JP6849912B2 - Method for improving fluidity of crystal nucleating agent for polyolefin resin - Google Patents

Description

The present invention relates to an improvement in the fluidity of a crystal nucleating agent for a polyolefin resin. Specifically, a method for improving the fluidity and at the same time improving the dispersibility, and the fluidity obtained by the method is excellent and dispersed. The present invention relates to a crystal nucleating agent for a polyolefin-based resin having excellent properties, a polyolefin-based resin composition containing the crystal nucleating agent, and a molded product thereof.

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

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

In recent years, in general-purpose plastics, further improvement in productivity has been promoted, and as a part of this, improvement in feedability of raw materials, that is, its fluidity has also been promoted. Under such circumstances, the poor fluidity of the above-mentioned crystal nucleating agent, especially the crystal nucleating agent of the diacetal compound, is a major bottleneck in improving productivity.

Therefore, various studies have been conducted on the improvement of the fluidity of crystal nucleating agents such as diacetal compounds. For example, a method of improving fluidity by granulating (Patent Documents 1 to 3) and a method of improving fluidity by adding a fluidity improving agent without granulating (Patent Documents 4 to 8) are available. Proposed.

In the case of the first granulation method, the fluidity is improved, but the dispersibility and solubility in the polyolefin resin tend to be deteriorated, and as a result, the performance such as the original transparency of the nucleating agent is deteriorated. There was a concern that not only the deterioration but also the appearance problems such as white spots would occur. Therefore, a method of adding an additive such as a binder is common and widely used. However, depending on the application, the above problem may not be completely solved even if an additive such as a binder is added, and further, there is a case where the influence on the performance of the additive such as a blended binder becomes a problem.

The second method of adding a fluidity improver without granulation is also effective for improving fluidity, and has less problems such as dispersibility such as granulation, and has been used in various applications so far. I came. However, as in the case of adding the above-mentioned binder, there is a case where the influence on the performance of the flow improver, which is the added additive, becomes a problem depending on the application.

Further, it is known that the performance of the crystal nucleating agent largely depends on the dispersibility and solubility of the crystal nucleating agent in the resin. Therefore, various studies have been made so far in order to improve the dispersibility and solubility in the resin. For example, a method of using a plurality of nucleating agents in combination, a method of adding an additive for improving dispersibility and solubility (Patent Documents 9 to 11), and the like have been proposed and put into practical use. Further, a method of reducing the particle size, that is, making the particles finer (Patent Document 12) is also an effective method and is widely used.

However, in the case of the method of adding the first additive, there is a concern that new problems such as bleeding due to the added additive may occur depending on the application. Further, in the case of the second micronization, although the dispersibility is very excellent, there is a concern that handling problems such as transferability may occur.

Furthermore, as a recent trend, in consideration of environmental issues in general and in order to ensure the flexibility of compounding formulations, unnecessary additives are not compounded as much as possible, and the above-mentioned fluidity and dispersion are being promoted. As for the improvement of the property, a method of improving the property without adding additives such as a binder, a fluidity improving agent and a dispersibility improving agent is desired. In particular, this tendency is particularly remarkable in medical applications, and there are strict restrictions on the additives that can be blended, and the development of an improvement method that essentially does not use additives is strongly desired.

WO98 / 33851 Japanese Unexamined Patent Publication No. 2001-81236 WO02 / 077094 Special Table 2009-507982 Japanese Unexamined Patent Publication No. 2013-209662 JP-A-2015-30849 Japanese Patent No. 5920524 Japanese Unexamined Patent Publication No. 2016-121303 Japanese Unexamined Patent Publication No. 60-101131 Japanese Unexamined Patent Publication No. 08-245843 Japanese Unexamined Patent Publication No. 2001-240698 Japanese Unexamined Patent Publication No. 06-145431

INDUSTRIAL APPLICABILITY The present invention is a method for improving the fluidity and dispersibility of a crystal nucleating agent for a polyolefin resin without using an additive, and improving the fluidity including the method and at the same time improving the dispersibility. A method for producing a crystal nucleating agent for a polyolefin-based resin, a crystal nucleating agent for a polyolefin-based resin having excellent fluidity and dispersibility obtained by the method, and a polyolefin-based resin containing the crystal nucleating agent. An object of the present invention is to provide a composition and a molded product thereof.

In view of the above situation, the present inventors have proceeded with various studies in order to solve the above problems. For example, Japanese Patent Application Laid-Open No. 2016-121303 reported that the fluidity can be improved by combining the above-mentioned fine particle crystal nucleating agent having improved dispersibility with a specific fatty acid metal salt. However, even in the above system, it was still in the category of the technical idea of improving the fluidity and dispersibility by using an additive called a fatty acid metal salt. Therefore, the present inventors have sought a method for improving the fluidity and dispersibility without adding any additives, and as a result of diligent studies, only adjusting the particles of the crystal nucleating agent to specific properties is required. The present invention is completed by finding that fluidity and dispersibility can be improved at the same time, in other words, a fine particle crystal nucleating agent having a specific particle shape or a mixture of crystal nucleating agents can satisfy fluidity and dispersibility at the same time. It came to.

That is, the present invention is a method for improving the fluidity of the crystal nucleating agent for polyolefin resins shown below and at the same time improving the dispersibility, and the crystal nucleating agent having excellent fluidity and dispersibility obtained by the method. Further, the present invention provides a polyolefin-based resin composition containing the crystal nucleating agent and a molded product thereof.

[Item 1] A crystal nucleating agent for polyolefin resins with improved fluidity.
A fine particle-like crystal nucleating agent characterized in that the average value of the particle size of the crystal nucleating agent determined by laser diffraction type particle size distribution measurement is 0.5 to 4.0 μm and the uniformity is 3 to 10. ..

[Item 2] The crystal nucleating agent is obtained from the crystal nucleating agent (A) having an average particle size of 0.5 to 2.0 μm obtained by the laser diffraction type particle size distribution measurement and the laser diffraction type particle size distribution measurement. Item 2. The crystal nucleating agent according to [Item 1], which is a mixture with the crystal nucleating agent (B) having an average particle size of 4.0 to 15.0 μm.

[Item 3] Further, the 50% value of the aspect ratio of the crystal nucleating agent determined by the particle image analysis method is 0.4 to 0.7, and the Lower value is 0.2 to 0.4. Item 4. The crystal nucleating agent according to [Item 1] or [Item 2].

[Item 4] The item according to any one of [Item 1] to [Item 3], wherein the average particle size of the crystal nucleating agent is 1.0 to 2.5 μm and the uniformity is 4 to 7. Crystal nucleating agent.

[Item 5] The crystal nucleating agent according to any one of [Item 1] to [Item 4], wherein the average value of the particle size of the crystal nucleating agent (A) is 0.5 to 1.5 μm.

[Item 6] The crystal nucleating agent according to any one of [Item 1] to [Item 5], wherein the 50% value of the aspect ratio of the crystal nucleating agent is 0.45 to 0.65.

[Item 7] The crystal nucleating agent according to any one of [Item 1] to [Item 6], wherein the crystal nucleating agent or the crystal nucleating agent (A) is a finely pulverized product obtained by an air flow type fine pulverizer.

[Item 8] The crystal nucleating agent according to [Item 7], wherein the airflow type pulverizer is a jet mill type pulverizer.

［式（１）中、Ｒ^１及びＲ^２は、同一又は異なって、それぞれ、水素原子、直鎖状若しくは分岐鎖状の炭素数１〜４のアルキル基、直鎖状若しくは分岐鎖状の炭素数１〜４のアルコキシ基、直鎖状若しくは分岐鎖状の炭素数１〜４のアルコキシカルボニル基又はハロゲン原子を示す。Ｒ^３は、水素原子、直鎖状若しくは分岐鎖状の炭素数１〜４のアルキル基、直鎖状若しくは分岐鎖状の炭素数２〜４のアルケニル基又は直鎖状若しくは分岐鎖状の炭素数１〜４のヒドロキシアルキル基を示す。ｍ及びｎは、それぞれ１〜５の整数を示す。ｐは０又は１を示す。２つのＲ^１は互いに結合してそれらが結合するベンゼン環と共にテトラリン環を形成していてもよい。２つのＲ^２基は互いに結合してそれらが結合するベンゼン環と共にテトラリン環を形成していてもよい。］ [Item 9] The crystal nucleating agent is a diacetal compound represented by the following general formula (1), or at least one of the crystal nucleating agent (A) and the crystal nucleating agent (B) is represented by the following general formula (1). Item 8. The crystal nucleating agent according to any one of [Item 1] to [Item 8], which is the diacetal compound shown.

[In the formula (1), R ¹ and R ² are the same or different, respectively, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched carbon. It indicates an alkoxy group having the number 1 to 4, 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 chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ]

[Item 10] In the general formula (1), R ¹ and R ² are the same or different, a methyl group or an ethyl group, R ³ is a hydrogen atom, and m and n are 1 or 2. Item 2. The crystal nucleating agent according to [Item 9], which is an integer and p is 1.

[Item 11] In the general formula (1), R ¹ and R ² are the same or different, a propyl group or a propoxy group, R ³ is a propyl group or a propenyl group, and m and n are 1. The crystal nucleating agent according to [Item 9], wherein p is 1.

[Item 12] A polyolefin-based resin composition comprising a polyolefin-based resin and the crystal nucleating agent according to any one of [Item 1] to [Item 11].

[Item 13] The polyolefin-based resin composition according to [Item 12], wherein the content of the crystal nucleating agent is 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyolefin-based resin.

[Item 14] The polyolefin-based resin composition according to [Item 13], wherein the content of the crystal nucleating agent is 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyolefin-based resin.

[Item 15] A polyolefin-based resin molded product using the polyolefin-based resin composition according to any one of [Item 12] to [Item 14] as a raw material.

[Item 16] A method for improving the fluidity of a crystal nucleating agent for a polyolefin resin.
A method characterized in that a finely pulverized product obtained by finely pulverizing the whole amount or a part of the crystal nucleating agent with an airflow type fine pulverizer has properties that simultaneously satisfy the following conditions (a) and (b).
(A) The average value of the particle size determined by the laser diffraction type particle size distribution measurement is 0.5 to 4.0 μm, and the uniformity is 3 to 10.
(B) The 50% value of the aspect ratio obtained by the particle image analysis method is 0.4 to 0.7, and the Lower value is 0.2 to 0.4.

[Item 17] The method according to [Item 16], wherein the average particle size of the crystal nucleating agent is 1.0 to 2.5 μm, and the uniformity is 4 to 7.

[Item 18] The method according to [Item 16] or [Item 17], wherein the 50% value of the aspect ratio of the crystal nucleating agent is 0.45 to 0.65.

[Item 19] The method according to any one of [Item 16] to [Item 18], wherein the airflow type pulverizer is a jet mill type pulverizer.

［式（１）中、Ｒ^１及びＲ^２は、同一又は異なって、それぞれ、水素原子、直鎖状若しくは分岐鎖状の炭素数１〜４のアルキル基、直鎖状若しくは分岐鎖状の炭素数１〜４のアルコキシ基、直鎖状若しくは分岐鎖状の炭素数１〜４のアルコキシカルボニル基又はハロゲン原子を示す。Ｒ^３は、水素原子、直鎖状若しくは分岐鎖状の炭素数１〜４のアルキル基、直鎖状若しくは分岐鎖状の炭素数２〜４のアルケニル基又は直鎖状若しくは分岐鎖状の炭素数１〜４のヒドロキシアルキル基を示す。ｍ及びｎは、それぞれ１〜５の整数を示す。ｐは０又は１を示す。２つのＲ^１は互いに結合してそれらが結合するベンゼン環と共にテトラリン環を形成していてもよい。２つのＲ^２基は互いに結合してそれらが結合するベンゼン環と共にテトラリン環を形成していてもよい。］ [Item 20] The method according to any one of [Item 16] to [Item 19], wherein the crystal nucleating agent 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, respectively, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched carbon. It indicates an alkoxy group having the number 1 to 4, 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 chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ]

[Item 21] In the general formula (1), R ¹ and R ² are the same or different, a methyl group or an ethyl group, R ³ is a hydrogen atom, and m and n are 1 or 2. The method according to [Item 20], which is an integer and p is 1.

[Item 22] In the general formula (1), R ¹ and R ² are the same or different, a propyl group or a propoxy group, R ³ is a propyl group or a propenyl group, and m and n are 1. The method according to [Item 20], wherein p is 1.

[Item 22] A method for improving the fluidity of a crystal nucleating agent for a polyolefin resin.
The crystal nucleating agent (A) having an average particle size of 0.5 to 2.0 μm of the crystal nucleating agent obtained by the laser diffraction type particle size distribution measurement and the crystal nucleating agent obtained by the laser diffraction type particle size distribution measurement. The mixture obtained by mixing the crystal nucleating agent (B) having an average particle size of 4.0 to 15.0 μm is defined to have properties that simultaneously satisfy the following conditions (a) and (b). How to feature.
(A) The average value of the particle size determined by the laser diffraction type particle size distribution measurement is 0.5 to 4.0 μm, and the uniformity is 3 to 10.
(B) The 50% value of the aspect ratio obtained by the particle image analysis method is 0.4 to 0.7, and the Lower value is 0.2 to 0.4.

[Item 23] The method according to [Item 22], wherein the average value of the particle size of the crystal nucleating agent (A) is 0.5 to 1.5.

［式（１）中、Ｒ^１及びＲ^２は、同一又は異なって、それぞれ、水素原子、直鎖状若しくは分岐鎖状の炭素数１〜４のアルキル基、直鎖状若しくは分岐鎖状の炭素数１〜４のアルコキシ基、直鎖状若しくは分岐鎖状の炭素数１〜４のアルコキシカルボニル基又はハロゲン原子を示す。Ｒ^３は、水素原子、直鎖状若しくは分岐鎖状の炭素数１〜４のアルキル基、直鎖状若しくは分岐鎖状の炭素数２〜４のアルケニル基又は直鎖状若しくは分岐鎖状の炭素数１〜４のヒドロキシアルキル基を示す。ｍ及びｎは、それぞれ１〜５の整数を示す。ｐは０又は１を示す。２つのＲ^１は互いに結合してそれらが結合するベンゼン環と共にテトラリン環を形成していてもよい。２つのＲ^２基は互いに結合してそれらが結合するベンゼン環と共にテトラリン環を形成していてもよい。］ [Item 24] The method according to [Item 22] or [Item 23], wherein at least one of the crystal nucleating agent (A) or the crystal nucleating agent (B) 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, respectively, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched carbon. It indicates an alkoxy group having the number 1 to 4, 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 chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ]

[Item 25] In the general formula (1), R ¹ and R ² are the same or different, a methyl group or an ethyl group, R ³ is a hydrogen atom, and m and n are 1 or 2. The method according to [Item 24], which is an integer and p is 1.

[Item 26] In the general formula (1), R ¹ and R ² are the same or different, a propyl group or a propoxy group, R ³ is a propyl group or a propenyl group, and m and n are 1. 24. The method according to [Item 24], wherein p is 1.

The crystal nucleating agent for polyolefin resins of the present invention is extremely excellent in fluidity and can greatly contribute to the improvement of productivity and the like. Further, the crystal nucleating agent for a polyolefin resin of the present invention is also very excellent in dispersibility and solubility in a polyolefin resin, and is very useful in terms of the performance of a molded product. Therefore, the crystal nucleating agent for polyolefin resins of the present invention has excellent productivity and can be widely used in various applications, and the obtained molded product has excellent performance and is used in many applications. Very useful in. In particular, in medical applications where the use of additives is restricted, future utilization is highly expected as a technology that can improve fluidity and dispersibility at the same time without using additives.

<Crystal nucleating agent for polyolefin resin>
The crystal nucleating agent of the present invention is a crystal nucleating agent for a polyolefin-based resin having improved fluidity, is a fine-grained crystal nucleating agent, and is obtained by a usual production method including a reaction step, a post-treatment step, and the like. A powder of a crystal nucleating agent having a general-purpose particle size is further finely pulverized by using a pulverizer such as a jet mill type airflow type pulverizer to adjust the pulverizing conditions and the like so as to have the properties of the crystal nucleating agent according to the present invention. It can be easily obtained by pulverizing. However, in the present invention, the production method is not limited, and the particle shape is adjusted in the production process such as reaction and post-treatment as long as the method can obtain the crystal nucleating agent having the properties according to the present invention. Any method may be used, and any post-production adjustment method may be used, from recrystallization to pulverization regardless of whether it is wet or dry. Further, the pulverization method is not particularly limited as long as the performance of the present invention can be obtained, from the dry airflow pulverization method to the wet pulverization method.

Further, a method is adopted in which the fine particle crystal nucleating agent such as the above-mentioned finely pulverized product and the crystal nucleating agent having a general-purpose particle size are simply mixed by adjusting the mixing ratio so as to have the properties of the crystal nucleating agent according to the present invention. You can also do it. In that case, the types of crystal nucleating agents to be mixed do not necessarily have to be the same as long as the effects of the present invention are obtained.

In the fine particle crystal nucleating agent of the present invention, the average value of the particle size of the crystal nucleating agent particles determined by laser diffraction type particle size distribution measurement is 0.5 to 4.0 μm, preferably 0.5 to 3.0 μm. It is more preferably 0.5 to 2.5 μm and has a uniformity of 3 to 7, preferably 4 to 7.

More preferably, the fine particle crystal nucleating agent of the present invention has a 50% value of the aspect ratio of the crystal nucleating agent determined by the particle image analysis method of 0.4 to 0.7, preferably 0.45 to 0. It is characterized in that it is 65 and the Lower value is 0.2 to 0.4.

Regarding the particle size, as described above, it is known that the smaller the average particle size and the smaller the number of particles having a large particle size, the better the dispersibility and solubility in the polyolefin resin. However, it is also well known that the crystal nucleating agent alone tends to decrease in fluidity as the particle size becomes smaller. On the contrary, it is known that the larger the average particle size, the better the fluidity. However, it is well known that the crystal nucleating agent alone tends to decrease in dispersibility and solubility as the particle size increases.

It is important to adjust the average particle size of the crystal nucleating agent of the present invention to a range that is neither too large nor too small, rather than the range in which the above-mentioned fluidity and dispersibility and solubility can be balanced, and further, the particle size distribution. It has the greatest feature in that it is possible to further improve the fluidity by adjusting the range of.

In the present specification and claims, the "mean particle size" means the particle size (d50) at a volume-based cumulative 50% in the particle size distribution obtained by laser diffraction particle size distribution measurement. In the present specification, the "average value of particle size" may be referred to as "average particle size". Similarly, the "uniformity of particle size" in the present specification and claims refers to the particle size (d60) at a volume-based cumulative 60% and the particle size (d10) at a volume-based cumulative 10% in the particle size distribution. ) (D60 / d10) was determined and used as the uniformity. The closer the value of d60 / d10 is to 1, the narrower the particle size distribution.

Further, for the laser diffraction particle size distribution measurement, a general-purpose method / condition method using a general-purpose device can be adopted. For example, specifically, the following method is exemplified; laser diffraction type. Using a particle size distribution meter (Malburn Instruments, "Mastersizer 3000"), the sample was dispersed in an aqueous solution to which a surfactant was added as a dispersant by sufficiently stirring and mixing in a wet measurement cell, followed by Then, while the obtained mixture is further stirred and circulated in the apparatus, ultrasonic waves are applied to disperse the mixture sufficiently uniformly in the apparatus, and then the particle size distribution of the sample can be measured while applying ultrasonic waves. ..

It is also known that the aspect ratio is one of the factors that affect the fluidity. However, in order to improve the fluidity, it depends on the type of the target compound and the state of the flow field, and there is no guideline for what factors should be examined. It is examined while imagining the combined action of the factors. In the present invention, as a result of measuring the aspect ratio of fine particles prepared under various conditions by a particle image analysis method, in the crystal nucleating agent for polyolefin resins, there are few particles having a large aspect ratio, and the aspect ratio is within a specific range. It was confirmed that the fine particles having a central shape affect the improvement of fluidity.

Regarding the proportion of particles having a large aspect ratio, the numerical value of the measurement result of the Lower value of the aspect ratio was used as an index, and the center of the aspect ratio was the numerical value of the measurement result of the cumulative 50% value of the aspect ratio. ..

That is, in the present specification and claims, the "50% value" is a cumulative 50% value in the distribution of the aspect ratio obtained by the measurement by the particle image analysis method, and the center of the aspect ratio is defined as described above. means. Similarly, the "Lower value" in the present specification and claims is a cumulative 10% value in the distribution of the aspect ratio obtained by the measurement by the particle image analysis method, and the larger the value is, the more the aspect is as described above. It means that the proportion of particles with a large ratio is small.

Further, for the measurement of the aspect ratio by the above particle image analysis method, a method based on a general-purpose method / condition using a general-purpose device can be adopted. For example, specifically, the following method is exemplified. After adding a surfactant as a dispersant to ion-exchanged water in the measurement container, the measurement sample is added and dispersion treatment is performed to uniformly disperse the measurement sample. After that, the measurement can be performed using a flow-type particle image analyzer (“FPIA-3000” manufactured by Malvern Instruments), and the distribution of the aspect ratio of the sample can be measured from the obtained data.

Method for Adjusting Properties of Crystal Nucleating Agent As described above, any method for adjusting the properties of the crystal nucleating agent according to the present invention may be used as long as the desired properties can be obtained, but it is preferable. Is recommended from the viewpoint of ease of adjustment, etc., by adjusting the crystal nucleating agent having a general-purpose particle size after production.

As the method of adjusting after production, for example, a method of finely pulverizing using a jet mill type airflow crusher or the like is recommended from the viewpoint of ease of adjusting properties such as particle size. In that case, a method of controlling the finely pulverized conditions so as to obtain the desired properties, or a previously finely pulverized crystal nucleating agent and an unground crystal nucleating agent (for example, a crystal nucleating agent having a general-purpose particle size) can be used as the desired properties. Examples thereof include a method of adjusting the ratio so as to be the same and mixing.

In the case of the method of mixing the finely pulverized crystal nucleating agent and the uncrushed crystal nucleating agent, the ratio varies depending on each particle size and does not necessarily have to be in a fixed range, but is usually a finely pulverized product / an uncrushed product. The method of adjusting the ratio in the range of about 1 / 1-3 / 1 is preferable in terms of productivity and performance. In particular, depending on the application, the desired performance may not be obtained with a single type of nucleating agent. In that case, the crystal nucleating agent of the present invention can be obtained by finely pulverizing only one of the crystal nucleating agents. Is possible and superior.

Types of Crystal Nucleating Agents The types of crystal nucleating agents for polyolefin resins of the present invention are not particularly limited as long as the effects of the present invention are exhibited, and are, for example, diacetal compounds, carboxylate compounds, and phosphoric acids. Examples thereof include ester salt compounds, amide compounds, and rosin compounds. Among them, the effect of the present invention is most remarkable in the diacetal compound.

［式（１）中、Ｒ^１及びＲ^２は、同一又は異なって、それぞれ、水素原子、直鎖状若しくは分岐鎖状の炭素数１〜４のアルキル基、直鎖状若しくは分岐鎖状の炭素数１〜４のアルコキシ基、直鎖状若しくは分岐鎖状の炭素数１〜４のアルコキシカルボニル基又はハロゲン原子を示す。Ｒ^３は、水素原子、直鎖状若しくは分岐鎖状の炭素数１〜４のアルキル基、直鎖状若しくは分岐鎖状の炭素数２〜４のアルケニル基又は直鎖状若しくは分岐鎖状の炭素数１〜４のヒドロキシアルキル基を示す。ｍ及びｎは、それぞれ１〜５の整数を示す。ｐは０又は１を示す。２つのＲ^１は互いに結合してそれらが結合するベンゼン環と共にテトラリン環を形成していてもよい。２つのＲ^２基は互いに結合してそれらが結合するベンゼン環と共にテトラリン環を形成していてもよい。］ 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, respectively, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched carbon. It indicates an alkoxy group having the number 1 to 4, 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 chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ]

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

Further, the following compounds can also be exemplified as more preferable compounds; in the above general formula (1), R ¹ and R ² are propyl groups or propoxy groups, and R ³ is a propyl group or propenyl group. A compound in which 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-isopropylbenzylylene) -D-sorbitol, 1,3: 2,4-bis-O- (m-isopropylbenzylylene) -D-sorbitol, 1,3: 2, 4-bis-O- (p-isopropylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (one-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- (o-n-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (mn-butylbenzylidene) -D-sorbitol, 1,3: 2,4- Bis-O- (pn-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (o-tert-butylbenzylidene) -D-sorbitol, 1,3: 2,4- Bis-O- (m-tert-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-tert-butylbenzylidene) -D-sorbitol, 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) '-Dimethylbenzitol) -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' -Trimethylbenzitol) -D-sorbitol, 1,3: 2,4-bis-O- (2', 4', 5'-triethylbenzitol) -D-sorbitol, 1,3: 2,4-bis-O -(3', 4', 5'-triethylbenzitolide) -D-sorbitol, 1,3: 2,4-bis-O- (o-methoxybenzylidene) -D-sorbitol, 1,3: 2,4- Bis-O- (m-methoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-methoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (O-ethoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-ethoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-ethoxy) Benzylidene) -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-isopropoxybenziliden) -D-sorbitol, 1,3: 2,4-bis-O- (one-propoxybenziliden)- D-sorbitol, 1,3: 2,4-bis-O- (mn-propoxybenziliden) -D-sorbitol, 1,3: 2,4-bis-O- (pn-propoxybenziliden)- D-sorbitol, 1,3: 2,4-bis-O- (o-methoxycarbonylbenzylene) -D-sorbitol, 1,3: 2, 4-bis-O- (m-methoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4-bis-O- (p-methoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4- Bis-O- (o-ethoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4-bis-O- (m-ethoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4-bis- O- (p-ethoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4-bis-O- (o-isopropoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4-bis-O -(M-Isopropoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4-bis-O- (p-isopropoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4-bis-O -(On-propoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (mn-propoxycarbonylbenzylene) -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: 2,4-bis-O- (o-bromobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-bromobenzylidene) -D-sorbitol , 1,3: 2,4-bis-O- (p-bromobenzylidene) -D-sorbitol, 1,3-O-benzylidene-2,4-O- (p-methylbenzylidene) -D-sorbitol, 1, , 3-O- (p-methylbenzylidene) -2,4-O-benzyllidene-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-bendylidene-2,4-O- (p-chlorobenzylidene) ) -D-sorbitol, 1,3-O- (p-chlorobenziliden) -2,4-O-benziliden-D-sorbitol, 1,3-O-benziliden-2,4-O- (2', 4) '-Dimethylbenziliden) -D-sorbitol, 1,3-O- (2', 4'-dimethylbenziliden) -2,4-O-benziliden-D-sorbitol, 1,3-O-benziliden-2,4 -O- (3', 4'-dimethylbenzylidene) -D-sorbitol, 1,3-O- (3', 4'-dimethylbenziliden) -2,4-O-benziliden-D-sorbitol, 1,3 -O- (p-methylbenzylidene) -2,4-O- (p-ethylbendylidene) -D-sorbitol, 1,3-O- (p-ethylbendylidene) -2,4-O- (p-methyl) Benzilidene) -D-sorbitol, 1,3-O- (p-methylbenziliden) -2,4-O- (3', 4'-dimethylbenzylidene) -D-sorbitol, 1,3-O- (3' , 4'-Dimethylbenziliden) -2,4-O-p-Methylbenziliden-D-sorbitol, 1,3-O- (p-ethylbendylidene) -2,4-O- (3', 4'-dimethyl Benzilidene) -D-sorbitol, 1,3-O- (3', 4'-dimethylbenziliden) -2,4-O-p-ethylbendylidene-D-sorbitol, 1,3-O- (p-methylbenziliden) ) -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-benzylidene-1-methylsorbitol, 1,3: 2,4-bis-O- (p-methylbenziliden) -1-methylsorbitol, 1,3: 2,4- Bis-O- (p-ethylbenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (pn-propylbenziliden) -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'-dimethylbenzylene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2', 6'-dimethylbenzylene) -1 -Methylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethi Rubendilidene) -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'-methoxybenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (3') , 4'-dichlorobenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (p-methoxycarbonylbenzylene) -1-methylsorbitol, 1,3: 2,4-bis-O- (3'-Methyl-4'-fluorobenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (3'-bromo-4'-ethylbendiliden) -1-methylsorbitol, 1, 3: 2,4-bis-O-benzylidene-1-ethylsorbitol, 1,3: 2,4-bis-O- (p-methylbenziliden) -1-ethylsorbitol, 1,3: 2,4-bis -O- (p-ethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (pn-propylbenziliden) -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'-diethi) Rubenzylidene) -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-methoxycarbonylbenzylene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3'-methyl-4'-fluoro) Benzilidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3'-bromo-4'-ethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- Benziliden-1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-methylbenziliden) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-) Ethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (pn-propylbenziliden) -1-n-propylsorbitol, 1,3: 2,4-bis-O -(2', 3'-dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 4'-dimethylbenzylidene) -1-n-propylsorbitol, 1 , 3: 2,4-bis-O- (2', 5'-dimethylbenzylene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 6'-dimethylbenzylene) ) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O -(3', 5'-Dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 3'-diethylbenzylidene) -1-n-propylsorbitol, 1 , 3: 2,4-bis-O- (2', 4'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 5'-diethylbenzylidene) ) -1-n-Propylsorbitol, 1,3: 2,4-bis-O- (2', 6'-dieti) Rubendilidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3', 4'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis -O- (3', 5'-diethylbenzylene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3'-methyl-4'-methoxybenzylene) -1-n- Propylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dichlorobenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-methoxycarbonyl) Benzilidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-ethoxycarbonylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- ( p-propoxycarbonylbenzylene) -1-n-propylsorbitol, 1,3-O- (pn-propylbenzylene) -2,4-O- (p-propoxybenzylidene) -1-n-propylsorbitol, 1 , 3-O- (p-propoxybenzylene) -2,4-O- (pn-propylbenzylene) -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'-ethylbendylidene) -1-n-propylsorbitol, 1, 3: 2,4-bis-O- (pn-propylbenzylene) -1-propenylsorbitol, 1,3: 2,4-bis-O- (p-ethoxycarbonylbenzylene) -1-propenylsorbitol, 1 , 3: 2,4-Bis-O- (p-propoxycarbonylbenzylene) -1-propenylsorbitol, 1,3-O- (pn-propylbenzylene) -2,4-O- (p-propoxybenzylene) ) -1-Propenylsorbitol, 1,3-O- (p-propoxybenzylidene) -2,4-O- (pn-propylbenzylene) -1-propenylsorbitol, 1,3: 2,4-bis- O-benzylidene-1-allyl sorbitol, 1,3: 2,4-bis-O- (p-methylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) ) -1-allyl sorbitol, 1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bi S-O- (2', 3'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 4'-dimethylbenzylidene) -1-allyl sorbitol, 1, 3: 2,4-bis-O- (2', 5'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 6'-dimethylbenzylidene) -1 -Allyl sorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3', 5') -Dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 3'-diethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 4'-diethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 5'-diethylbenzylidene) -1-allyl sorbitol, 1,3: 2, 4-Bis-O- (2', 6'-diethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3', 4'-diethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (p-ethoxycarbonylbenzylene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (p-propoxycarbonylbenzylidene) -1-allyl sorbitol, 1,3-O- (pn-propylbenziliden) -2,4-O- (p-propoxybenzylidene) -1-allyl sorbitol, 1,3-O- (p-propoxybenzylidene) -2,4- O- (pn-propylbenzylene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3', 5'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3'-methyl-4'-methoxybenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3', 4'-dichlorobenzylidene) -1 -Allyl sorbitol, 1,3: 2,4-bis-O- (p-methoxycarbonylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3'-methyl-4'- Fluorobenzylene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3'-bromo-4'-ethylbenzylidene) -1-allyl sorbitol and the like are exemplified.

Particularly preferred embodiments are 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.

Further, the diacetal compound of the above specific embodiment may be used alone, but from the viewpoint of other performance, for example, low temperature processability, two or more kinds of diacetal compounds may be used in combination or in a premixed manner. May be good.

When used in combination or in a 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 and 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol and 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene)- Combination of D-sorbitol, combination of 1,3: 2,4-dibenzylidene-D-sorbitol and 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -D-sorbitol, Of 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol and 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -D-sorbitol Combination, 1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol and 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -D- An example is a combination of sorbitol, and only one of them may be finely pulverized and used.

The diacetal compound is produced, for example, as described in JP-A-48-43748, JP-A-53-5165, JP-A-57-185287, JP-A-2-231488, and the like. It can be easily manufactured by using or the like. In addition, general-purpose grains such as those currently commercially available as crystal nucleating agents for polyolefins, such as Millad 3988 and Millad NX8000 from Milliken (USA), Gelol D, Gelol MD, and Gelol DXR from Shin Nihon Rika Co., Ltd., are used. It may be used as it is as a crystal nucleating agent having a diameter (for example, a crystal nucleating agent (B)), or a finely pulverized crystal nucleating agent (for example, a crystal nucleating agent for a polyolefin resin having improved fluidity or a crystal nucleating agent (A). )) May be used as a raw material crystal nucleating agent.

［式中、Ｍ_１及びＭ_２は、いずれもリチウムイオンを示すか、またはＭ_１とＭ_２の２つの金属イオンが単一の金属イオンにまとめられてなる二価の金属カチオン：カルシウム、ストロンチウム、亜鉛、マグネシウム若しくは一塩基性アルミニウムを示す。Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６は、同一又は異なって、水素原子、炭素数１〜９のアルキル基（ここで、いずれか２つのビシナル（隣接炭素に結合）またはジェミナル（同一炭素に結合）アルキル基は、一緒になって６個までの炭素原子を有する炭化水素環を形成してもよい）、ヒドロキシ基、炭素数１〜９のアルコキシ基、炭素数１〜９のアルキレンオキシ基、アミノ基、炭素数１〜９のアルキルアミノ基、ハロゲン原子（フッ素、塩素、臭素および沃素）又はフェニル基を示す。］

［式中、Ｍ_３及びＭ_４は、同一又は異なって、金属カチオン若しくは有機カチオンを示すか、または該２つの金属イオンがまとめられてなる単一の金属イオン（二価の金属カチオン、例えばカルシウムイオン等）を示す。Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、及びＲ^２６は、同一又は異なって、それぞれ、水素原子、炭素数１〜９のアルキル基、ヒドロキシ基、炭素数１〜９のアルコキシ基、炭素数１〜９のアルキレンオキシ基、アミノ基、及び炭素数１〜９のアルキルアミノ基、ハロゲン原子、フェニル基、アルキルフェニル基又は最大９個の炭素原子を有するジェミナル若しくはまたはビシナルの炭素環を示す。好ましくは、金属カチオンはカルシウム、ストロンチウム、バリウム、マグネシウム、アルミニウム、銀、ナトリウム、リチウム、ルビジウム、カリウム等から成る群から選択される。］

［式中、Ｒ^２７〜Ｒ^３０は、同一又は異なって、水素原子又は炭素数１〜９のアルキル基を表し、Ｒ^３１は水素原子又は炭素数１〜３のアルキル基を表し、ｄは１又は２の整数であり、ｄが１のとき、Ｍ_５はアルカリ金属を表し、ｄが２のとき、Ｍ_５はアルカリ土類金属、亜鉛又はヒドロキシアルミニウムを表す。］

［式中、ｆは、２〜６の整数を表す。Ｒ^３２は、炭素数２〜１８の飽和若しくは不飽和の脂肪族ポリカルボン酸残基、炭素数３〜１８の脂環族ポリカルボン酸残基又は炭素数６〜１８の芳香族ポリカルボン酸残基を表す。２〜６個のＲ^３３は、同一又は異なって、それぞれ、炭素数５〜３０の飽和若しくは不飽和の脂肪族アミン残基、炭素数５〜３０の脂環族アミン残基又は炭素数６〜３０の芳香族アミン残基を表す。］

［式中、Ｒ^３４ 、Ｒ^３５ およびＲ^３６ は、水素原子、アルキル基、シクロアルキル基またはアリール基を示し、それぞれ同一であっても異なっていてもよい。］ Examples of the crystal nucleating agent other than the diacetal compound according to the present invention include a sodium benzoate salt, a p-tert-butyl benzoate aluminum salt, a cyclohexanedicarboxylic acid metal salt represented by the following general formula (3), and the following. A carboxylate compound such as a norbornandicarboxylic acid metal salt represented by the general formula (4), a phosphate ester salt compound represented by the following general formula (5), and an amide compound represented by the following general formula (6). , Rodin-based compounds such as loginic acid represented by the following general formula (7) or a metal salt compound thereof (for example, an alkali metal salt such as lithium, sodium, potassium, magnesium) and the like are exemplified.

[In the formula, M ₁ and M ₂ both represent lithium ions, or _{divalent metal cations consisting of two metal ions M 1} and M ₂ combined into a single metal ion: calcium, strontium. , Zinc, magnesium or monobasic aluminum. R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different, hydrogen atoms, alkyl groups with 1 to 9 carbon atoms (here). , Any two vicinal (bonded to adjacent carbons) or genomic (bonded to the same carbon) alkyl group may together form a hydrocarbon ring with up to 6 carbon atoms), hydroxy group, It represents an alkoxy group having 1 to 9 carbon atoms, an alkyleneoxy group having 1 to 9 carbon atoms, an amino group, an alkylamino group having 1 to 9 carbon atoms, a halogen atom (fluorine, chlorine, bromine and iodine) or a phenyl group. ]

[In the formula, M ₃ and M ₄ represent the same or different metal cation or organic cation, or a single metal ion (divalent metal cation, for example calcium) formed by combining the two metal ions. Ions, etc.) are shown. R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are the same or different, and are the same or different alkyl groups having a hydrogen atom and 1 to 9 carbon atoms, respectively. , Hydroxy group, alkoxy group with 1 to 9 carbon atoms, alkyleneoxy group with 1 to 9 carbon atoms, amino group, and alkylamino group with 1 to 9 carbon atoms, halogen atom, phenyl group, alkylphenyl group or up to 9 pieces. Indicates a genomic or vicinal carbon ring having a carbon atom of. Preferably, the metal cation is selected from the group consisting of calcium, strontium, barium, magnesium, aluminum, silver, sodium, lithium, rubidium, potassium and the like. ]

[In the formula, R ^{27 to} R ³⁰ represent the same or different alkyl group having a hydrogen atom or carbon number 1 to 9, R ³¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, 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 the formula, f represents an integer of 2 to 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. The 2 to 6 R ^33s are the same or different, respectively, 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, respectively. 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, which may be the same or different from each other. ]

<Polyolefin-based resin composition>
In the polyolefin-based resin composition of the present invention, a finely divided crystal nucleating agent for polyolefin-based resin and a polyolefin-based resin having improved fluidity of the present invention are added, and if necessary, other additives for polyolefin-based resin are added. It can be easily obtained by dry-blending at room temperature and then melt-mixing under predetermined conditions.

The concentration of the crystal nucleating agent of the present invention in the polyolefin-based resin is not particularly limited as long as it is effective as the crystal nucleating agent for the polyolefin-based resin, but is preferably 0.001 with respect to 100 parts by weight of the polyolefin-based resin. It is preferably 10 parts by weight, more preferably 0.01 to 5 parts by weight.

[Polyolefin-based 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 resins, polypropylene-based resins, polybutene-based resins, and polymethylpentene. Examples thereof include based resins and polybutadiene resins. More specifically, high-density polyethylene, medium-density polyethylene, linear polyethylene, ethylene copolymer having an ethylene content of 50% by weight or more, preferably 70% by weight or more, propylene homopolymer, propylene by 50% by weight or more, preferably 70% by weight. % 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 and the like. Further, the above-mentioned copolymer may be a random copolymer or a block copolymer. Further, if these resins have stereoregularity, they may be isotactic or syndiotactic. Specific examples of the comonomer that can constitute the above copolymer include α-olefins having 2 to 12 carbon atoms such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene, 1,4-. Examples thereof include bicyclo-type monomers such as endomethylenecyclohexene, (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate, and vinyl acetate.

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

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

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

Examples of the additives for polyolefin resins include various additives described in "Handbook of Additives on the Positive List" (January 2002) edited by the Polyolefin Hygiene Council. Specifically, fluorescent whitening agents (2,5-thiophendiyl (5-tert-butyl-1,3-benzoxazole), 4,4'-bis (benzoxazole-2-yl) stilben, etc.), Antioxidants, stabilizers (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants, lubricants (paraffin, wax, etc.) Aliper hydrocarbons, higher fatty acids with 8 to 22 carbon atoms, higher fatty acid metal (Al, Ca) salts with 8 to 22 carbon atoms, higher aliphatic alcohols with 8 to 22 carbon atoms, polyglycols, 4 to 22 carbon atoms. Esters of higher fatty acids and aliphatic monovalent alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives, etc., fillers (talc, hydrotalcite, mica, zeolite, pearlite, etc.) , Silica, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agent, foaming aid, polymer additive, plastic compound (dialkylphthalate, dialkylhexahydrophthalate, etc.), cross-linking agent, cross-linking accelerator, antistatic agent, flame retardant, dispersion Examples thereof include various additives such as agents, organic-inorganic pigments (indigo compounds, phthalocyanine compounds, anthraquinone compounds, ultramarine compounds, cobalt aluminate compounds, etc.), processing aids, and other nucleating agents.

When these additives are used, the amount used may be within the range normally used as long as the effects of the present invention are not impaired. For example, the amount used is preferably 0 with respect to 100 parts by weight of the polyolefin-based resin. It is generally used in an amount of about .0001 to 100 parts by weight, more preferably about 0.001 to 50 parts by weight.

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

<Polyolefin-based resin molded product>
The polyolefin-based resin molded article of the present invention can be obtained by molding using the above-mentioned polyolefin-based resin composition of the present invention according to a conventional molding method. The molding method is not particularly limited as long as the effects of the present invention are exhibited, and any conventionally known molding method such as injection molding, extrusion molding, blow molding, pressure molding, rotary molding, or film molding can be adopted.

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

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

[Characteristics of crystal nucleating agent]
(1) Measurement of particle size distribution A laser diffraction type particle size distribution meter (“Mastersizer 3000” manufactured by Malvern Instruments) was used for measurement by the following method. First, the sample is dispersed in an aqueous solution to which a nonionic surfactant is added as a dispersant by sufficiently stirring and mixing using a wet measurement cell, and then the obtained mixture is further stirred in the apparatus. While circulating, ultrasonic waves were applied to disperse the mixture sufficiently uniformly in the apparatus. Then, the particle size distribution of the sample was measured while applying ultrasonic waves. From the obtained particle size distribution, a volume-based cumulative 50% particle size (d50) was determined and used as the average particle size. Similarly, the volume-based cumulative 60% particle size (d60) and the volume-based cumulative 10% particle size (d10) were obtained from the particle size distribution, and the ratio (d60 / d10) was calculated to obtain the uniformity of the particle size. It can be said that the closer the value of d60 / d10 is to 1, the more uniform the particle size, that is, the closer the particle size distribution is to monodisperse.

(2) Aspect ratio measurement Using a flow-type particle image analyzer (“FPIA-3000” manufactured by Malvern Instruments), the aspect ratio was measured by the following method. After adding a surfactant as a dispersant to 30 ml of ion-exchanged water in the measurement container, 20 mg of the measurement sample was added and dispersion treatment was performed for 5 minutes to uniformly disperse the sample to prepare a measurement sample. The measurement is performed using the obtained measurement sample, the aspect ratio distribution is obtained by the analysis software attached to the above device, and the cumulative 50% value and the cumulative 10% value are obtained from the distribution, and each is the center of the aspect ratio. The value was set to 50%, which means, and the Lower value, which is a guideline for the proportion of particles having a large aspect ratio. As described above, it can be said that the larger the value of the Lower value, the smaller the proportion of particles having a large aspect ratio.

[Evaluation of liquidity]
(3) Powder fluidity test (funnel test)
The crystal nucleating agent is poured into the upper mouth of a metal funnel with an opening diameter of 15 cm and a hole diameter of 1.5 cm from a height where the distance to the upper edge of the funnel is 5 cm, and the funnel lower mouth is not vibrated. Drop more. From the state of discharge from the funnel of the crystal nucleating agent, the fluidity of the crystal nucleating agent was judged by a four-step evaluation according to the following criteria.
(Evaluation criteria)
⊚: All the crystal nucleating agent is quickly discharged from the funnel, and almost no deposits on the inner wall of the funnel are confirmed. ○: The crystal nucleating agent remains slightly without being discharged from the funnel, but the crystal nucleating agent remaining due to a slight impact also remains. All are 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 only a slight impact. ×: The crystal nucleating agent is discharged from the funnel. It remains in large quantities without being left untreated, and it is difficult to discharge the crystal nucleating agent remaining on the funnel even if an impact is applied.

[Characteristics of molded product]
(4) Measurement of haze value The haze value was measured by a method according to JIS K7136 (2000) using a haze meter manufactured by Toyo Seiki Seisakusho. As the evaluation sample, a polypropylene-based resin molded product having a thickness of 1 mm was used. The smaller the obtained haze value, the better the transparency.

(5) Evaluation of white spots An injection-molded polyolefin resin molded product having a shape of 50 mm × 50 mm × 1 mm was used as an evaluation sample, and the number of white spots in the molded product was counted by visual observation. The obtained result was taken as the average value of 5 samples and used as the number of white spots on the sample, and the superiority or inferiority was judged from the obtained evaluation result according to the following criteria.
Very good: The number of white spots is less than 3, which is a level at which there is no problem in terms of the performance of the molded product.
Good: The number of white spots is in the range of 3 to 15, and there is no problem in terms of performance as a crystal nucleating agent, but there is a possibility that undispersed substances may affect other physical properties.
Deficiency: The presence of more than 15 white spots was confirmed, and apparently the effect was not sufficiently exhibited in terms of the performance of the crystal nucleating agent, and the undispersed substance may cause problems in various physical properties. Is high.

Abbreviation of compound in Examples EDBS: 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol DMDBS: 1,3: 2,4-bis-O- (3', 4) '-Dimethylbenzylidene) -D-sorbitol PDBN: 1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-n-propylsorbitol CDBS: 1,3: 2,4-bis- O- (p-chlorobenzylidene) -D-sorbitol

[Example 1]
Using a jet crusher "Single Track Jet Mill STJ-400" manufactured by Seishin Co., Ltd., DMDBS with a general-purpose particle size under the conditions of room temperature, pressure 0.7 MPa, and processing amount 30 kg / hour. Gelol DXR, manufactured by Shin Nihon Rika Co., Ltd.) was finely pulverized to prepare a fine particle crystal nucleating agent. The particle size distribution of the obtained fine particle crystal nucleating agent was measured, and the average value and uniformity obtained from the particle size distribution are shown in Table 1. In addition, the aspect ratio of the obtained fine particle crystal nucleating agent was measured, and the 50% value and Lower value obtained from the distribution are shown in Table 1. Subsequently, the powder fluidity was evaluated by a powder fluidity test (funnel test) using the obtained crystal nucleating agent, and the results are also shown in Table 1.

Next, 100 parts by weight of a polypropylene random copolymer (MFR = 7 g / 10 minutes (load 2160 g, temperature 230 ° C.), Prime Polymer Co., Ltd., R-720) as a polyolefin resin was obtained as a crystal nucleating agent. 0.2 parts by weight of crystal nucleating agent, 0.05 parts by weight of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name "Ca-St") as other additives, tetrakis [methylene-3- (3,5-) Di-tert-butyl-4-hydroxyphenyl) propionate] methane (manufactured by BASF Japan Co., Ltd., trade name "IRGANOX1010") 0.05 parts by weight, tetrakis (2,4-di-tert-butylphenyl) phosphite (2,4-di-tert-butylphenyl) BAS F Japan Co., Ltd., trade name "IRGAFOS168") 0.05 parts by weight was dry-blended. The dry blend is melt-mixed at a barrel temperature of 250 ° C. using a uniaxial extruder (VS-20 manufactured by Tanabe Plastics Machinery Co., Ltd.), the extruded strands are cooled, and the extruded strands are cut with a pelletizer to obtain a polyolefin resin. The composition was prepared.

Subsequently, using the obtained polyolefin resin composition, an injection molding machine (NS40-5A manufactured by Nissei Resin Industry Co., Ltd.) was used to inject molding temperature (heating temperature) 240 ° C. and mold temperature (cooling temperature) 40 ° C. A polyolefin-based resin molded product having a thickness of 1 mm was obtained by molding under the above conditions. The haze value was measured using the obtained molded product as an evaluation sample, and the obtained results are also shown in Table 1. Moreover, as a result of white spot evaluation using the same evaluation sample, it was confirmed that the above crystal nucleating agent showed very good dispersibility in the polyolefin resin.

[Example 2]
The same procedure as in Example 1 was carried out except that EDBS was used instead of DMDBS to prepare the crystal nucleating agent of the present invention, and the particle size distribution, aspect ratio measurement, and powder fluidity of the obtained crystal nucleating agent were measured. The evaluation was performed and the results are shown in Table 1. Subsequently, the same procedure as in Example 1 was carried out to obtain a polypropylene-based resin molded product. The haze value was measured using the obtained molded product, and the results are shown in Table 1. Moreover, from the result of the white point evaluation, the dispersibility of the above crystal nucleating agent in the polyolefin resin was very good.

[Example 3]
The same procedure as in Example 1 was carried out except that PDBN was used instead of DMDBS to prepare the crystal nucleating agent of the present invention, and the particle size distribution, aspect ratio measurement, and powder fluidity of the obtained crystal nucleating agent were measured. The evaluation was performed and the results are shown in Table 1. Subsequently, the same procedure as in Example 1 was carried out to obtain a polypropylene-based resin molded product. The haze value was measured using the obtained molded product, and the results are shown in Table 1. Moreover, from the result of the white point evaluation, the dispersibility of the above crystal nucleating agent in the polyolefin resin was very good.

[Comparative Example 1]
The fine particle crystal nucleating agent obtained in Example 1 is again finely pulverized under the same conditions as in Example 1 to prepare a finer fine particle crystal nucleating agent to obtain a crystal nucleating agent other than the present invention. It was. The particle size distribution, aspect ratio, and powder fluidity of the obtained crystal nucleating agent were evaluated, and the results are shown in Table 1. Subsequently, the same procedure as in Example 1 was carried out to obtain a polypropylene-based resin molded product. The haze value was measured using the obtained molded product, and the results are shown in Table 1. Moreover, from the result of the white point evaluation, the dispersibility of the above crystal nucleating agent in the polyolefin resin was very good.

[Comparative Example 2]
The powder fluidity was evaluated using a general-purpose particle size DMDBS before pulverization, and the results are shown in Table 1 together with the particle size distribution and aspect ratio numbers. Subsequently, the same procedure as in Example 1 was carried out to obtain a polypropylene-based resin molded product, and the haze value was measured using the obtained molded product, and the results are shown in Table 1. Moreover, from the result of the white point evaluation, the dispersibility of the crystal nucleating agent in the polyolefin resin was good.

[Comparative Example 3]
The powder fluidity was evaluated using EDBS having a general-purpose particle size before pulverization, and the results are shown in Table 1 together with the numerical values of the particle size distribution and the aspect ratio. Subsequently, the same procedure as in Example 1 was carried out to obtain a polypropylene-based resin molded product. The haze value was measured using the obtained molded product, and the results are shown in Table 1. Moreover, from the result of the white point evaluation, the dispersibility of the above crystal nucleating agent in the polyolefin resin was good.

[Comparative Example 4]
The powder fluidity was evaluated using a PDBN having a general-purpose particle size before pulverization, and the results are shown in Table 1 together with the numerical values of the particle size distribution and the aspect ratio. Subsequently, the same procedure as in Example 1 was carried out to obtain a polypropylene-based resin molded product. The haze value was measured using the obtained molded product, and the results are shown in Table 1. Moreover, from the result of the white point evaluation, the dispersibility of the above crystal nucleating agent in the polyolefin resin was very good.

[Example 4]
Using the fine crystal nucleating agent obtained in Comparative Example 1 as the crystal nucleating agent (A) and DMDBS before pulverization as the crystal nucleating agent (B), (A) / (B) = at room temperature. The crystal nucleating agent of the present invention was prepared by mixing at a ratio of 2/1 (weight ratio). The particle size distribution, aspect ratio, and powder fluidity of the obtained crystal nucleating agent were evaluated, and the results are shown in Table 2. Subsequently, the same procedure as in Example 1 was carried out to obtain a polypropylene-based resin molded product. The haze value was measured using the obtained molded product, and the results are shown in Table 2. Moreover, from the result of the white point evaluation, the dispersibility of the above crystal nucleating agent in the polyolefin resin was very good.

[Example 5]
A crystal nucleating agent was prepared in the same manner as in Example 4 except that EDBS before pulverization was used as the crystal nucleating agent (B), and the particle size distribution and aspect ratio of the obtained crystal nucleating agent were measured. The powder fluidity was evaluated and the results are shown in Table 2. Subsequently, the same procedure as in Example 1 was carried out to obtain a polypropylene-based resin molded product. The haze value was measured using the obtained molded product, and the results are shown in Table 2. Moreover, from the result of the white point evaluation, the dispersibility of the above crystal nucleating agent in the polyolefin resin was very good.

[Example 6]
An uncrushed CDBS (average particle size 7.5, uniformity 4.1) was used as the crystal nucleating agent (B), and the same procedure as in Example 4 was carried out to prepare a crystal nucleating agent. The particle size distribution, aspect ratio, and powder fluidity of the obtained crystal nucleating agent were evaluated, and the results are shown in Table 2. Subsequently, the same procedure as in Example 1 was carried out to obtain a polypropylene-based resin molded product. The haze value was measured using the obtained molded product, and the results are shown in Table 2. Moreover, from the result of the white point evaluation, the dispersibility of the above crystal nucleating agent in the polyolefin resin was very good.

From the results of Tables 1 and 2 above, the crystal nucleating agent having properties within the range of the present invention (Examples 1 to 6) is a powder as compared with the crystal nucleating agent having properties outside the range of the present invention. It can be seen that the fluidity is very good. Further, from the results of Tables 1 and 2, the crystal nucleating agent of the present invention has the same or better performance as the conventional crystal nucleating agent as a crystal nucleating agent for polyolefin resins. It can be confirmed that it is shown. From this result, by using the crystal nucleating agent of the present invention, the workability at the time of blending with the polyolefin-based resin and during the molding process after blending is greatly improved, and further, the polyolefin-based resin using the crystal nucleating agent of the present invention is improved. It can be seen that the composition and its molded product have very excellent performance and are very useful in various applications.

The crystal nucleating agent of the present invention has greatly improved fluidity by adjusting to specific properties, and the crystal nucleating agent can be used for various purposes as a crystal nucleating agent having extremely excellent fluidity. Can be done. Further, the crystal nucleating agent of the present invention has the same or better performance as the conventional crystal nucleating agent with respect to the transparency of the molded product, which is the original performance as the crystal nucleating agent for polyolefin resins, and is an automobile member. , Electrical parts, mechanical parts, daily miscellaneous goods, cases for clothes, containers for food, etc., can be used for various purposes. In particular, in medical applications where the mixing of unnecessary additives and the like is avoided, it is a technology that is highly expected to be utilized in the future as a technology that can improve the fluidity without adding additives.

Claims (9)

A crystal nucleating agent for polyolefin resins with improved fluidity.
A crystal nucleating agent for a polyolefin resin is a crystal nucleating agent composed of a diacetal compound represented by the following general formula (1).
Or
The diacetal compound (A) represented by the following general formula (1) and the particle size obtained by the laser diffraction type particle size distribution measurement, in which the average value of the particle size obtained by the laser diffraction type particle size distribution measurement is 0.5 to 2.0 μm. It is a crystal nucleating agent composed of a mixture with the diacetal compound (B) represented by the following general formula (1) having an average value of 4.0 to 15.0 μm.
A fine particle crystal nucleating agent having an average particle size of 0.5 to 4.0 μm and a uniformity of 3 to 10 determined by laser diffraction type particle size distribution measurement.

[In the formula (1), R ¹ and R ² are the same or different, respectively, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched carbon. It indicates an alkoxy group having the number 1 to 4, 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 chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ] Further, the 50% value of the aspect ratio of the crystal nucleating agent obtained by the particle image analysis method is 0.4 to 0.7, and the Lower value is 0.2 to 0.4. The crystal nucleating agent according to claim 1. In the general formula (1), R ¹ and R ² are the same or different, and are a methyl group or an ethyl group, R ³ is a hydrogen atom, and m and n are integers of 1 or 2. The crystal nucleating agent according to claim 1, wherein p is 1. In the general formula (1), R ¹ and R ² are the same or different, a propyl group or a propoxy group, R ³ is a propyl group or a propenyl group, m and n are 1, and p. The crystal nucleating agent according to claim 1, wherein is 1. The production of the crystal nucleating agent according to claim 1 or 2 , wherein the crystal nucleating agent composed of the diacetal compound represented by the following general formula (1) or the diacetal compound (A) is a pulverized product by an air flow type pulverizer. Method.

[In the formula (1), R ¹ and R ² are the same or different, respectively, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched carbon. It indicates an alkoxy group having the number 1 to 4, 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 chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ] A polyolefin-based resin composition comprising a polyolefin-based resin and the crystal nucleating agent according to any one of claims 1 to 4. A polyolefin-based resin molded product using the polyolefin-based resin composition according to claim 6 as a raw material. A method for improving the fluidity of a crystal nucleating agent for polyolefin resins.
The crystal nucleating agent for a polyolefin resin is a crystal nucleating agent composed of a diacetal compound represented by the following general formula (1), and the crystal nucleating agent is finely pulverized in whole amount or partially by an air flow type fine pulverizer. method characterized in that the object is subject to simultaneously satisfy properties following (a) and (b).
(A) The average value of the particle size determined by the laser diffraction type particle size distribution measurement is 0.5 to 4.0 μm, and the uniformity is 3 to 10.
(B) The 50% value of the aspect ratio obtained by the particle image analysis method is 0.4 to 0.7, and the Lower value is 0.2 to 0.4.

[In the formula (1), R ¹ and R ² are the same or different, respectively, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched carbon. It indicates an alkoxy group having the number 1 to 4, 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 chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ] A method for improving the fluidity of a crystal nucleating agent for polyolefin resins .
Diacetal compounds average particle diameter determined by the LES Za diffraction type particle size distribution measurement is represented by the following general formula (1) is 0.5~2.0μm and (A), was determined from laser diffraction particle size distribution measurement polyolefin resin for crystallization nucleating agent obtained by mixing a diacetal compound (B) represented by the following general formula average particle diameter of 4.0~15.0μm (1) is the following (a) A method characterized in that the properties satisfy the condition (b) at the same time.
(A) The average value of the particle size determined by the laser diffraction type particle size distribution measurement is 0.5 to 4.0 μm, and the uniformity is 3 to 10.
(B) The 50% value of the aspect ratio obtained by the particle image analysis method is 0.4 to 0.7, and the Lower value is 0.2 to 0.4.

[In the formula (1), R ¹ and R ² are the same or different, respectively, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched carbon. It indicates an alkoxy group having the number 1 to 4, 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 chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ]