such as zinc. Among them, stearic acid, behenic acid, 12-hydroxystearic acid calcium salt, magnesium salt, zinc salt and the like are recommended as particularly preferable compounds.

  Specifically, examples of the hindered phenol compound 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-t-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-t-butyl-4-hydroxyphenyl) butane, 2,4,6-tris (3,5-di-t-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-t-butyl-5-methylbenzyl) -4-methylphenol, bis [2-t-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-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'- Butylidene bis (3-methyl-6-t-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-t-butyl-4-hydroxyphenyl) propionamide], 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1, Three , 5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,2'-ethylidene bis (4,6-di-t-butylphenol), 2,2'-ethylidene Compounds such as bis (4-s-butyl-6-t-butylphenol), 1,3,5-tris [(3,5-di-t-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-t-butyl-4) -Hydroxyphenyl) butane, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) mesitylene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl) -4'-Hydroxyphenyl) propionate] methane, 2,2'-thiodiethylbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N '-(1,6 -Hexanediyl) bis [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate and other compounds are recommended 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-t-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 especially recommended, and further tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4). '-Hydroxyphenyl) propionate] methane is most recommended.

  Examples of the phosphite compound include triphenylphosphite, trisnonylphenylphosphite, tricresylphosphite, triethylphosphite, tris (2-ethylhexyl) phosphite, tridecylphosphite, trilaurylphosphite. , Tris (tridecyl) phosphite, trioleylphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, diphenylmono (tridecyl) phosphite, trilauryltrithiophosphite, tetraphenyldipropyleneglycoldiphosphite Fight, a mixture of tetraphenyl (tetratridecyl) pentaerythritol tetraphosphite and bis (2-ethylhexyl) phthalate, tetra (C12-C15 alkyl)- , 4'-isopropylidenediphenyldiphosphite, a 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 them, tris (2,4-di-t-butylphenyl) phosphite is particularly recommended.

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

  Further, if the proportion of the component (B) exceeds 30% by weight, the risk of caking increases, and if the proportion of the total of the components (B) and (C) exceeds 40% by weight, a crystal nucleating agent for a polyolefin resin. There is a concern that performance problems may occur, and neither is preferable.

Production of Crystal Nucleating Agent for Granular Polyolefin Resin The production method of the crystal nucleating agent for granular polyolefin resin of the present invention will be described in detail below with reference to more 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) a crystal nucleating agent for polyolefin resin, (B) an organic acid monoglyceride, and (C) an organic compound having a melting point of 100 ° C. or higher, a powder temperature of the melting point of the component (B) or higher, Granulation with stirring is performed while controlling the temperature within the melting point of the component (C).

Step (ii): (D) A crystal nucleating agent for polyolefin resin is added to the crystal nucleating agent for core polyolefin resin (core) obtained in step (i) to adjust the powder temperature to the component (B). The mixture is heated and mixed while being controlled in a temperature range not lower than the melting point of the above and less than the powder temperature of the step (i).

  The agitation granulation in the step (i) may be performed as long as granulation can be performed while stirring, and a heatable agitation granulator having a stirring blade inside a general-purpose stirring tank can be used. Typical agitation granulators include, for example, agitation tumbling granulators (high-speed mixers, etc.), high-speed agitation granulators (Henschel mixers, etc.), vertical granulators, pharmaceutical matrices, super mixers, GRAL-grall, Vertical mixers such as Shugi mixer, high speeder, new speed kneader, etc., horizontal mixers such as Loedige mixer, Spartan Luzer, pin mixer, etc. are exemplified. Among them, stirring rolling granulator and high speed stirring granulator Are especially recommended.

  The heating and mixing in the step (ii) may be performed as long as it can be mixed under heating, and a general-purpose stirring mixer such as a universal mixer can be used, but in view of productivity, it is used in the step (i). The method using the stirring granulator as it is is efficient and preferable.

  The method of charging each component in the above step (i) is not particularly limited. For example, a method of simultaneously charging three components and then stirring and granulating under heating, or a method of charging only component (A) in advance and stirring under heating. In the meantime, a method of adding the remaining components (B) and (C) all at once or sequentially and performing granulation with stirring can be mentioned.

  The "powder temperature" in the claims and the specification of the present invention means the actual temperature of powder which is a powder or a granular mixture at the time of stirring granulation, stirring and 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, for example, by heating the heating means of the stirrer, specifically, by heating a heating medium through a jacket of the stirrer to raise the temperature, and then measuring the actual powder temperature with a thermometer installed in the apparatus. Examples of the method include controlling the powder temperature by adjusting the heating by the heat medium or the heating by shearing heat while measuring, or by adjusting the cooling by the refrigerant when the heating 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), and specifically, the powder temperature in the step (i) is preferably (B). It is recommended that the temperature range is not lower than the melting point of the component and not higher than the melting point of the component (C), and particularly preferably a temperature range 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 is recommended to be lower than the heating temperature of step (i). .

<Polyolefin resin composition>
The polyolefin resin composition of the present invention is a crystal nucleating agent for a polyolefin resin according to the present invention and a polyolefin resin, and optionally other polyolefin resin additives are added, and dry blended at room temperature. Then, it can be easily obtained by melt mixing under predetermined conditions.

  The concentration of the polyolefin-based resin crystal nucleating agent according to the present invention in the polyolefin-based resin is not particularly limited as long as the effect as the polyolefin-based resin crystal nucleating agent according to the present invention is exhibited, but the polyolefin-based resin 100 parts by weight. On the other hand, it is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight.

[Polyolefin resin]
The polyolefin-based resin is not particularly limited as long as the effects of the present invention are exhibited, and conventionally known polyolefin-based resins can be used. For example, polyethylene-based resin, polypropylene-based resin, polybutene-based resin, polymethylpentene Examples thereof include resin based resins and polybutadiene based resins. More specifically, high density polyethylene, medium density polyethylene, linear polyethylene, ethylene content 50% by weight or more, preferably 70% by weight or more ethylene copolymer, propylene homopolymer, propylene 50% by weight or more, preferably 70% by weight. % Or more 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 or more methylpentene copolymer , Polybutadiene, etc. are exemplified. The above copolymer may be a random copolymer or a block copolymer. Further, when these resins have stereoregularity, they may be isotactic or syndiotactic. Specific examples of the comonomer that can form the copolymer include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene. Examples thereof include bicyclo type monomers such as endomethylene cyclohexene, methyl (meth) acrylate, (meth) acrylates such as ethyl (meth) acrylate, vinyl acetate and the like.

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

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

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

  Examples of the above-mentioned additives for polyolefin resins include various additives described in "Positive List Additives Manual" (January 2002) edited by the Hygiene Council for Polyolefins. Specifically, optical brighteners (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.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants, lubricants (paraffins, waxes, 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, having 4 to 22 carbon atoms Ester of higher fatty acid and aliphatic monohydric alcohol having 4 to 18 carbon atoms, higher fatty acid amide having 8 to 22 carbon atoms, silicone oil, rosin derivative, etc., filler (talc, high Rotalsite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agent, foaming aid, polymer additive, plasticizer (dialkyl phthalate, dialkyl hexahydrophthalate, etc.), cross-linking agent, cross-linking accelerator, charging Various additives such as inhibitors, flame retardants, dispersants, organic and inorganic pigments (indigo compounds, phthalocyanine compounds, anthraquinone compounds, ultramarine compounds, cobalt aluminate compounds, etc.), processing aids, other nucleating agents, etc. It is illustrated.

  When these additives are used, the amount thereof may be used within a range usually used unless the effects of the present invention are impaired. For example, it is preferable to use 100 parts by weight of the polyolefin resin. It is generally used in an amount of about 0.0001 to 100 parts by weight, more preferably about 0.001 to 50 parts by weight.

  As the above-mentioned antioxidant, in addition to the above-mentioned phenol compound or phosphite ester-based compound, a phenol-based antioxidant, a phosphite-based antioxidant may be added, and further a sulfur-based antioxidant should be 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, alkyl disulfides, thiodipropionates, sulfur antioxidants such as benzothiazole, 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 ] Examples include phosphite-based antioxidants such as undecane. Among them, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, which is a phenolic antioxidant, and tris (2,2, 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 is especially recommended.

<Polyolefin resin molding>
The polyolefin-based resin molded product of the present invention can be obtained by molding the above-mentioned polyolefin-based resin composition of the present invention according to a commonly used 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, film molding, etc. can be adopted.

  The polyolefin resin molded product thus obtained has excellent optical properties such as transparency and mechanical properties such as impact resistance, and is used as molded products, sheets and films for automobile parts, electrical parts, mechanical parts, daily life It is very useful for various purposes such as sundries.

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

[Properties of crystal nucleating agent]
(1) Measurement of average particle size of raw material crystal nucleating agent (laser diffraction type particle size distribution measurement)
It measured by the following method using the laser-diffraction-type particle size distribution meter (The Malvern Instruments company make, "Mastersizer 3000"). First, by using a wet measurement cell, by thoroughly stirring and mixing, the sample is dispersed in an aqueous solution containing a nonionic surfactant as a dispersant, and subsequently, the obtained mixture is further stirred in the apparatus, While circulating, ultrasonic waves were applied to disperse the particles sufficiently uniformly in the apparatus. Then, the particle size distribution of the sample was measured while applying ultrasonic waves. From the obtained particle size distribution, a volume-based cumulative 50% particle size (d50) was determined and defined as an average particle size.

(2) Measurement of particle size of crystal nucleating agent for granular polyolefin resin of the present invention (sieving test)
A sieving test was carried out under the conditions according to JIS K0069 (1992) 6.1, and the weight of the residue on the JIS test sieve having an opening of 600 μm was accurately measured using an analytical balance. The ratio of the sample used in the test to the total weight was determined from the weight of the obtained sieve having a mesh size of 600 μm.

(3) Measurement of compression ratio The funnel was held vertically at 2 cm above the opening of the graduated cylinder and with its axis aligned, and 100 cm ³ of the crystal nucleating agent was slowly passed through the funnel into the graduated cylinder of 100 cm ^3. I put it in. The weight of the crystal nucleating agent in the measuring cylinder was measured to the order of 0.1 g using a balance. The loosened 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 on the rubber sheet was repeated 50 times. The volume of the crystal nucleating agent in the graduated cylinder was read up to the digit of 0.1 cm ³ , and the bulk density was determined using the following formula (2). The compression ratio was determined from the obtained loose bulk density and firm bulk density using the following formula (3). It is generally 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);
Firm 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 liquidity]
(4) Measurement of the angle of repose Under the conditions of 25 ° C. and humidity of 60%, 30 g of the crystal nucleating agent was placed on a funnel having a diameter of an opening of 9 cm and a hole of 1 cm from a height of 1 cm from the upper edge of the funnel. It is poured into a circular table having a diameter of 9 cm at a position 10 cm from the bottom of the funnel without shaking. The height of the falling cone-shaped deposit was measured, and the angle formed by the horizontal plane and the generatrix was calculated and used as the angle of repose (unit: degree). The smaller the angle of repose, the better the powder fluidity.

(5) Powder fluidity 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 funnel lower opening without vibrating. From the discharge state of the crystal nucleating agent from the funnel, the fluidity of the crystal nucleating agent was evaluated by a 4-step evaluation according to the following criteria.
(Evaluation criteria)
⊚: All the crystal nucleating agent was quickly discharged from the funnel, and almost no deposits were confirmed on the inner wall of the funnel.
◯: The crystal nucleating agent slightly remains without being discharged from the funnel, but the crystal nucleating agent remaining due to a slight impact is also completely discharged.
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 with a slight impact.
X: A large amount of the crystal nucleating agent remains 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 property]
(6) Caking test 10 g of the granular crystal nucleating agent was placed 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 visually confirmed. The following four grades were used for classification and evaluation.
A: No lump is formed.
○: Almost no lumps are formed, or even if lumps are formed, it is very brittle and soft.
Δ: A lump is formed, but it easily collapses, which poses practically no problem.
X: It becomes a lump as a whole, and it needs to be crushed before it can be used.

[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 the evaluation sample, a polypropylene-based resin molded body of 1 mm thick injection molded product was used. The smaller the obtained haze value, the better the transparency.

(8) White spot evaluation An injection-molded polyolefin resin molded body of 50 mm x 50 mm x 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 using them as the number of white points of the sample, and from the obtained evaluation results, classification and evaluation were performed according to the following 3 grades.
A: The number of white points is less than 3. There is no problem in terms of the performance of the molded product.
◯: The number of white points is in the range of 3 to 15. There is no problem in terms of performance as a nucleating agent, but the undispersed substance may affect other physical properties.
X: Existence is confirmed when the number of white points exceeds 15. Apparently, the effect of the nucleating agent has not been sufficiently exhibited, and the undispersed substance is likely to cause problems in various physical properties.

Abbreviations for compounds in Examples DMDBS: 1,3: 2,4-bis-O- (3 ', 4'-dimethylbenzylidene) -D-sorbitol PDBN: 1,3: 2,4-bis-O- ( p-n-propylbenzylidene) -1-n-propylsorbitol GMS: stearic acid monoglyceride Irg1010: tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (BASF Japan ( Co., Ltd., trade name "IRGANOX1010")
CaSt: calcium stearate

[Example 1]
1.5 kg of DMDBS (manufactured by Shin Nippon Rika Co., Ltd., Gelol DXR, average particle size 6.2 μm), GMS (manufactured by Riken Vitamin Co., Ltd.) at room temperature in a 20 L super mixer (manufactured by Kawata Co., Ltd.) equipped with a thermometer. , Melting point: 65 ° C.) and Irg1010 (melting point; 120 ° C.) 0.3 kg were added, and the mixture was stirred at a stirring speed of 300 rpm while heating the jacket with steam. After the powder temperature 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 a granular crystal nucleating agent of the present invention. The final powder temperature was 96 ° C. From the results of the sieving test, it was confirmed that the obtained granular crystal nucleating agent had a ratio of the residue on the sieve having an opening of 600 μm of 30% by weight based on the total weight.
Then, 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, the obtained granular crystal nucleating agent was used to evaluate caking properties and powder fluidity by a powder fluidity test (funnel test), and 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. According to the result of the sieving test, the obtained granular crystal nucleating agent was found to have 58% by weight of the residue on the sieve having an opening of 600 μm based on the total weight. confirmed.
Then, 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, and 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. From the results of the sieving test, it was confirmed that the obtained granular crystal nucleating agent had a ratio of the residue on the sieve having an opening of 600 μm of 99% by weight based on the total weight.
Then, 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, and the results are summarized in Table 1. It was shown to.

[Example 4]
To a 20 L super mixer equipped with a thermometer, 1.4 kg of DMDBS, 0.3 kg of GMS and 0.3 kg of Irg1010 were charged at room temperature, and the jacket was stirred at a stirring speed of 300 rpm while heating with steam. After raising the powder temperature to 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 to be the core. The powder temperature at this time was 96 ° C. Then, the stirring was stopped, 0.1 kg of DMDBS was additionally charged into the super mixer, and the mixture was stirred again at a stirring speed of 1500 rpm for 3 minutes. The final powder temperature was 90 ° C. From the results of the sieving test, it was confirmed that the obtained granular crystal nucleating agent had a ratio of residue of 98% by weight based on the total weight on the sieve having an opening of 600 μm.
Then, 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, and 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 additionally charged was changed to 0.2 kg. The final powder temperature was 87 ° C. From the results of the sieving test, it was confirmed that the obtained granular crystal nucleating agent had a ratio of the residue on the sieve having openings of 600 μm of 84% by weight based on the total weight.
Then, 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, and 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. From the results of the sieving test, it was confirmed that the obtained granular crystal nucleating agent had a ratio of the residue on the sieve having an opening of 600 μm of 50% by weight based on the total weight.
Then, 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, and 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 KK, melting point: 148 ° C). The final powder temperature was 100 ° C. From the results of the sieving test, it was confirmed that the obtained granular crystal nucleating agent had a ratio of the residue on the sieve having an opening of 600 μm of 99% by weight based on the total weight.
Then, 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, and the results are summarized in Table 1. It was shown to.

[Example 8]
Polypropylene random copolymer as a polyolefin resin (MFR = 7 g / 10 min (load 2160 g, temperature 230 ° C.), R-720 manufactured by Prime Polymer Co., Ltd.) 100 parts by weight, obtained in Example 1 as a crystal nucleating agent 0.31 part by weight of a granular crystal nucleating agent, 0.05 part by weight of calcium stearate (CaSt) as another additive, 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 (manufactured by BASF Japan Ltd., trade name "IRGAFOS168") were dry blended. The dry blend was melt-mixed at a barrel temperature of 250 ° C. using a single-screw extruder (VS-20 manufactured by Tanabe Plastics Machinery Co., Ltd.), and the extruded strand was cooled and cut with a pelletizer to obtain a polyolefin resin. A composition was prepared.

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

  The haze value was measured using the molded body obtained above as an evaluation sample, and the obtained results are shown in Table 2. Subsequently, the white spots in the molded body were visually evaluated by the above method, and the results are also shown in Table 2.

[Example 9]
A polyolefin-based resin composition and a polyolefin-based resin molded product 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 2 was used as the crystal nucleating agent. Obtained. The haze value was measured using the obtained molded body, and the obtained results are shown in Table 2. Subsequently, the white spots in the molded body were visually evaluated by the above method, and the results are also shown in Table 2.

[Example 10]
As a crystal nucleating agent, 0.29 parts by weight of the granular crystal nucleating agent obtained in Example 3 was used, and the same procedure as in Example 8 was carried out except that the amount of Irg1010 was changed to 0.02 parts by weight, A polyolefin resin composition and a polyolefin resin molded product were obtained. The haze value was measured using the obtained molded body, and the obtained results are shown in Table 2. Subsequently, the white spots in the molded body were visually evaluated by the above method, and the results are also shown in Table 2.

[Example 11]
A polyolefin-based resin composition and a polyolefin-based resin molded product were obtained in the same manner as in Example 8, except that 0.28 part by weight of the granular crystal nucleating agent obtained in Example 4 was used as the crystal nucleating agent. Obtained. The haze value was measured using the obtained molded body, and the obtained results are shown in Table 2. Subsequently, the white spots in the molded body were visually evaluated by the above method, and the results are also shown in Table 2.

[Example 12]
A polyolefin-based resin composition and a polyolefin-based resin molded product were obtained in the same manner as in Example 8, except that 0.28 part by weight of the granular crystal nucleating agent obtained in Example 5 was used as the crystal nucleating agent. Obtained. The haze value was measured using the obtained molded body, and the obtained results are shown in Table 2. Subsequently, the white spots in the molded body were visually evaluated by the above method, and the results are also shown in Table 2.

[Example 13]
A polyolefin-based resin composition and a polyolefin-based resin molded product 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. The haze value was measured using the obtained molded body, and the obtained results are shown in Table 2. Subsequently, the white spots in the molded body were visually evaluated by the above method, and the results are also 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. Was carried out in the same manner as in Example 8 to obtain a polyolefin resin composition and a polyolefin resin molded product. The haze value was measured using the obtained molded body, and the obtained results are shown in Table 2. Subsequently, the white spots in the molded body were visually evaluated by the above method, and the results are also shown in Table 2.

  From the results of Table 1 and Table 2 above, the granular crystal nucleating agent according to the present invention has very excellent fluidity and further contributes to the improvement in productivity without problems such as caking, and It can be seen that the polyolefin-based resin molded product containing the granular crystal nucleating agent does not have a problem such as white spots and has excellent transparency, and is very useful for various applications.

  The crystal nucleating agent for a granular polyolefin resin of the present invention has greatly improved fluidity and can be used in various applications as a crystal nucleating agent having excellent fluidity. Further, the crystal nucleating agent for granular polyolefin-based resin of the present invention has the same or higher performance as the conventional crystal nucleating agent with respect to dispersibility and solubility in the polyolefin-based resin. Is also very useful. Therefore, the crystal nucleating agent for granular polyolefin-based resin of the present invention can greatly contribute to the improvement of productivity in various applications, and the obtained polyolefin-based resin molded product has no crystal nucleating agent. It has no defects such as white spots due to dispersions and undissolved substances, and has excellent optical properties such as transparency and mechanical properties such as impact resistance, and is used for automobile parts, electrical parts, mechanical parts, daily necessities, It can be widely used for various purposes such as clothes cases and food containers.

Claims (8)

Particles of a crystal nucleating agent for a polyolefin resin, which comprises (D) a diacetal compound represented by the following general formula (1), are attached to the core portion of the crystal nucleating agent composition for a polyolefin resin,
The crystal nucleating agent composition for a granular polyolefin resin in the core portion comprises (A) a crystal nucleating agent for a polyolefin resin composed of a diacetal compound represented by the following general formula (1) , (B) an organic acid monoglyceride, ( C) comprising a hindered phenolic compound having a melting point above 100 ° C.,
The proportion of the component (A) in the crystal nucleus agent composition for a granular polyolefin resin of the core portion is 60 to 80% by weight, the proportion of the component (B) is 10 to 30% by weight, and ) Component and (C) component in a total proportion of 20 to 40% by weight, and
In the crystal nucleating agent composition for a granular polyolefin resin of the core portion, 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 powder the body temperature of component (B) above the melting point, while controlling the following temperatures the melting point of component (C) state, and are not heated stirring granulation, further,
In screening tests conducted under the conditions conforming to JIS K0069 (1992), granular polyolefin which relative to the total weight of the residue on sieve for JIS test mesh opening 600μm is characterized der Rukoto 10 wt% or more A crystal nucleating agent composition for resins.
[In the 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, a linear or branched carbon atom, respectively. It represents 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. 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 groups of the numbers 1 to 4 are shown. m and n each represent an integer of 1 to 5. p represents 0 or 1. Two R ^1's may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. The 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 for granular polyolefin resin according to claim 1 , wherein the adhered amount of the component (D) is 1 to 20 parts by weight with respect to 100 parts by weight of the crystal nucleating agent composition for granular polyolefin resin in the core portion. Nucleating agent composition . The crystal nucleating agent composition for a granular polyolefin resin according to claim 1 or 2 , wherein the component (B) is a monoglyceride of a fatty acid which may have at least one hydroxyl group in the molecule. The angle of repose is not more than 40 degrees of the granular polyolefin resin for crystallization nucleating agent composition, and loosen the compression ratio obtained from the bulk density for Toka bulk density of 1.2 or less, any claim 1-3 granular polyolefin resin for crystallization nucleating agent composition crab according. A method for producing a crystal nucleating agent composition for a granular polyolefin resin, which has improved fluidity,
(I) (A) A crystal nucleating agent for a polyolefin resin, which comprises a diacetal compound represented by the following general formula (1) , (B) an organic acid monoglyceride, and (C) a hindered phenol system having a melting point of 100 ° C. or higher. The step of stirring and granulating the compound while controlling the powder temperature in the temperature range from the melting point of the component (B) to the melting point of the component (C) to obtain a granular nucleating agent composition for polyolefin resin. ,
(Ii) In addition to the granular nucleating agent composition for polyolefin resin obtained in step (i), (D) a crystalline nucleating agent for polyolefin resin comprising a diacetal compound represented by the following general formula (1). In addition, while controlling the powder temperature in the temperature range not lower than the melting point of the component (B) and lower than the powder temperature in the step (i), heating and mixing are performed to obtain a crystal nucleating agent composition for granular polyolefin resin. In the sieving test conducted by the crystal nucleating agent composition for granular polyolefin resin under the conditions according to JIS K0069 (1992), the total weight of the residue on the JIS test sieve having an opening of 600 μm A manufacturing method characterized in that the proportion is 10% by weight or more .
[In the 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, a linear or branched carbon atom, respectively. It represents 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. 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 groups of the numbers 1 to 4 are shown. m and n each represent an integer of 1 to 5. p represents 0 or 1. Two R ^1's may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. The 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. ] Polyolefin resin as defined in Claim 1 granular polyolefin resin for crystallization nucleating agent composition comprising at polyolefin resin composition according to any one of 4. A polyolefin-based resin molded product, comprising the polyolefin-based resin composition according to claim 6 as a raw material. (A) A crystal nucleating agent for a polyolefin resin composed of a diacetal compound represented by the following general formula (1) , (B) an organic acid monoglyceride, and (C) a hindered phenol compound having a melting point of 100 ° C. or higher are powdered. While controlling the body temperature in the temperature range above the melting point of the component (B) and below the melting point of the component (C), the mixture is agitated and mixed to form granules .
The granular crystal nucleating agent composition for polyolefin resin obtained above and (D) a crystal nucleating agent for polyolefin resin composed of a diacetal compound represented by the following general formula (1) In a sieving test carried out under the conditions according to JIS K0069 (1992) by heating and mixing while controlling the body temperature to a temperature range not lower than the melting point of the component (B) and lower than the powder temperature at the time of stirring and mixing , A method for improving the fluidity of a crystal nucleating agent composition for a polyolefin-based resin, which comprises a granule having a ratio of 10% by weight or more to the total weight of the residue on a JIS test sieve having an opening of 600 μm .
[In the 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, a linear or branched carbon atom, respectively. It represents 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. 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 groups of the numbers 1 to 4 are shown. m and n each represent an integer of 1 to 5. p represents 0 or 1. Two R ^1's may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. The 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. ]