JP2021066150A - High rigidity polypropylene resin molding and method for producing the same - Google Patents

Abstract

To provide a high rigidity polypropylene resin molding that maintains the lightweightness that a polypropylene resin originally has, while achieving improved moldability and impact resistance and a method of producing the same.SOLUTION: It is found out that: a polypropylene resin composition is used as raw material, the polypropylene resin composition prepared under specific conditions and containing a specific polypropylene resin and a specific diacetal compound; and the polypropylene resin composition is then molded under specific conditions, resulting in a polypropylene resin molding with significantly improved rigidity.SELECTED DRAWING: None

Description

The present invention relates to a high-rigidity polypropylene-based resin molded product and a method for producing the same. Specifically, the present invention comprises a polypropylene-based resin composition prepared under specific conditions containing a specific polypropylene-based resin and a specific diacetal compound under specific conditions. The present invention relates to a high-rigidity polypropylene-based resin molded article having extremely excellent rigidity obtained by molding with.

Polyolefin-based resins such as polyethylene-based resins and polypropylene-based resins are inexpensive and have very well-balanced performance, and are widely used in various applications. Among them, polypropylene-based resins have greatly improved mechanical properties such as rigidity and thermal properties such as heat resistance due to the improvements made so far, and are being replaced with other materials in fields such as automobile materials and industrial materials. .. In particular, in the field of automobile materials, in the recent trend of energy saving, the switch to polypropylene resin is about to be further promoted from the viewpoint of weight reduction.

As described above, the mechanical properties of polypropylene-based resins have been greatly improved by the improvements made so far. However, for example, in order to reduce the weight of automobile materials, it is necessary to further reduce the amount of filler and the like and reduce the wall thickness. For that purpose, further improvement in the rigidity of polypropylene-based resin is required.

There are roughly two methods for improving the rigidity of polypropylene-based resin: improvement of polypropylene-based resin and improvement by blending additives. For example, in the case of improving a polypropylene resin, the rigidity can be improved by controlling the molecular weight, its distribution, crystallinity, and various higher-order structures (Patent Documents 1 to 3). Further, when blending additives, the simplest method is blending a filler, but in that case, there is a problem that the weight increases, and other methods are used in the above-mentioned fields such as automobile materials for which weight reduction is required. For example, a method of controlling the orientation of a resin by blending a crystal nucleating agent or the like is also widely used (Patent Documents 4 to 6).

As for the orientation of the resin, it is possible to bring about a constant orientation depending on the molding method and molding conditions, and various measures such as designing the mold have been attempted to increase the rigidity, but as a simpler method. For example, a technique for orienting a polypropylene resin by blending an additive such as a needle-shaped or plate-shaped filler and orienting the additive in a specific direction is widely used (Patent Documents 7 and 8). ). In addition, a certain orientation can be obtained by so-called orientation gel molding using a specific nucleating agent (Patent Document 9).

Japanese Unexamined Patent Publication No. 3-2207 Japanese Unexamined Patent Publication No. 8-217823 Japanese Unexamined Patent Publication No. 11-12322 Japanese Unexamined Patent Publication No. 11-293084 Japanese Unexamined Patent Publication No. 2014-95045 JP-A-2018-168386 Japanese Unexamined Patent Publication No. 5-279526 Japanese Unexamined Patent Publication No. 7-236537 International release 99/24496

As described above, various methods have been tried to improve the rigidity of polypropylene-based resins, but the current situation is that sufficient rigidity has not yet been obtained except for the method of blending a filler. As described above, the filler compounding system is strongly desired to be improved in automobile applications where weight reduction is required.

The present invention provides a high-rigidity polypropylene-based resin molded product that does not have the above-mentioned problems, that is, does not impair the original lightness of the polypropylene-based resin, and is also excellent in moldability and impact resistance, and a method for producing the same. The purpose is.

In view of the above situation, as a result of diligent studies to solve the above problems, the present inventors have made a polypropylene resin containing a specific polypropylene resin and a specific diacetal compound, and prepared under specific conditions. We have found that the rigidity of the obtained polypropylene-based resin molded product is remarkably improved by molding the composition under specific conditions using the composition as a raw material, and have completed the present invention.

That is, the present invention is a high-rigidity polypropylene-based composition obtained by molding a polypropylene-based resin composition obtained under specific conditions containing a specific polypropylene-based resin and a specific diacetal compound shown below under specific conditions. It provides a resin molded product and a method for producing the same.

［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 1] A high-rigidity polypropylene-based resin molded product molded by using a polypropylene-based resin composition containing a polypropylene-based resin and a diacetal compound.
The polypropylene-based resin has a high stereoregularity in which the isotactic pentad fraction by the 13C-NMR method is in the range of 0.96 to 0.995, and the molecular weight distribution (Mw / Mn) by the GPC method. ) Is a highly crystalline polypropylene resin in the range of 4 to 16.
The diacetal compound is a diacetal compound represented by the following general formula (1).
The polypropylene-based resin composition is a polypropylene-based resin composition that is melt-mixed at a temperature equal to or higher than the temperature at which the diacetal compound is melted in the melted polypropylene-based resin, and then cooled and solidified.
The molding method is an orientation gel molding method in which a diacetal compound is molded at a temperature lower than the temperature at which it is melted in a molten polypropylene-based resin.
High-rigidity polypropylene resin molded product.

[In formula (1), R ¹ and R ² are the same or different, hydrogen atom, linear or branched alkyl group having 1 to 4 carbon atoms, linear or branched carbon, respectively. It represents an alkoxy group having the number 1 to 4, a linear or branched-chain alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ]

[Item 2] The high-rigidity polypropylene-based resin molded product according to [Item 1], wherein the melt flow rate (230 ° C.) of the polypropylene-based resin is 30 g / 10 min or more.

[Item 3] The high-rigidity polypropylene-based resin according to [Item 1] or [Item 2], wherein the isotactic pentad fraction of the polypropylene-based resin by the 13C-NMR method is in the range of 0.97 to 0.99. Molded body.

[Item 4] The high-rigidity polypropylene-based resin molded product according to any one of [Item 1] to [Item 3], wherein the molecular weight distribution (Mw / Mn) of the polypropylene-based resin by the GPC method is in the range of 4 to 10.

[Item 5] The high-rigidity polypropylene-based resin molded product according to any one of [Item 1] to [Item 4], wherein the polypropylene-based resin has a melt flow rate (230 ° C.) of 35 g / 10 min or more.

[Item 6] In the general formula (1), R ¹ and R ² are the same or different, and are a methyl group or an ethyl group, R ³ is a hydrogen atom, and m and n are 1 or 2. The high-rigidity polypropylene-based resin molded product according to any one of [Item 1] to [Item 5], which is an integer and p is 1.

[Item 7] 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 high-rigidity polypropylene-based resin molded product according to any one of [Item 1] to [Item 5], wherein p is 1.

［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 8] A method for producing a high-rigidity polypropylene-based resin molded product containing a polypropylene-based resin and a diacetal compound.
The polypropylene-based resin has a high stereoregularity in which the isotactic pentad fraction by the 13C-NMR method is in the range of 0.96 to 0.995, and the molecular weight distribution (Mw / Mn) by the GPC method. ) Is a highly crystalline polypropylene resin in the range of 4 to 16.
The diacetal compound is a diacetal compound represented by the following general formula (1).
After the diacetal compound is dissolved in the melted polypropylene resin, it is cooled and solidified to prepare a polypropylene resin composition, and then the polypropylene resin composition is molded at a temperature lower than the temperature at which the diacetal compound is melted in the melted polypropylene resin. A method for producing a high-rigidity polypropylene-based resin molded body, which is characterized by the above.

[In formula (1), R ¹ and R ² are the same or different, hydrogen atom, linear or branched alkyl group having 1 to 4 carbon atoms, linear or branched carbon, respectively. It represents an alkoxy group having the number 1 to 4, a linear or branched-chain alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ]

[Item 9] The method for producing a high-rigidity polypropylene-based resin molded product according to [Item 8], wherein the melt flow rate (230 ° C.) of the polypropylene-based resin is 30 g / 10 min or more.

[Item 10] The high-rigidity polypropylene-based resin according to [Item 8] or [Item 9], wherein the isotactic pentad fraction of the polypropylene-based resin by the 13C-NMR method is in the range of 0.97 to 0.99. A method for manufacturing a molded product.

[Item 11] The high-rigidity polypropylene-based resin molded product according to any one of [Item 8] to [Item 10], wherein the molecular weight distribution (Mw / Mn) of the polypropylene-based resin by the GPC method is in the range of 4 to 10. Production method.

[Item 12] The method for producing a high-rigidity polypropylene-based resin molded product according to any one of [Item 8] to [Item 11], wherein the melt flow rate (230 ° C.) of the polypropylene-based resin is 35 g / 10 min or more.

[Item 13] In the general formula (1), R ¹ and R ² are the same or different, and are a methyl group or an ethyl group, R ³ is a hydrogen atom, and m and n are 1 or 2. The method for producing a high-rigidity polypropylene-based resin molded product according to any one of [Item 8] to [Item 12], which is an integer and p is 1.

[Item 14] 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 for producing a high-rigidity polypropylene-based resin molded product according to any one of [Item 8] to [Item 12], wherein p is 1.

_{[Item 15] Any of [Item 8] to [Item 14], wherein the melt-mixing temperature (T 1} ) when producing the polypropylene-based resin-based resin composition is in the temperature range represented by the following formula (1). A method for producing a high-rigidity polypropylene-based resin molded product according to the above.
(Equation 1) Tm ≤ T ₁ <Tm + 15
Tm is the temperature at which the blended diacetal compound dissolves in the melted polypropylene-based resin.

_{[Item 16] Any of [Item 8] to [Item 14], wherein the molding temperature (T 2} ) when producing the polypropylene-based resin-based resin molded product is in the temperature range represented by the following formula (1). A method for producing a high-rigidity polypropylene-based resin molded product according to.
(Equation 2) T _m- 15 ≤ T ₂ <T _m
Tm is the temperature at which the blended diacetal compound dissolves in the melted polypropylene-based resin.

By molding a polypropylene-based resin composition containing the above-mentioned specific polypropylene-based resin and a specific diacetal compound under specific conditions under specific conditions, the rigidity of the obtained molded product can be greatly improved. Taking advantage of the characteristics of polypropylene-based resin, which is inexpensive and lightweight, it is possible to expand the range of use in various fields such as automobile materials, even for applications that could not be put into practical use due to insufficient rigidity. It has become possible.

The polypropylene-based resin molded product of the present invention is molded under specific conditions using a polypropylene-based resin composition containing a specific polypropylene-based resin and a specific diacetal compound and prepared under specific conditions as a raw material. It is characterized by.

<Polypropylene resin composition>
As described above, the first feature of the polypropylene-based resin composition of the present invention is that it contains (1) a specific polypropylene-based resin and (2) a specific diacetal compound.

(1) Polypropylene-based resin The polypropylene-based resin of the present invention has an isotactic pentad fraction (hereinafter referred to as mmmm fraction) by the 13C-NMR method of 0.96 to 0.995, preferably 0.97 to 0.97. A highly crystalline polypropylene resin having a high stereoregularity in the range of 0.99 and having a molecular weight distribution (Mw / Mn) of 4 to 16, preferably 4 to 10 by the GPC method. It is characterized by being. By setting the mmmm fraction to 0.96 or more, high rigidity can be imparted in the configuration of the present invention. Further, although it is possible to impart high rigidity even when the mm mm fraction is 0.995 or more, it is difficult to manufacture a polypropylene resin having a mm mm fraction of 0.995 or more, which is not realistic.

Further, when the molecular weight distribution is within the above range, the rigidity can be improved even in the configuration of the present invention without significantly impairing the moldability and the impact resistance. Specifically, when the molecular weight distribution is 16 or less, the impact resistance is less likely to decrease, and when the molecular weight distribution is 4 or more, there is no concern that a problem of moldability in injection molding or the like will occur.

Further, the polypropylene-based resin of the present invention has a melt flow rate of 30 g / 10 min or more, preferably 35 g / 10 min or more, measured at 230 ° C. in accordance with JIS K7210 (1999). The improvement effect can be further exerted.

The isotactic pentad fraction (mmmm fraction) is an isotactic chain in pentad units in a polypropylene resin molecular chain measured using 13C-NMR, and five consecutive isotropic chains in propylene monomer units. It is a fraction of the propylene monomer unit at the center of the mesobonded chain. Actually, it can be obtained as a fraction of the mmmm peak in the total absorption peak of the methyl carbon region measured by the 13C-NMR spectrum.

［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。］ (2) Diacetal Compound The diacetal compound of the present invention is specifically a diacetal compound represented by the following general formula (1).

[In formula (1), R ¹ and R ² are the same or different, hydrogen atom, linear or branched alkyl group having 1 to 4 carbon atoms, linear or branched carbon, respectively. It represents an alkoxy group having the number 1 to 4, a linear or branched-chain alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ]

Among the diacetal 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, and m and n are. A compound which is an integer of 1 or 2 and p is 1, and R ^{1 and R 2} in the above general formula (1) are propyl groups or propyloxy groups, and R ³ is a propyl group or propenyl group. A compound having m and n of 1 and p of 1 is more preferable from the viewpoint of the effect of improving rigidity.

Further, among the above diacetal compounds, the following compounds can also be exemplified as more preferable compounds from the viewpoint of the nuclear agent effect. In the above general formula (1), a compound in which R ¹ and R ² are propyl groups or propyloxy groups, R ³ is a propyl group or a propenyl group, m and n are 1, and p is 1. Etc. are more preferable from the viewpoint of the effect of improving rigidity.

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-isopropylbenzylidene) -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- (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- (orn-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- (ot-butylbenzylidene) -D-sorbitol, 1,3: 2,4- Bis-O- (mt-butylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (pt-butylbenzylidene) -D-sorbitol, 1,3: 2,4- Bis-O- (dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2', 3'-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis- O- (2', 4'-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (2', 5'-dimethylbenzylidene) -D-sorbitol, 1,3: 2, 4-bis-O- (2', 6'-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzyl) LIDEN) -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'-trimethylbendylidene) ) -D-sorbitol, 1,3: 2,4-bis-O- (2', 4', 5'-triethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3) ', 4', 5'-triethylbenzitol) -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-) Ethoxybenzyllidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-ethoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-ethoxybenzylidene)- D-sorbitol, 1,3: 2,4-bis-O- (o-isopropoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-isopropoxybenzylidene) -D- Sorbitol, 1,3: 2,4-bis-O- (p-isopropoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (one-propoxybenzylidene) -D-sorbitol , 1,3: 2,4-bis-O- (mn-propoxybenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (pn-propoxybenzylidene) -D-sorbitol , 1,3: 2,4-bis-O- (o-methoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m) -Methoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4-bis-O- (p-methoxycarbonylbenzylene) -D-sorbitol, 1,3: 2,4-bis-O- (o-ethoxy) Carbonylbenzylidene) -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-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- (one-propoxycarbonyl) Benzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (mn-propoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (pn-) Propoxycarbonylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (o-fluorobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-fluorobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-fluorobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (o-chlorobenzylidene) -D-sorbitol , 1,3: 2,4-bis-O- (m-chlorobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol, 1,3 : 2,4-bis-O- (o-bromobenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (m-bromobenzylidene) -D-sorbitol, 1,3: 2,4 -Bis-O- (p-bromobenzylidene) -D-sorbitol, 1,3-O-benzylidene-2,4-O- (p-methylbenzylidene) -D-sorbitol, 1,3-O- (p-) Methylbenzylidene) -2,4-O-benzylidene-D-sorbitol, 1,3-O-benzylidene-2,4-O- (p-ethylbendylidene) -D-sorbitol, 1,3-O- (p-) Ethylbenzylidene) -2,4-O-benzylidene-D-sorbitol, 1,3-O-benzylidene-2,4-O- (p-chlorobenzylidene) -D-sorbitol Le, 1,3-O- (p-chlorobenzylidene) -2,4-O-benziliden-D-sorbitol, 1,3-O-benziliden-2,4-O- (2', 4'-dimethylbenzylidene) ) -D-Sorbitol, 1,3-O- (2', 4'-Dimethylbenziliden) -2,4-O-Benzilidene-D-Sorbitol, 1,3-O-Benzilidene-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-methylbendylidene) -D -Sorbitol, 1,3-O- (p-methylbenzylene) -2,4-O- (3', 4'-dimethylbenziliden) -D-Sorbitol, 1,3-O- (3', 4'- Dimethylbenzylidene) -2,4-O-p-methylbendylidene-D-sorbitol, 1,3-O- (p-ethylbendiliden) -2,4-O- (3', 4'-dimethylbendylidene) -D -Sorbitol, 1,3-O- (3', 4'-dimethylbenzylidene) -2,4-O-p-ethylbendylidene-D-sorbitol, 1,3-O- (p-methylbendylidene) -2, 4-O- (p-chlorobenzylidene) -D-sorbitol, 1,3-O- (p-chlorobenzylidene) -2,4-O- (p-methylbendylidene) -D-sorbitol, 1,3: 2 , 4-bis-O- (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-ethylbendylidene) -1-methylsorbitol, 1,3: 2,4-bis-O -(Pn-propylbenzylene) -1-methylsorbitol, 1,3: 2,4-bis-O- (2', 3'-dimethylbenzylene) -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-me Chilsorbitol, 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'-methoxybenzylidene) ) -1-Methylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dichlorobenzylidene) -1-methylsorbitol, 1,3: 2,4-bis-O- (p-) Methylcarbonylbenzylidene) -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-propylbenzylene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (2', 3'-dimethylbenzylene) -1-ethylsorbitol, 1,3: 2,4-bis -O- (2', 4'-dimethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (2', 5'-dimethylbenzylidene) -1-ethylsorbitol, 1,3 : 2,4-bis-O- (2', 6'-dimethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -1- Ethylsorbitol, 1,3: 2,4-bis-O- (3', 5'-dimethylbenzylidene) -1-d Chilsorbitol, 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-methoxycarbonylbenzylene) -1 -Ethyl sorbitol, 1,3: 2,4-bis-O- (3'-methyl-4'-fluorobenzylidene) -1-ethyl sorbitol, 1,3: 2,4-bis-O- (3'- Bromo-4'-ethylbenzylidene) -1-ethylsorbitol, 1,3: 2,4-bis-O-benzylidene-1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-) Methylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- ( pn-propylbenzylene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 3'-dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2 , 4-Bis-O- (2', 4'-Dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-Bis-O- (2', 5'-Dimethylbenzylidene) -1- n-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-propylsorbitol, 1,3: 2,4-bis-O- (3', 5'-dimethylbenzylidene) -1-n-propylsorbitol, 1,3: 2 , 4-Bis-O- (2', 3'-diethylbenzylidene) -1-n-propylsorbitol, 1, 3: 2,4-bis-O- (2', 4'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 5'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (2', 6'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3', 4'-diethylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3', 5'-diethylbenzylidene) -1-n-propylsorbitol, 1, 3: 2,4-bis-O- (3'-methyl-4'-methoxybenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (3', 4'-dichloro Benzilidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-methoxycarbonylbenzylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- ( p-ethoxycarbonylbenzylene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (p-propoxycarbonylbenzylene) -1-n-propylsorbitol, 1,3-O- (p-) n-Propylbenzylidene) -2,4-O- (p-propoxybendiliden) -1-n-propylsorbitol, 1,3-O- (p-propoxybendiliden) -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'-ethylbendylidene) -1-n-propylsorbitol, 1,3: 2,4-bis-O- (pn-propylbendylidene) -1-propenylsorbitol , 1,3: 2,4-bis-O- (p-ethoxycarbonylbenzylene) -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-propoxybendiliden) -2,4 -O- (pn-propylbenzylene) -1-propenylsorbitol, 1,3: 2,4-bis-O-benzylidene-1-allylsorbitol, 1,3: 2,4-bis-O- ( p-methylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (p-) n-propylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 3'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O -(2', 4'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 5'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2 , 4-bis-O- (2', 6'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -1-allyl sorbitol , 1,3: 2,4-bis-O- (3', 5'-dimethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 3'-diethylbenzylidene) ) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2', 4'-diethylbenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (2') , 5'-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-ethoxycarbonylbenzylidene) -1-allyl sorbitol, 1,3: 2, 4-Bis-O- (p-propoxycarbonylbenzylene) -1-allyl sorbitol, 1,3-O- (pn-propylbenzylene) -2,4-O- (p-propoxybenzyllidene) -1-allyl Sorbitol, 1,3-O- (p-propoxybenzylidene) -2,4-O- (pn-propylbenziliden) -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-allylsorbitol, 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-) Examples thereof include 4'-fluorobenzylidene) -1-allyl sorbitol, 1,3: 2,4-bis-O- (3'-bromo-4'-ethylbenzylidene) -1-allyl sorbitol and the like.

Among the above diacetal compounds, 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p) from the viewpoint of improving rigidity. -Ethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O- (p) -N-propylbenzylidene) -1-propylsorbitol and the like are particularly preferable.

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. You may.

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, 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-chlorobenzylidene) -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)- An example is a combination of D-sorbitol.

The diacetal compound is manufactured as described in, for example, Japanese Patent Application Laid-Open No. 48-43748, Japanese Patent Application Laid-Open No. 53-5165, Japanese Patent Application Laid-Open No. 57-185287, Japanese Patent Application Laid-Open No. 2-231488 and the like. It can be easily produced by using a method or the like. Further, those currently commercially available as crystal nucleating agents for polyolefins, for example, Gelol D, Gelol MD, Gelol DXR of New Japan Chemical Co., Ltd., Mirad 3988, Millad NX8000, etc. of Milliken (USA) are used as they are. May be good.

The second feature of the polypropylene-based resin composition of the present invention is a solid substance such as pellets obtained by melting and mixing at a temperature higher than the temperature at which the diacetal compound is melted and then cooling and solidifying. That is.

The temperature at which the diacetal dissolves in the molten polypropylene-based resin may be a temperature at which the effect of the present invention is exhibited, and 100% of the diacetal compound does not necessarily have to be dissolved. For example, 70 in the contained diacetal compound. It means the temperature at which% or more, preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more are melted.

Further, from the viewpoint of deterioration such as coloring of the resin, _{it is not preferable that the temperature (T 1} ) at the time of melting and mixing is too high, and for example, it is particularly recommended that the temperature is in the following range.
(Equation 1) T _m ≤ T ₁ <T _m +15
Tm is the temperature at which the blended diacetal compound dissolves in the melted polypropylene-based resin.

A third feature of the polypropylene-based resin composition of the present invention is that the molding method of the polypropylene-based resin molded product is an orientation gel molding method in which the diacetal compound is molded at a temperature lower than the temperature at which it is melted in the polypropylene-based resin. Is.

The temperature below the temperature at which the diacetal dissolves in the molten polypropylene-based resin may be a temperature at which the effect of the present invention is exhibited, and it is not always necessary that 100% of the diacetal compound is not dissolved, and the diacetal compound is contained, for example. It means a temperature in which 70% or more, preferably 80% or more, more preferably 90% or more, particularly preferably 95% or more of the diacetal compound is in an undissolved state.

Further, from the viewpoint of moldability, it is not preferable that the temperature at the time of molding (T ₂ ) is too low, and for example, it is particularly recommended that the temperature is in the following range.
(Equation 2) T _m- 15 ≤ T ₂ <T _m
Tm is the temperature at which the blended diacetal compound dissolves in the melted polypropylene-based resin.

<Polypropylene resin molded product>
The polypropylene-based resin molded product of the present invention is characterized by being molded by an orientation gel molding method using the polypropylene-based resin composition obtained above as a raw material and molding at a temperature lower than the temperature at which the diacetal compound is melted in the melted polypropylene-based resin. And.

The temperature at which the diacetal dissolves in the molten polypropylene-based resin may be a temperature at which the effect of the present invention is exhibited, and 100% of the diacetal compound does not necessarily have to be dissolved. For example, 70 in the contained diacetal compound. It means the temperature at which% or more, preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more are melted.

Further, from the viewpoint of moldability, it is not preferable that the temperature at the time of molding (T ₂ ) is too low, and for example, it is particularly recommended that the temperature is in the following range.
(Equation 2) T _m- 15 ≤ T ₂ <T _m
Tm is the temperature at which the blended diacetal compound dissolves in the melted polypropylene-based resin.

<Manufacturing method of polypropylene resin molded product>
As described above, the polypropylene-based resin molded article of the present invention is made from a polypropylene-based resin composition containing the above-mentioned specific polypropylene-based resin and a specific diacetal compound and prepared under the above-mentioned specific conditions as a raw material. It is manufactured by orientation gel molding under the above conditions. More specifically, for example, a manufacturing method including the following steps (i) to (iii) is exemplified.
(I) A predetermined amount of the diacetal compound of the present invention and other additives are blended with 100 parts by mass of the polypropylene-based resin of the present invention and dry-blended.
(Ii) After melting and mixing at a temperature higher than the temperature at which the diacetal compound containing the dry blend obtained above dissolves in the melted polypropylene resin, it is cooled and solidified, and if necessary, it is cut into a pellet shape or the like. Obtain a polypropylene-based resin composition.
(Iii) Using the polypropylene-based resin composition obtained above as a raw material, molding is performed at a temperature lower than the temperature at which the contained diacetal compound dissolves in the molten polypropylene-based resin to obtain a polypropylene-based resin molded product having a predetermined shape. The molding method is not particularly limited as long as the effect of the present invention is exhibited, and any conventionally known molding method such as injection molding, extrusion molding, blow molding, pneumatic molding, rotary molding, or film molding can be adopted. ..

The polypropylene-based resin molded product thus obtained is extremely excellent in mechanical properties such as rigidity and impact resistance, and thermal properties such as heat resistance. , Machine parts, daily miscellaneous goods, etc., very useful. In particular, mechanical properties such as rigidity have been greatly improved compared to conventional ones, and it is expected that their applications will expand in the fields of automobile materials and industrial materials, where lack of rigidity has been an issue so far. ..

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 and properties of the polypropylene-based resin used in the examples, the abbreviations of the diacetal compounds in the examples, and the measurement method of each characteristic are as follows.

Abbreviation and properties of polypropylene resin used in the examples PP-1: Homopolypropylene resin, isotactic pentad fraction 0.96, molecular weight distribution (Mw / Mn) 5.0, melt flow rate (230 ° C) 30g / 10min
PP-2: Homopolypropylene resin, isotactic pentad fraction 0.965, molecular weight distribution (Mw / Mn) 5.2, melt flow rate (230 ° C) 15 g / 10 min
PP-3: Homopolypropylene resin, isotactic pentad fraction 0.98, molecular weight distribution (Mw / Mn) 5.0, melt flow rate (230 ° C) 7 g / 10 min
PP-4: Homopolypropylene resin, isotactic pentad fraction 0.96, molecular weight distribution (Mw / Mn) 5.1, melt flow rate (230 ° C) 35 g / 10 min

Abbreviation of diacetal compound in Examples DMDBS: 1,3: 2,4-bis-O- (3', 4'-dimethylbenzylidene) -D-sorbitol EDBS: 1,3: 2,4-bis-O- (P-Ethylbenzylidene) -D-sorbitol PDBN: 1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-n-propylsorbitol

Measurement method of each characteristic (1) Bending elastic modulus and bending strength Using a universal material tester (manufactured by Instron), a bending test was conducted according to JIS K 7171 (2016), and the bending elasticity was obtained based on the obtained results. The modulus and bending strength were determined. The test temperature was 25 ° C. and the test speed was 10 mm / min.

(2) Izod Impact Strength Using an Izod impact tester (manufactured by Yasuda Seiki Co., Ltd., D258), an Izod impact test was conducted by a method according to JIS K 7110 (1999) to determine the Izod impact strength without a notch. The test temperature was 23 ° C.

[Example 1]
100 parts by mass of "PP-1" as a polypropylene resin, 0.3 parts by mass of "DMDBS" as a diacetal compound, and tetrakis [methylene-3- (3,5-di-tert-butyl-4-) as other additives. Hydroxyphenyl) propionate] Methane (manufactured by BASF Japan Co., Ltd., trade name "IRGANOX1010") 0.05 parts by mass, tris (2,4-di-tert-butylphenyl) phosphite (manufactured by BASF Japan Co., Ltd., product) Name "IRGAFOS168") 0.05 parts by mass was dry blended. The dry blend is melt-mixed at a melt extrusion temperature of 230 ° C. using a twin-screw extruder (L / D = 45 manufactured by Technobel Co., Ltd., screw diameter 15 mm, die diameter 5 mm), and then the extruded strands are cooled. Then, it was cut with a pelletizer to prepare a polypropylene-based resin composition.

Subsequently, using the obtained polypropylene-based resin composition, an injection molding machine (NS40-5A manufactured by Nissei Resin Industry Co., Ltd.) was used to inject molding temperature (heating temperature) 190 ° C. and mold temperature (cooling temperature) 40. The polypropylene-based resin molded article (test piece) of the present invention was prepared by molding under the condition of ° C. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 1.

[Example 2]
The polypropylene-based resin molded product (test piece) of the present invention was prepared in the same manner as in Example 1 except that the compounding amount of the diacetal compound was changed to 0.4 parts by mass and the injection molding temperature was changed to 200 ° C. .. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 1.

[Example 3]
The polypropylene-based resin molded product (test piece) of the present invention was prepared in the same manner as in Example 2 except that the blending amount of the diacetal compound was changed to 0.5 parts by mass and the melt extrusion temperature was changed to 240 ° C. .. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 1.

[Example 4]
The polypropylene-based resin molded product (test piece) of the present invention was prepared in the same manner as in Example 2 except that "MDBS" was used instead of "DMDBS" as the diacetal compound. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 1.

[Example 5]
The polypropylene-based resin molded product (test piece) of the present invention was prepared in the same manner as in Example 2 except that "EDBS" was used instead of "DMDBS" as the diacetal compound. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 1.

[Example 6]
A test piece having a predetermined shape was prepared in the same manner as in Example 1 except that "PDBN" was used as the diacetal compound instead of "DMDBS" and the blending amount was changed to 0.8 parts by mass. did. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 1.

[Example 7]
The polypropylene-based resin molded product (test piece) of the present invention was prepared in the same manner as in Example 2 except that "PP-2" was used instead of "PP-1" as the polypropylene-based resin. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 1.

[Example 8]
The polypropylene-based resin molded product (test piece) of the present invention was prepared in the same manner as in Example 2 except that "PP-3" was used instead of "PP-1" as the polypropylene-based resin. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 1.

[Example 9]
The polypropylene-based resin molded product (test piece) of the present invention was prepared in the same manner as in Example 2 except that "PP-4" was used instead of "PP-1" as the polypropylene-based resin. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 1.

[Comparative Example 1]
A polypropylene-based resin molded product (test piece) other than the present invention was prepared in the same manner as in Example 2 except that the injection temperature was changed to 230 ° C. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 2.

[Comparative Example 2]
A polypropylene-based resin molded product (test piece) other than the present invention was prepared in the same manner as in Example 2 except that the diacetal compound was not blended. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 2.

[Comparative Example 3]
2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, which is a general-purpose rigidity-imparting type crystal nucleating agent, instead of 0.4 parts by mass of the diacetal compound "DMDBS" A polypropylene-based resin molded product (test piece) other than the present invention was carried out in the same manner as in Example 2 except that 0.2 part by mass of sodium (manufactured by ADEKA Corporation, trade name "ADEKA STUB NA-11") was blended. ) Was prepared. Using the obtained test pieces, a bending test and an Izod impact test were performed, and the obtained results are summarized in Table 2.

The polypropylene-based resin molded product of the present invention has extremely high rigidity, little decrease in impact resistance, and exhibits extremely excellent strength. Therefore, automobile parts, mechanical engineering parts, chemical industry parts, and home appliance parts. It can be used as a molded product such as, and is particularly useful for automobile parts applications that require high rigidity.

Claims (14)

A high-rigidity polypropylene-based resin molded product molded using a polypropylene-based resin composition containing a polypropylene-based resin and a diacetal compound.
The polypropylene-based resin has a high stereoregularity in which the isotactic pentad fraction by the 13C-NMR method is in the range of 0.96 to 0.995, and the molecular weight distribution (Mw / Mn) by the GPC method. ) Is a highly crystalline polypropylene resin in the range of 4 to 16.
The diacetal compound is a diacetal compound represented by the following general formula (1).
The polypropylene-based resin composition is a polypropylene-based resin composition that is melt-mixed at a temperature equal to or higher than the temperature at which the diacetal compound is melted in the melted polypropylene-based resin, and then cooled and solidified.
The molding method is an orientation gel molding method in which a diacetal compound is molded at a temperature lower than the temperature at which it is melted in a molten polypropylene-based resin.
High-rigidity polypropylene resin molded product.

[In formula (1), R ¹ and R ² are the same or different, hydrogen atom, linear or branched alkyl group having 1 to 4 carbon atoms, linear or branched carbon, respectively. It represents an alkoxy group having the number 1 to 4, a linear or branched-chain alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ] The high-rigidity polypropylene-based resin molded product according to claim 1, wherein the melt flow rate (230 ° C.) of the polypropylene-based resin is 30 g / 10 min or more. The high-rigidity polypropylene-based resin molded product according to claim 1 or 2, wherein the isotactic pentad fraction of the polypropylene-based resin by the 13C-NMR method is in the range of 0.97 to 0.99. The high-rigidity polypropylene-based resin molded product according to any one of claims 1 to 3, wherein the polypropylene-based resin has a molecular weight distribution (Mw / Mn) of 4 to 10 according to the GPC method. The high-rigidity polypropylene-based resin molded product according to any one of claims 1 to 4, wherein the polypropylene-based resin has a melt flow rate (230 ° C.) of 35 g / 10 min or more. 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 high-rigidity polypropylene-based resin molded product according to any one of claims 1 to 5, 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 high-rigidity polypropylene-based resin molded product according to any one of claims 1 to 5, wherein is 1. A method for producing a high-rigidity polypropylene-based resin molded product containing a polypropylene-based resin and a diacetal compound.
The polypropylene-based resin has a high stereoregularity in which the isotactic pentad fraction by the 13C-NMR method is in the range of 0.96 to 0.995, and the molecular weight distribution (Mw / Mn) by the GPC method. ) Is a highly crystalline polypropylene resin in the range of 4 to 16.
The diacetal compound is a diacetal compound represented by the following general formula (1).
After the diacetal compound is dissolved in the melted polypropylene resin, it is cooled and solidified to prepare a polypropylene resin composition, and then the polypropylene resin composition is molded at a temperature lower than the temperature at which the diacetal compound is melted in the melted polypropylene resin. A method for producing a high-rigidity polypropylene-based resin molded body, which is characterized by the above.

[In formula (1), R ¹ and R ² are the same or different, hydrogen atom, linear or branched alkyl group having 1 to 4 carbon atoms, linear or branched carbon, respectively. It represents an alkoxy group having the number 1 to 4, a linear or branched-chain alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom. R ³ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched chain alkenyl group having 2 to 4 carbon atoms, or a linear or branched chain carbon. The number 1 to 4 hydroxyalkyl groups are shown. m and n represent integers of 1 to 5, respectively. p indicates 0 or 1. The two R ^1s may be bonded to each other to form a tetralin ring with the benzene ring to which they are bonded. Two R ² groups may form a tetralin ring together with a benzene ring to which they are attached. ] The method for producing a high-rigidity polypropylene-based resin molded product according to claim 8, wherein the melt flow rate (230 ° C.) of the polypropylene-based resin is 30 g / 10 min or more. The method for producing a high-rigidity polypropylene-based resin molded product according to claim 8 or 9, wherein the isotactic pentad fraction of the polypropylene-based resin by the 13C-NMR method is in the range of 0.97 to 0.99. The method for producing a high-rigidity polypropylene-based resin molded product according to any one of claims 8 to 10, wherein the molecular weight distribution (Mw / Mn) of the polypropylene-based resin by the GPC method is in the range of 4 to 10. The method for producing a high-rigidity polypropylene-based resin molded product according to any one of claims 8 to 11, wherein the melt flow rate (230 ° C.) of the polypropylene-based resin is 35 g / 10 min or more. 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 method for producing a high-rigidity polypropylene-based resin molded product according to any one of claims 8 to 12, 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 method for producing a high-rigidity polypropylene-based resin molded product according to any one of claims 8 to 12, wherein the number is 1.