JP2013256613A - Method of manufacturing polypropylene resin shaped article including method of refining crystal of amide compound, polypropylene resin shaped article obtained by the manufacturing method, and secondary processed product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for refining a crystal in a process that manufactures a polypropylene-based resin composition in a system that contains a needle crystal of an amide compound existing in a polypropylene-based resin; a method of manufacturing the polypropylene resin shaped article including the method; the polypropylene resin shaped article obtained by the manufacturing method; and a secondary processing molding of the same.SOLUTION: A method of manufacturing a polypropylene resin shaped article is characterized by adjusting a diameter of a strand at cooling solidification to a range from 0.5 mm to 2.0 mm in a process to cool a molten polypropylene-based resin composition to deposit a needle crystal of an amide compound.

Description

  The present invention relates to a method for producing a polypropylene resin molded product including a method for refining needle-like crystals of an amide compound when molding a polypropylene resin composition, a polypropylene resin molded product obtained by the production method, and the method It relates to secondary processed molded products.

  Polypropylene resins have crystal forms such as α crystals and β crystals, but β crystals can be preferentially produced by blending specific crystallization conditions and β crystal nucleating agents. β crystals have significantly different thermal and mechanical properties than normal α crystals, and by preferentially expressing β crystals, various physical properties such as heat resistance and impact resistance can be improved. Are known. As a method of forming β crystals, there is a method of molding under a thermal gradient, but it is known that more β crystals can be efficiently formed by adding a certain amide compound (Patent Document). 1-5).

JP-A-5-255551 JP-A-5-262936 JP-A-5-310665 JP-A-7-188246 JP-A-8-100088

  The present invention relates to a method of making a crystal further finer in a step of producing a polypropylene resin composition in a system containing acicular crystals of an amide compound present in a polypropylene resin, and a polypropylene resin molding including the method It aims at providing the manufacturing method of a body, the polypropylene-type resin molding obtained by this manufacturing method, and its secondary fabrication molded product.

  In the process of searching for a method for easily obtaining a polypropylene-based resin molded article having excellent characteristics, the inventors of the present invention have made the crystals acicular, that is, when the amide compound dissolved in the molten polypropylene-based resin is crystallized. It was confirmed that the mechanical properties and thermal properties of the obtained molded body were further improved by promoting the crystal growth in the longitudinal direction. Furthermore, it has been confirmed that the finer the acicular crystal, the greater the effect. That is, it is important to obtain a polypropylene resin molded article having excellent characteristics and a secondary processed molded article thereof by making the needle-like crystals of the amide compound finer when molding the polypropylene resin composition. I found out.

  Therefore, the present inventors have added a amide compound to produce a polypropylene-based molded article having excellent characteristics, and relates to a method for further miniaturizing the needle-like crystals of the amide compound contained in the polypropylene-based resin composition. As a result of intensive studies, it was found that the above problems can be satisfied by controlling the shape of the polypropylene resin composition obtained in the process of producing the polypropylene resin composition, and the present invention is completed based on such knowledge. It came.

  That is, the present invention controls the shape of a polypropylene resin composition in a method for producing a polypropylene resin composition comprising a step of molding a polypropylene resin composition containing needle crystals of the following amide compound. The present invention provides a method for producing a polypropylene-based resin molded product including a method for further miniaturizing the acicular crystals contained therein, a polypropylene-based resin molded product obtained by the production method, and a secondary processed molded product thereof.

［式（１）中、Ｒ^１は、炭素数１〜２４の飽和若しくは不飽和の脂肪族ジカルボン酸残基、炭素数４〜２８の飽和若しくは不飽和の脂環族ジカルボン酸残基、又は炭素数６〜２８の芳香族ジカルボン酸残基を表し、Ｒ^２及びＲ^３は、同一又は異なって、それぞれ炭素数３〜１８のシクロアルキル基、下記の一般式（ａ）、一般式（ｂ）、一般式（ｃ）又は一般式（ｄ）で示される基を表す

（式（ａ）〜（ｄ）中、Ｒ^４は水素原子、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、炭素数６〜１０のシクロアルキル基又はフェニル基を表し、Ｒ^５は炭素数１〜１２の直鎖状又は分岐鎖状のアルキル基を表し、Ｒ^６は、炭素数１〜４の直鎖状又は分岐鎖状のアルキレン基を表し、Ｒ^７は、炭素数１〜４の直鎖状又は分岐鎖状のアルキレン基を表す）。］ (Claim 1)
A method for producing a polypropylene resin molded body comprising a step of molding a polypropylene resin composition containing needle-like crystals of at least one amide compound represented by the following general formula (1),
The shape of the polypropylene resin composition is a pellet shape having a minor axis of 0.5 mm or more and 2.0 mm or less, and needle crystals of the amide compound are present in the molten polypropylene resin at the time of molding. A method for producing a polypropylene-based resin molded product.
General formula (1):

[In the formula (1), R ¹ is a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 24 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 4 to 28 carbon atoms, or carbon. Represents an aromatic dicarboxylic acid residue having a number of 6 to 28, and R ² and R ³ are the same or different and are each a cycloalkyl group having 3 to 18 carbon atoms, the following general formulas (a) and (b): Represents a group represented by general formula (c) or general formula (d)

(In the formulas (a) to (d), R ⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or a phenyl group; ⁵ represents a linear or branched alkyl group having 1 to 12 carbon atoms, R ⁶ represents a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁷ represents a carbon number. 1-4 represents a linear or branched alkylene group). ]

(Section 2)
A polypropylene resin composition containing needle-like crystals of an amide compound, (i) heating an unkneaded raw material containing the polypropylene resin and the amide compound, and dissolving the amide compound in the molten polypropylene resin; ii) A composition obtained by a production method comprising a step of cooling the molten polypropylene resin composition obtained in the step (i) to precipitate acicular crystals of an amide compound,
The melting temperature of the polypropylene resin composition in the step (i) is in the range of T _dis or more and T _dis + 50 ° C. or less (T _dis represents the temperature at which the amide compound is dissolved in the polypropylene resin), and
In the step (ii), the diameter of the strand at the time of cooling and solidification is adjusted to a range of 0.5 mm or more and 2.0 mm or less, and the method for producing a polypropylene resin molded article according to (Item 1).

(Section 3)
In General Formula (1), R ¹ is a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 12 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 6 to 10 carbon atoms, or the number of carbon atoms Represents an aromatic dicarboxylic acid residue having 6 to 20 and R ² and R ³ are the same or different and each represents a cycloalkyl group having 3 to 12 carbon atoms, or a general formula (a), a general formula (b), a general formula The method for producing a polypropylene resin molded article according to (Item 1) or (Item 2), which represents a group represented by the formula (c) or the general formula (d).

(Section 4)
In the general formula (1), R ¹ is a saturated aliphatic dicarboxylic acid residue having 4 to 8 carbon atoms, a saturated alicyclic dicarboxylic acid residue having 6 to 8 carbon atoms, or an aromatic dicarboxylic acid having 6 to 20 carbon atoms. R ² and R ³ are the same or different and each is a cyclohexyl group or a phenyl group which may be substituted with one alkyl group having 1 to 4 carbon atoms (Claim 1) to (Claim). 3) The method for producing a polypropylene resin molded article according to any one of the above.

で表される芳香族ジカルボン酸残基であり、Ｒ^２及びＲ^３が、同一又は異なって、それぞれ１個の炭素数１〜４のアルキル基で置換されていてもよいシクロヘキシル基である請求（項１）〜（項４）の何れかに記載のポリプロピレン系樹脂成形体の製造方法。 (Section 5)
In the general formula (1), R ¹ represents the general formula (e) or the general formula (f).

Wherein R ² and R ³ are the same or different and each is a cyclohexyl group optionally substituted by one alkyl group having 1 to 4 carbon atoms ( The manufacturing method of the polypropylene resin molding in any one of claim | item 1)-(item 4).

(Claim 6)
The method for producing a polypropylene resin molded article according to any one of (Item 1) to (Item 5), wherein the amide compound is N, N′-dicyclohexyl-2,6-naphthalenedicarboxamide.

(Claim 7)
The manufacturing method of the polypropylene resin composition molded article according to any one of (Item 1) to (Item 6), containing 0.03 to 0.5 parts by weight of the amide compound with respect to 100 parts by weight of the polypropylene resin. .

(Section 8)
In the polypropylene-based resin composition, the amide compound and at least one compound selected from the group consisting of a saturated or unsaturated fatty acid metal salt coexist (Claim 1) to (Claim 7). The manufacturing method of the polypropylene resin molding of description.

(Claim 9)
The method for producing a polypropylene resin molded article according to any one of (Item 1) to (Item 8), wherein the fatty acid metal salt coexisting with the amide compound in the polypropylene resin composition is calcium stearate or calcium behenate.

(Section 10)
The method for producing a polypropylene resin molded article according to any one of (Item 1) to (Item 9), wherein a melt flow rate of the polypropylene resin at 230 ° C. and a load of 2160 g is 0.5 to 60.0 g / 10 minutes.

(Item 11)
The crystallization completion time (Tend) in isothermal crystallization at 135 ° C. measured with a differential scanning calorimeter (DSC) of the polypropylene resin composition is 1.2 minutes or less (Claim 1) to (Claim 10) A method for producing a polypropylene resin molded article according to claim 1.

［式（１）中、Ｒ^１は、炭素数１〜２４の飽和若しくは不飽和の脂肪族ジカルボン酸残基、炭素数４〜２８の飽和若しくは不飽和の脂環族ジカルボン酸残基、又は炭素数６〜２８の芳香族ジカルボン酸残基を表し、Ｒ^２及びＲ^３は、同一又は異なって、それぞれ炭素数３〜１８のシクロアルキル基、下記の一般式（ａ）、一般式（ｂ）、一般式（ｃ）又は一般式（ｄ）で示される基を表す

（式（ａ）〜（ｄ）中、Ｒ^４は水素原子、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、炭素数６〜１０のシクロアルキル基又はフェニル基を表し、Ｒ^５は炭素数１〜１２の直鎖状又は分岐鎖状のアルキル基を表し、Ｒ^６は、炭素数１〜４の直鎖状又は分岐鎖状のアルキレン基を表し、Ｒ^７は、炭素数１〜４の直鎖状又は分岐鎖状のアルキレン基を表す）。］ (Clause 12)
A method of refining needle-like crystals of at least one amide compound represented by the following general formula (1) contained in a polypropylene resin composition,
(I) a step of heating an unkneaded raw material containing a polypropylene resin and an amide compound to dissolve the amide compound in the molten polypropylene resin, and (ii) a molten polypropylene system obtained in the step (i). A method comprising cooling the resin composition to precipitate amide compound needle crystals; and
In the step (ii), the diameter of the strand at the time of cooling and solidification is adjusted to a range of 0.5 mm or more and 2.0 mm or less.
General formula (1):

[In the formula (1), R ¹ is a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 24 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 4 to 28 carbon atoms, or carbon. Represents an aromatic dicarboxylic acid residue having a number of 6 to 28, and R ² and R ³ are the same or different and are each a cycloalkyl group having 3 to 18 carbon atoms, the following general formulas (a) and (b): Represents a group represented by general formula (c) or general formula (d)

(In the formulas (a) to (d), R ⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or a phenyl group; ⁵ represents a linear or branched alkyl group having 1 to 12 carbon atoms, R ⁶ represents a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁷ represents a carbon number. 1-4 represents a linear or branched alkylene group). ]

(Section 13)
In General Formula (1), R ¹ is a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 12 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 6 to 10 carbon atoms, or carbon Represents an aromatic dicarboxylic acid residue having a number of 6 to 20, and R ² and R ³ are the same or different and each represents a cycloalkyl group having 3 to 12 carbon atoms, or a general formula (a), a general formula (b), The method according to (Item 12), which represents a group represented by General Formula (c) or General Formula (d).

(Item 14)
In the general formula (1), R ¹ is a saturated aliphatic dicarboxylic acid residue having 4 to 8 carbon atoms, a saturated alicyclic dicarboxylic acid residue having 6 to 8 carbon atoms, or an aromatic dicarboxylic acid having 6 to 20 carbon atoms. A residue, R ² and R ³ are the same or different and each is a cyclohexyl group or a phenyl group which may be substituted with one alkyl group having 1 to 4 carbon atoms (claim 12) or (claim) The method according to 13).

で表される芳香族ジカルボン酸残基であり、Ｒ^２及びＲ^３が、同一又は異なって、それぞれ１個の炭素数１〜４のアルキル基で置換されていてもよいシクロヘキシル基である（項１２）〜（項１４）の何れかに記載の方法。 (Item 14)
In General Formula (1), R ¹ is General Formula (e) or General Formula (f)

Wherein R ² and R ³ are the same or different and each is a cyclohexyl group optionally substituted with one alkyl group having 1 to 4 carbon atoms (section) The method according to any one of 12) to (14).

(Section 16)
The method according to any one of (Item 12) to (Item 15), wherein the amide compound is N, N′-dicyclohexyl-2,6-naphthalenedicarboxamide.

［式（１）中、Ｒ^１は一般式（e）、又は一般式（f）

で表される芳香族ジカルボン酸残基を表し、Ｒ^２及びＲ^３は、同一又は異なって、それぞれ１個の炭素数１〜４のアルキル基で置換されていてもよいシクロヘキシル基を表す］ (Section 17)
(I) a step of heating an unkneaded raw material containing at least one amide compound represented by the following general formula (1), and dissolving the amide compound in the molten polypropylene resin;
(Ii) a step of cooling the molten polypropylene resin composition obtained in the step (i) to precipitate needle crystals of the amide compound; and (iii) the amide obtained in the step (ii). Obtained by a method for producing a polypropylene resin molded article comprising a step of melting and molding a polypropylene resin composition in which needle crystals of a compound are precipitated in a temperature range of T _m + 10 ° C. to T _dis -10 ° C., A polypropylene resin molded body,
A polypropylene-based resin composition in which the pellet shape of the polypropylene-based resin composition containing acicular crystals of the amide compound obtained in the step (ii) is in the range of 0.5 mm to 2.0 mm in the minor axis. Resin molded body.
General formula (1):

[In Formula (1), R ¹ is General Formula (e) or General Formula (f)

Wherein R ² and R ³ are the same or different and each represents a cyclohexyl group which may be substituted with one alkyl group having 1 to 4 carbon atoms]

(Item 18)
The polypropylene resin molded article according to (17), wherein the amide compound is N, N′-dicyclohexyl-2,6-naphthalenedicarboxamide.

(Section 19)
A secondary processed molded article obtained by further molding the polypropylene resin molded article according to (Item 17) or (Item 18).

  The present invention will be described in detail below.

<Polypropylene resin>
The polypropylene resin used in the present invention is a polymer having propylene as a main component, and specifically includes a propylene homopolymer and a random or block propylene copolymer mainly composed of propylene. it can.

  Examples of the propylene copolymer include a random copolymer or a block copolymer of propylene and a comonomer, which is mainly composed of propylene. Examples of the comonomer include 1-alkenes other than propylene (ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene, etc.) and other comonomers such as styrene, maleic anhydride, (meth) Acrylic acid etc. can be illustrated. The copolymer may be a propylene-ethylene multi-component copolymer. For example, in addition to propylene and ethylene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,4- Examples include copolymers containing hexadiene and the like.

  The propylene content in the copolymer is preferably about 70 to 99% by weight, particularly about 80 to 98% by weight. Of the copolymers mainly composed of propylene, propylene-ethylene copolymers are preferred. The propylene-ethylene copolymer is preferably a copolymer having an ethylene content of about 1 to 30% by weight, particularly about 2 to 20% by weight.

  In the present specification, the “ethylene content” means an ethylene content (content of a structural portion derived from ethylene) contained in a propylene-ethylene copolymer. The ethylene content can be generally measured by an infrared spectrum method (J. Polym. Sci., 7, 203 (1964)).

  Moreover, you may use the said polypropylene resin as a polymer blend containing a small amount of thermoplastic resins, for example, high-density polyethylene, polybutene-1, poly-4-methylpentene-1, etc. The content of the polypropylene resin in these polymer blends is preferably about 70 to 99% by weight, particularly about 80 to 98% by weight in the resin.

  As the melt flow rate (abbreviated as “MFR”) of these polypropylene resins, JIS K-7210 (1999) is recommended to be about 0.5 to 60 g / 10 minutes, preferably about 2 to 30 g / 10 minutes. The In the case of an injection molded product, about 5 to 60 g / 10 min, preferably about 10 to 30 g / 10 min is recommended. In the case of an extrusion-molded product, about 0.5 to 40 g / 10 minutes, preferably about 2 to 15 g / 10 minutes is recommended. In addition, said MFR is a numerical value in load 2160g and 230 degreeC.

  It has been confirmed that the MFR of the polypropylene resin used in the present invention affects the mechanical properties such as rigidity and impact resistance of the obtained molded product.

［式（１）中、Ｒ^１は、炭素数１〜２４の飽和若しくは不飽和の脂肪族ジカルボン酸残基、炭素数４〜２８の飽和若しくは不飽和の脂環族ジカルボン酸残基又は炭素数６〜２８の芳香族ジカルボン酸残基を表す。Ｒ^２及びＲ^３は同一又は異なって、それぞれ炭素数３〜１８のシクロアルキル基、下記の一般式（ａ）、一般式（ｂ）、一般式（ｃ）又は一般式（ｄ）で示される基を表す

（式（ａ）〜（ｄ）中、Ｒ^４は水素原子、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、炭素数６〜１０のシクロアルキル基又はフェニル基を表し、Ｒ^５は炭素数１〜１２の直鎖状又は分岐鎖状のアルキル基を表し、Ｒ^６は、炭素数１〜４の直鎖状又は分岐鎖状のアルキレン基を表し、Ｒ^７は、炭素数１〜４の直鎖状又は分岐鎖状のアルキレン基を表す）。］ <Amide compound>
The amide compound used in the present invention is exemplified by an amide compound represented by the following general formula (1). The amide compound is frequently used as a β crystal nucleating agent.
General formula (1):

[In formula (1), R ¹ is a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 24 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 4 to 28 carbon atoms, or a carbon number. It represents 6 to 28 aromatic dicarboxylic acid residues. R ² and R ³ are the same or different and are each represented by a cycloalkyl group having 3 to 18 carbon atoms, the following general formula (a), general formula (b), general formula (c), or general formula (d). Represents group

(In the formulas (a) to (d), R ⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or a phenyl group; ⁵ represents a linear or branched alkyl group having 1 to 12 carbon atoms, R ⁶ represents a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁷ represents a carbon number. 1-4 represents a linear or branched alkylene group). ]

In the present specification and claims, the saturated or unsaturated aliphatic dicarboxylic acid residue, saturated or unsaturated alicyclic dicarboxylic acid residue or aromatic dicarboxylic acid residue represented by R ¹ is: A group obtained by removing two carboxyl groups from the corresponding dicarboxylic acid.

In the present specification and claims, the saturated or unsaturated aliphatic dicarboxylic acid residue, saturated or unsaturated alicyclic dicarboxylic acid residue or aromatic dicarboxylic acid residue represented by R ¹ The number of carbons means the number of carbons as a dicarboxylic acid residue (that is, the number of carbons of dicarboxylic acid minus two carbons).

［式中、Ｒ^８は前記一般式（１）におけるＲ^１と同義である。］
で表される脂肪族、脂環族、又は芳香族のジカルボン酸と一般式（１ｂ）

［式中、Ｒ^９は前記一般式（１）におけるＲ^２及びＲ^３と同義である。］
で表される１種若しくは２種の脂環族又は芳香族のモノアミンをアミド化することにより容易に調製することができる。 The amide compound represented by the general formula (1) is represented by the general formula (1a)

[Wherein, R ⁸ has the same meaning as R ¹ in the general formula (1). ]
An aliphatic, alicyclic or aromatic dicarboxylic acid represented by the general formula (1b)

[Wherein, R ⁹ has the same meaning as R ² and R ³ in formula (1). ]
It can be easily prepared by amidating one or two alicyclic or aromatic monoamines represented by:

  The amide compounds according to the present invention are known or can be prepared according to known methods. For example, it can be produced by carrying out an amidation reaction using a dicarboxylic acid and a monoamine as raw materials according to the descriptions in JP-A-5-310665 and JP-A-7-188246. It can also be produced by subjecting a reactive derivative such as an acid anhydride, chloride, or ester compound of the dicarboxylic acid and a lower alcohol having about 1 to 4 carbon atoms to amidation. The amide compound produced according to a known method may contain some impurities, but 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 97% by weight or more is recommended. Examples of the impurities include partially amidated products derived from reaction intermediates or unreacted materials, imide compounds derived from side reaction products, and the like.

  Examples of the aliphatic dicarboxylic acid include saturated or unsaturated aliphatic dicarboxylic acids having 3 to 26 carbon atoms, preferably about 3 to 14 carbon atoms. More specifically, malonic acid, diphenylmalonic acid, succinic acid, phenyl Succinic acid, diphenyl succinic acid, glutaric acid, 3,3-dimethyl glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1 , 18-octadecanedioic acid. Examples of the alicyclic dicarboxylic acid include alicyclic dicarboxylic acids having 6 to 30 carbon atoms, preferably about 8 to 12 carbon atoms, and more specifically 1,2-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples include acid and 1,4-cyclohexanediacetic acid.

  Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids having 8 to 30 carbon atoms, preferably about 8 to 22 carbon atoms. More specifically, p-phenylene diacetic acid, p-phenylene diethanoic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, terephthalic acid, 1,8-naphthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid Acid, diphenic acid, 3,3′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-binaphthyldicarboxylic acid, bis (3-carboxyphenyl) methane, bis (4-carboxyphenyl) methane, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 3,3′-sulfonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 3,3′-oxydibenzoic acid, 4,4′-oxydibenzoic acid, 3,3′-carbonyldibenzoic acid, 4,4 '-Carbonyldibenzoic acid, 3,3'-thiodibenzoic acid, 4,4'-thiodibenzoic acid, 4,4'-(p-phenylenedioxy) dibenzoic acid, 4,4'-isophthaloyldibenzoic acid, 4,4'-terephthaloyldibenzoic acid, dithiosalicylic acid, 3,9-bis (p-carboxyphenyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (m- Carboxyphenyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (o-carboxyphenyl) -2,4,8,10-tetraoxaspiro [5,5] Undecane Aromatic dicarboxylic acids are exemplified.

［式中、Ｒ^１０は前記一般式（ｂ）におけるＲ^５と同義である。］
で表される化合物、又は一般式（３）

［式中、Ｒ^１１は前記一般式（ｄ）におけるＲ^７と同義である。］
で表される化合物が例示される。 Examples of the alicyclic monoamine include cycloalkylamine having 3 to 18 carbon atoms, and general formula (2).

[Wherein, R ¹⁰ has the same meaning as R ⁵ in formula (b). ]
Or a compound represented by the general formula (3)

[Wherein, R ¹¹ has the same meaning as R ⁷ in formula (d). ]
The compound represented by these is illustrated.

  More specifically, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2 -Propylcyclohexylamine, 2-isopropylcyclohexylamine, 4-propylcyclohexylamine, 4-isopropylcyclohexylamine, 2-tert-butylcyclohexylamine, 4-n-butylcyclohexylamine, 4-isobutylcyclohexylamine, 4-sec-butyl Cyclohexylamine, 4-tert-butylcyclohexylamine, 4-n-amylcyclohexylamine, 4-isoamylcyclohexyl Min, 4-sec-amylcyclohexylamine, 4-tert-amylcyclohexylamine, 4-hexylcyclohexylamine, 4-heptylcyclohexylamine, 4-octylcyclohexylamine, 4-nonylcyclohexylamine, 4-decylcyclohexylamine, 4-decylcyclohexylamine Undecylcyclohexylamine, 4-dodecylcyclohexylamine, 4-cyclohexylcyclohexylamine, 4-phenylcyclohexylamine, cycloheptylamine, cyclododecylamine, cyclohexylmethylamine, α-cyclohexylethylamine, β-cyclohexylethylamine, α-cyclohexylpropylamine , Β-cyclohexylpropylamine, and γ-cyclohexylpropylamine.

［式中、Ｒ^１２は前記一般式（ａ）におけるＲ^４と同義である。］
で表される化合物、又は一般式（５）

［式中、Ｒ^１３は前記一般式（ｃ）におけるＲ^６と同義である。］
で表される化合物が例示される。 As an aromatic monoamine, general formula (4)

[Wherein, R ¹² has the same meaning as R ⁴ in formula (a). ]
Or a compound represented by the general formula (5)

[Wherein, R ¹³ has the same meaning as R ⁶ in formula (c). ]
The compound represented by these is illustrated.

  More specifically, aniline, o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, p-ethylaniline, o-propylaniline, m-propylaniline, p-propylaniline, o-cumidine, m -Cumidine, p-cumidine, o-tert-butylaniline, pn-butylaniline, p-isobutylaniline, p-sec-butylaniline, p-tert-butylaniline, pn-amylaniline, p-isoamyl Aniline, p-sec-amylaniline, p-tert-amylaniline, p-hexylaniline, p-heptylaniline, p-octylaniline, p-nonylaniline, p-decylaniline, p-undecylaniline, p-dodecyl Aniline, p-cyclohexylaniline, o-aminodiphenyl, - diaminodiphenyl, p- amino diphenyl, benzylamine, alpha-phenylethylamine, beta-phenylethylamine, alpha-phenylpropylamine, beta-phenylpropylamine, .gamma. phenylpropylamine are exemplified.

Among the compounds of the general formula (1), R ¹ is preferably a saturated or unsaturated aliphatic dicarboxylic acid residue having about 1 to 12 carbon atoms, a saturated or unsaturated alicyclic ring having about 6 to 10 carbon atoms. Represents an aromatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue having about 6 to 20 carbon atoms, and R ² and R ³ are the same or different, and a cycloalkyl group having about 3 to 12 carbon atoms, or a general formula ( It is a group represented by a), general formula (b), general formula (c) or general formula (d).

More preferably, R ¹ is a saturated aliphatic dicarboxylic acid residue having about 4 to 8 carbon atoms, a saturated alicyclic dicarboxylic acid residue having about 6 to 8 carbon atoms, or an aromatic dicarboxylic acid residue having about 6 to 20 carbon atoms. R ² and R ³ are a cyclohexyl group or a phenyl group which may be substituted with one alkyl group having about 1 to 4 carbon atoms.

More preferably, R ¹ is an aromatic dicarboxylic acid residue having about 6 to 20 carbon atoms, and R ² and R ³ may be substituted with one alkyl group having about 1 to 4 carbon atoms. It is a group.

In particular, R ¹ is an aromatic dicarboxylic acid residue represented by the following general formula (e) or general formula (f), and R ² and R ³ are one alkyl group having about 1 to 4 carbon atoms. It is recommended that it be an optionally substituted cyclohexyl group.

  Among the amide compounds represented by the general formula (1), preferred compounds include adipic acid dianilide, terephthalic acid di (cyclohexylamide), terephthalic acid di (2-methylcyclohexylamide), and N, N′-dicyclohexyl-2. , 6-Naphthalenedicarboxamide, N, N′-di (2-methylcyclohexyl) -2,6-naphthalenedicarboxamide, 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8 , 10-tetraoxaspiro [5,5] undecane, 3,9-bis [4- (N-4-tert-butylcyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5,5 ] Undecane, 3,9-bis {4- [N- (2,4-di-tert-butylcyclohexyl) carbamoyl] fur Sulfonyl} -2,4,8,10-spiro [5,5] undecane can be exemplified, and as the particularly preferred compound N, N'-dicyclohexyl-2,6-naphthalene dicarboxamide is recommended.

  The maximum particle size of the amide compound before being dissolved in the polypropylene resin in step (i) is recommended to be 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less. When the maximum particle size exceeds 20 μm, the amide compound is not completely dissolved in the step (i), and there is a possibility that undissolved residue may be generated. The undissolved undissolved amide compound causes the enlargement of the crystal (enlargement) in the next molding process, the impact strength of the obtained molded product decreases, and further causes the fracture during the secondary processing, It is not preferable. Here, the maximum particle size refers to the particle size when measured by a method based on the laser diffraction method.

<Fatty acid metal salt>
Examples of the fatty acid metal salt used in the present invention include calcium salts, magnesium salts, zinc salts and the like of saturated or unsaturated fatty acids having 12 to 32 carbon atoms, preferably 16 to 28 carbon atoms. Examples of the saturated fatty acid having 12 to 32 carbon atoms include lauric acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, serotic acid, carbocelic acid, montanic acid, mellicic acid, and racemic acid.

  Examples of unsaturated fatty acids having 12 to 32 carbon atoms include myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, docosadienoic acid, adrenic acid, ozbondic acid, succinic acid, nervonic acid, tetracosa. Examples include pentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, and nisic acid.

  These may be used alone or in appropriate combination of two or more.

  Of these, saturated fatty acid calcium salts having about 16 to 28 carbon atoms are preferred, and stearic acid and behenic acid calcium salts are particularly preferred.

<Other additives>
In the polypropylene resin composition according to the present invention, a conventionally known modifier for polyolefin may be appropriately blended within a range that does not impair the effects of the present invention, depending on the purpose of use and its use. In particular, an additive that inhibits the nucleating agent effect of the β crystal nucleating agent by the amide compound is preferably blended within a range that does not impair the nucleating agent effect.

  Examples of such a polyolefin modifier include various additives described in “Polylist Additives Manual” (May 2001) edited by the Sanitation Council for Polyolefins, and more specifically, Agents (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, phenolic compounds, UV absorbers, etc.), surfactants (nonionic, anionic, amphoteric, cationic, etc.), lubricants (Aliphatic hydrocarbons such as paraffin and wax, higher fatty acids having about 8 to 22 carbon atoms, aliphatic alcohols having about 8 to 18 carbon atoms, polyglycol, higher fatty acids having about 4 to 22 carbon atoms and 4 to 18 carbon atoms. Ester with aliphatic monohydric alcohol of about grade, higher fatty acid amide having about 8 to 22 carbon atoms, silicone oil, rosin derivative, etc.), filler (oxide, hydroxide, charcoal) , Sulfates, silicates, etc.), foaming agent, foaming aid, polymer additives, various additives organic nucleating agent other than the amide compound according to the present invention is illustrated.

  Examples of the organic nucleating agent include conventionally known nucleating agents for β-crystal polypropylene.

［式中、Ｒ^１４は水素原子、炭素数１〜１２程度の直鎖状若しくは分岐鎖状のアルキル基、フェニル基、ベンジル基、シクロヘキシル基又はカルボキシル基を表し、ａは０〜１２程度の整数を表し、Ａは下記の一般式（ｇ）、一般式（ｈ）、一般式（ｉ）、一般式（ｊ）又は一般式（ｋ）で表される基を表す

（式(ｇ)〜(ｋ)中、Ｒ^１５は、水素原子、炭素数１〜１２程度の直鎖状若しくは分岐鎖状のアルキル基又はハロゲン原子を表し、ｘは１〜４程度の整数、ｙは１〜６程度の整数を表す。尚、ｘ又はｙが２以上の整数の場合、２以上のＲ^１５は同一又は異なってもよい）。］
で表される化合物、有機二塩基酸のカルシウム塩、マグネシウム塩、バリウム塩（例えばピメリン酸カルシウム、テレフタル酸カルシウム等）、１２−ヒドロキシステアリン酸カリウム、安息香酸マグネシウム、コハク酸マグネシウム、フタル酸マグネシウム等、ベンゼンスルホン酸ナトリウム、ナフタリンスルホン酸ナトリウム等の芳香族スルホン酸化合物、ジカルボン酸ジエステル類又はトリカルボン酸トリエステル類、テトラオキサスピロ化合物類、イミドカルボン酸誘導体、フタロシアニンブルー等のフタロシアニン系、キナクリドン、キナクリドンキノン等のキナクリドン系等の顔料、前記有機二塩基酸と周期律表第IIＡ族金属の酸化物、水酸化物又は塩とからなる二成分系等が例示される。 Specifically, the following general formula (6)

[Wherein, R ¹⁴ represents a hydrogen atom, a linear or branched alkyl group having about 1 to 12 carbon atoms, a phenyl group, a benzyl group, a cyclohexyl group or a carboxyl group, and a is an integer of about 0 to 12] A represents a group represented by the following general formula (g), general formula (h), general formula (i), general formula (j) or general formula (k).

(In the formulas (g) to (k), R ¹⁵ represents a hydrogen atom, a linear or branched alkyl group having about 1 to 12 carbon atoms, or a halogen atom, x is an integer of about 1 to 4, y represents an integer of about 1 to 6. When x or y is an integer of 2 or more, R ¹⁵ of 2 or more may be the same or different. ]
A compound represented by the formula: calcium salt of organic dibasic acid, magnesium salt, barium salt (eg, calcium pimelate, calcium terephthalate, etc.), potassium 12-hydroxystearate, magnesium benzoate, magnesium succinate, magnesium phthalate, etc. , Aromatic sulfonic acid compounds such as sodium benzene sulfonate and sodium naphthalene sulfonate, dicarboxylic acid diesters or tricarboxylic acid triesters, tetraoxaspiro compounds, imide carboxylic acid derivatives, phthalocyanine series such as phthalocyanine blue, quinacridone, quinacridone Examples thereof include quinacridone-based pigments such as quinones, and two-component systems composed of the organic dibasic acids and Group IIA metal oxides, hydroxides or salts of the periodic table.

<Method for Producing Polypropylene Resin Molded Body and Secondary Processed Molded Product>
The method for producing a polypropylene resin molded body of the present invention comprises a step of molding a molten polypropylene resin composition in which needle-like crystals of an amide compound are present in a molten polypropylene resin, and the molten polypropylene resin Is molded in a state containing a fine acicular crystalline amide compound obtained by the method according to the present invention. Furthermore, a secondary processed molded product is obtained by molding the obtained polypropylene-based resin molded body by a method adopted in the technical field. For example, when the molded body is used as a raw fabric sheet, a secondary processed molded product is obtained by subjecting the raw fabric sheet to thermoforming.

  Hereinafter, the recommended manufacturing conditions of the polypropylene resin molded body and the secondary processed molded product will be described in detail along the manufacturing process.

  First, as a method for producing a polypropylene resin molded article, the following procedure (step) is usually employed.

  A polypropylene resin (powder or flake), an amide compound, and other additives as required are mixed to obtain a dry blend (unkneaded raw material). There is no restriction | limiting in particular in a mixing method, It mixes using well-known mixers, such as a Henschel mixer, a V blender, a super mixer, and a tumbler type. The mixing temperature is usually about room temperature to 100 ° C., and the mixing time is generally about 1 to 60 minutes, although it depends on the rotational speed of the apparatus.

The polypropylene resin composition according to the present invention is, for example, a high concentration additive blended with a polypropylene resin (powder or flakes), an amide compound, a fatty acid calcium salt, and other additives as necessary. An unmixed raw material in which a product (for example, a masterbatch in which the above additives are blended with a polypropylene resin at a high concentration) is blended with a polypropylene resin (powder or flakes) or other additives as necessary is fed into an extruder It can also be produced by charging, melt-kneading, and extruding.

Subsequently, the dry blend product is kneaded in a range where the kneading temperature is T _dis or higher and T _dis + 50 ° C. or lower by a uniaxial or twin screw extruder, a tandem kneading extruder, etc. employed in the technical field, The molten polypropylene resin composition discharged from the die is quickly guided to a coolant tank such as water and solidified by cooling. Next, the cooled and solidified strand-shaped polypropylene resin composition is cut into an appropriate length by a breaker such as a pelletizer to obtain a pellet-shaped polypropylene resin composition.

Here, _Tdis represents the temperature at which the amide compound is dissolved in the polypropylene resin, and the temperature at which the polypropylene resin composition was completely transparent by heating on the hot stage was defined as _Tdis .

  The kneading temperature refers to the temperature of the molten resin at the time of kneading, and the actual set temperature of the molding machine does not necessarily need to be in the above range depending on the degree of application such as shearing.

  Here, from the viewpoint of the rigidity and heat resistance of the polypropylene resin molded product, it is important that the amide compound in the polypropylene resin composition is a needle crystal, and the needle crystal is finer. It is to be. As a method for obtaining a polypropylene-based resin composition containing an acicular amide compound, there is a method in which an acicular amide compound is added in advance and kneaded under a condition in which the amide compound does not dissolve. In order to obtain crystals, a method in which the added amide compound is once dissolved in a molten polypropylene resin and then precipitated into a polypropylene resin as needle crystals when cooled and pelletized, that is, the polypropylene resin and The step of heating the polypropylene resin composition containing the amide compound to dissolve the amide compound in the molten polypropylene resin, and cooling the molten polypropylene resin composition obtained in the step, A method using a step of precipitating crystals is effective.

  In general, the faster the cooling rate at which crystals are precipitated from the dissolved state, the easier the crystal becomes, and in the present invention, the faster the cooling rate in step (ii), the finer needle-like crystals are obtained. In order to increase the cooling rate, it is also preferable to increase the temperature difference between the molten polypropylene resin composition and the refrigerant, but from the viewpoint of the overall cooling rate including the central portion of the strand-shaped polypropylene resin composition. Then, the influence of the distance from the surface in contact with the refrigerant has a greater influence. This is because the cooling rate of the central portion of the strand-shaped polypropylene resin composition is proportional to the first power of the temperature difference between the resin temperature and the refrigerant, whereas the center and surface of the strand-shaped polypropylene resin composition are This is considered to be inversely proportional to the square of the distance.

  Therefore, in the present invention, in order to further refine the needle-like crystals, the diameter of the strands of the molten polypropylene resin composition that has come out of the die when cooled and solidified in the refrigerant is controlled within a certain range. is important.

  The range of the strand diameter is preferably 0.5 mm or more and 2.0 mm or less, and more preferably 0.7 mm or more and 1.5 mm or less.

  If the strand diameter is less than 0.5 mm, the resulting pellet has extremely high adhesion to the hopper, and it is difficult to bite the screw into the molding machine. Exceeding is insufficient for improvement of rigidity and heat resistance, which are the effects of the present invention.

  The thin strand polypropylene resin composition obtained above is then cut to an appropriate length by a breaker to form a pellet-shaped forming raw material. The cutting length in the present invention is preferably larger than the diameter of the strand than the workability at the time of forming, the diameter in the flow direction becomes the long diameter of the obtained pellet, and the diameter in the direction perpendicular to the flow direction becomes the short diameter. . Therefore, the short diameter of the polypropylene resin composition and the strand diameter are synonymous. The pellet shape may be any of a cylindrical shape, an elliptical shape, and a cubic shape. In the case where the pellet has a shape other than the columnar shape, the pellet diameter can be determined by the length of the shortest portion between the pellet surfaces passing through the center portion of the pellet.

  By making the needle-like crystals of the amide compound in the polypropylene resin composition finer, the nucleation ability of the amide compound in the polypropylene resin composition can be improved. It can be confirmed by thermal analysis. Specifically, using a differential scanning calorimeter (DSC), the propylene resin composition pellets are melted, then rapidly cooled to the crystallization temperature, the polypropylene resin is isothermally crystallized, and the crystallization end time ( It can be determined by measuring Tend). Using the Tend of the obtained polypropylene resin composition as a guide, a change in the needle crystal shape can be confirmed. That is, the finer the crystal, the more the essential nucleating agent effect as a nucleating agent, and as a result, Tend tends to be shortened.

  It is recommended that the Tend of the polypropylene resin composition in the present invention is 1.2 minutes or less, more preferably 1.15 minutes or less, more preferably 1.10 minutes or less. When Tend exceeds 1.2 minutes, the improvement of rigidity and heat resistance, which are the effects of the present invention, is insufficient.

<Polypropylene-based resin molding>
The polypropylene resin molded body according to the present invention is an injection molding machine employed in the technical field, an extrusion molding machine equipped with a T die, and an inflation molding equipped with a circular die. It is manufactured through a molding process using a known molding machine such as a machine.

  In this case as well, it is important that the amide compound at the time of molding the polypropylene resin molded body is a needle crystal.

In the step of molding a molten polypropylene resin composition in which the needle-like crystals of the amide compound according to the present invention are present in a molten polypropylene resin, the range of the melting temperature for the molten polypropylene resin composition is as follows: Preferably, T _m + 10 ° C. or more and less than T _dis −10 ° C. (T _m represents the melting point of the polypropylene resin), more preferably T _m + 15 ° C. or more, less than T _dis −15 ° C., particularly T _m + 20 ° C. or more. _Tdis <-15 ° C. is recommended. The relationship between the temperature ranges is (T _m + 10 ° C.) <(T _dis −10 ° C.), (T _m + 15 ° C.) <(T _dis −15 ° C.), or (T _m + 20 ° C.) <(T _dis- 15 ° C) holds.

  More specifically, the melting temperature (resin temperature) in the molding step is about 190 to 260 ° C., preferably about 200 to 240 ° C., more preferably 200 to 200 ° C., although it depends on the type and amount of the amide compound. The range is about 230 ° C. By setting the melting temperature (resin temperature) to 190 ° C. or higher, generation of unmelted resin is suppressed, and by setting it to 260 ° C. or lower, physical properties such as rigidity and heat resistance of the polypropylene-based resin molded product are superior. There is a tendency to improve.

  In addition, by setting the melting temperature within the recommended range, it may have a positive effect on the secondary processed molded product. For example, the occurrence of breakage in the thermoforming process during secondary processing can be significantly suppressed. ,

  As the mold temperature (crystallization temperature) for injection molding or the like, a range of usually about 30 to 90 ° C, preferably about 40 to 80 ° C is recommended. Within the recommended range, there is a tendency for the rigidity and heat resistance of the obtained molded product to be significantly improved. It is also advantageous in terms of productivity. From the viewpoint of the β crystal content of a polypropylene-based molded product (injection molded product), a similar mold temperature range is recommended.

  In addition, the surface temperature (crystallization temperature) of the chill roll in the case of extrusion sheet molding is usually about 50 to 120 ° C, preferably about 70 to 110 ° C. When it is desired to increase the β crystal content of the polypropylene-based molded body (raw fabric sheet) as much as possible, about 110 to 130 ° C is preferable, and about 115 to 125 ° C is particularly preferable.

The β crystal content of the polypropylene resin molded product is selected from a range that does not impair the effects of the present invention, but is usually preferably about 40 to 90%, particularly preferably about 60 to 90%. .
The β crystal content was measured by differential scanning with a DSC apparatus (“Diamond DSC” manufactured by PerkinElmer Co., Ltd.) under a nitrogen atmosphere at a heating rate of 20 ° C./min. A calorimetric analysis is performed, and a value obtained from the heat of fusion of α crystal and β crystal of the DSC thermogram obtained at this time according to the following formula.
β crystal content (%) = 100 × H _β / (H _α + H _β )
[Wherein, H _β represents the heat of fusion of the β crystal, and H _α represents the heat of fusion of the α crystal. ].

<Secondary processed molded products>
As the secondary processing method according to the present invention, usual methods such as thermoforming such as vacuum forming and pressure forming are used.

  The thus obtained polypropylene resin molded product according to the present invention is excellent in rigidity and heat resistance, both of which can be used in the same fields as those in which conventionally known polypropylene resin molded products have been used. it can. Particularly, since the impact strength is high, it can be used as a molded product such as an automobile part, a mechanical optical part, a chemical industry part, or a home appliance part. Further, the obtained molded body is excellent in secondary workability, and can be used for conventionally known secondary processing molding such as vacuum molding and pressure forming, and in the field of conventionally known secondary processing molded products. Can be used.

  Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, strand transparency, measurement of polypropylene resin composition pellet diameter, crystallization completion time, handling during molding, rigidity (flexural modulus) of polypropylene resin molding, heat resistance (thermal deformation temperature), polypropylene The tensile elastic modulus of the resin molded body (extruded sheet) was determined by the following method.

(1) Strand transparency The molten polypropylene resin composition discharged from the dice was visually observed. When the amide compound is completely dissolved, it is transparent (o), and when an undissolved substance remains, it is cloudy (x).

(2) Measurement of pellet diameter (short diameter) About 10 sample pellets obtained in each Example and Comparative Example, 10 pellets were arbitrarily collected, the sample pellet diameter was measured with precision calipers, and the average value was determined as the pellet diameter (short Diameter). In addition, about the case where a pellet is flat, the diameter of the location with the smallest pellet diameter was measured as a short diameter.

(3) Crystallization completion time (Tend)
Using a differential scanning calorimeter (manufactured by Perkin Elmer, trade name “Diamond DSC”), a measurement sample (sample weight = 10 mg, pellets obtained in each example and comparative example) was heated at a rate of 100 ° C./min. The temperature was raised to 200 ° C. and held for 5 minutes after reaching that temperature. Next, the polypropylene resin was isothermally crystallized at a cooling rate of 300 ° C./minute and rapidly cooled to a measurement temperature of 135 ° C. of “crystallization end time”. The time when the sample was rapidly cooled and reached the measurement temperature was defined as the measurement start time of “crystallization end time”. From the obtained differential scanning calorimetry (DSC) chart, an extension line obtained by extending the long-time base line to the short-time side and a tangent line drawn at the point where the long-term curve slope of the exothermic peak is maximized. The time corresponding to the intersection point was recorded, and the same measurement and recording were repeated three times, and the average value was defined as “crystallization end time” (minutes). Note that the shorter the “crystallization end time”, the higher the nucleation ability.

(4) Handling at the time of molding About the sample pellet obtained by each Example and the comparative example, the adhesiveness to the hopper of a molding machine and the pellet biting to the screw were confirmed. The case where there was no adhesion or very weakness and the screwing of the molding machine was good was judged as ◯, and the case where the adhesion was strong or the screwing of the extruder was poor, was judged as x. In the case of a highly adherent material, pellets adhere to a hopper or the like, and in the case of poor biting into the screw, it is difficult to supply to the molding machine in step (iii) and cannot be used.

(5) Rigidity: Flexural modulus Measured using a polypropylene resin molded body at 25 ° C. in accordance with ASTM D790.

(6) Heat resistance: heat distortion temperature (HDT)
In accordance with JIS K 7207, the heat distortion temperature of the polypropylene resin molded body at a load of 4.6 kgf / cm ² was measured. The higher the heat distortion temperature, the better the heat resistance.

(7) Tensile modulus (sheet)
The tensile test piece was cut on a strip of 10 mm width in the resin flow direction (MD direction), and a polypropylene resin molded body at a measurement length of 50 mm and a tensile speed of 50 m / min at 25 ° C. in accordance with JIS K 7227. It measured using.
<Example 1>

  Polypropylene homopolymer (MPR = 10 g / 10 min (load 2160 g, temperature 230 ° C.), melting point: 168 ° C.) 100 parts by weight as a polypropylene resin, N, N′-dicyclohexyl-2,6-naphthalenedicarboxamide ( Product name: NG Star NU-100, manufactured by Shin Nippon Rika Co., Ltd., 0.3 parts by weight, and fatty acid calcium salt, calcium behenate (manufactured by Nitto Kasei Kogyo Co., Ltd., product name “CS-7”) 0.05 weight Part, and tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (trade name “IRGANOX1010” manufactured by Ciba Specialty Chemicals) as a polyolefin modifier. 05 parts by weight, tetrakis (2,4-di-tert-butyl Nyl) phosphite (Ciba Specialty Chemicals, trade name “IRGAFOS168”) 0.10 parts by weight, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanur Dry blend of 0.1 parts by weight of a 1: 2 (weight ratio) blend of acid and (2,4-di-tert-butylphenyl) phosphite (trade name, “Sianox 2777”, manufactured by Cytec Industries) did. The dry blend was melt-kneaded at a kneading temperature (resin temperature) of 300 ° C. with a twin-screw extruder (L / D = 45, manufactured by Technobel Co., Ltd., screw diameter 15 mm, die diameter 5 mm), and N, N ′ -Dicyclohexyl-2,6-naphthalenedicarboxamide was dissolved, and the extruded strand was cooled and cut with a pelletizer to prepare a polypropylene resin composition pellet. The pellets were produced so that the strands were passed through a 25 ° C. water tank, the take-up speed of the pelletizer was controlled, and the pellet diameter was 1.3 mm. Moreover, the said strand was transparent and the undissolved material was not recognized. The crystallization completion time of the obtained polypropylene resin composition pellets was measured, and the results are summarized in Table 1.

Next, the obtained polypropylene resin composition was injected under conditions of an injection temperature of 200 ° C. and a mold temperature of 40 ° C. to obtain a polypropylene resin molded body (test piece) of the present invention. The obtained test pieces were measured for flexural modulus and heat distortion temperature, and the results are summarized in Table 1.
<Example 2>

Except that the polypropylene resin composition pellet was produced so that the pellet diameter was 0.8 mm, the same operation as in Example 1 was performed to obtain a polypropylene resin composition pellet and a polypropylene resin molded body. The composition, production conditions, and results obtained are summarized in Table 1.
<Example 3>

A polypropylene resin composition pellet and a polypropylene resin molded article were obtained in the same manner as in Example 1 except that the polypropylene resin composition pellet was produced so that the pellet diameter was 1.7 mm. The composition, production conditions, and results obtained are summarized in Table 1.
<Example 4>

A polypropylene resin molded body was obtained by performing the same operation as in Example 1 except that the water temperature of the water tank required for strand cooling was changed to 55 ° C. The composition, production conditions, and results obtained are summarized in Table 1.
<Example 5>

A polypropylene resin molded article was obtained in the same manner as in Example 1 except that the amount of the amide compound was changed to 0.1 parts by weight and the kneading temperature (resin temperature) was changed to ° C. The composition, production conditions, and results obtained are summarized in Table 1.
<Example 6>

Except that the injection molding temperature was changed to 240 ° C., the same operation as in Example 1 was performed to obtain a polypropylene resin molded body. The composition, production conditions, and results obtained are summarized in Table 1.
<Example 7>

Except for using calcium stearate as the fatty acid calcium salt, the same operation as in Example 1 was performed to obtain a polypropylene resin molded body. The composition, production conditions, and results obtained are summarized in Table 1.
<Example 8>

Implementation was carried out except that 0.2 parts by weight of 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane was used as the amide compound. The same operation as in Example 1 was performed to obtain a polypropylene resin molded body. The composition, production conditions, and results obtained are summarized in Table 1.
<Comparative Example 1>

Except that the polypropylene resin composition pellets were produced so as to have a pellet diameter of 2.4 mm, the same operations as in Example 1 were performed to obtain polypropylene resin composition pellets and polypropylene resin molded bodies. The composition, production conditions, and results obtained are summarized in Table 1.
<Comparative example 2>

Except that the polypropylene resin composition pellets were produced so as to have a pellet diameter of 2.1 mm, the same operations as in Example 1 were performed to obtain polypropylene resin composition pellets and a polypropylene resin molded body. The composition, production conditions, and results obtained are summarized in Table 1.
<Comparative Example 3>

Except that the polypropylene resin composition pellet was produced so that the pellet diameter was 0.6 mm, the same operation as in Example 1 was performed to obtain a polypropylene resin composition pellet and a polypropylene resin molded body. The composition, production conditions, and results obtained are summarized in Table 1.
<Comparative example 4>

Except for melt-kneading at a kneading temperature (resin temperature) of 250 ° C., the same operation as in Example 1 was performed to obtain a polypropylene resin composition pellet and a polypropylene resin molded body. The composition, production conditions, and results obtained are summarized in Table 1.
<Comparative Example 5>

Except having changed the injection molding temperature to 270 degreeC, operation similar to Example 1 was performed and the polypropylene resin composition pellet and the polypropylene resin molding were obtained. The composition, production conditions, and results obtained are summarized in Table 1.
<Comparative Example 6>

Except not mix | blending an amide type compound, operation similar to Example 1 was performed and the polypropylene resin composition pellet and the polypropylene resin molding were obtained. The composition, production conditions, and results obtained are summarized in Table 1.

＜実施例９＞

<Example 9>

The polypropylene resin composition pellets obtained in Example 1 were melt kneaded at a resin temperature of 200 ° C. using a T-die uniaxial extruder (manufactured by Technobell, L / D = 28, screw diameter 25 mm). Then, it was melt-extruded at a screw rotation number of 20 rpm and cooled and solidified with a chill roll having a surface temperature of 120 ° C. to obtain a polypropylene resin molded body (extruded sheet) having a thickness of 300 μm. The composition, production conditions, and results obtained are summarized in Table 2.
<Example 10>

Except having used the polypropylene resin composition pellet obtained in Example 2, the same operation as in Example 9 was performed to obtain a polypropylene resin composition pellet and a polypropylene resin molded body. The composition, production conditions, and results obtained are summarized in Table 2.
<Comparative Example 7>

Except having used the polypropylene resin composition pellet obtained in Comparative Example 1, the same operation as in Example 9 was performed to obtain a polypropylene resin composition pellet and a polypropylene resin molded article. The composition, production conditions, and results obtained are summarized in Table 2.
<Comparative Example 8>

  Except having used the polypropylene resin composition pellet obtained in Comparative Example 2, the same operation as in Example 9 was performed to obtain a polypropylene resin composition pellet and a polypropylene resin molded article. The composition, production conditions, and results obtained are summarized in Table 2.

  By this invention, refinement | miniaturization of the amide compound in a polypropylene resin composition is achieved, As a result, the rigidity and heat resistance of the molded article which used this polypropylene resin composition as a raw material are attained. In addition, the tensile modulus of the extruded sheet is improved, and further, the secondary workability and the properties of the obtained secondary work product when producing a thermoformed product that is a secondary work product can be greatly improved. .

Claims (18)

A method for producing a polypropylene resin molded body comprising a step of molding a polypropylene resin composition containing needle-like crystals of at least one amide compound represented by the following general formula (1),
The shape of the polypropylene resin composition is a pellet shape having a minor axis of 0.5 mm or more and 2.0 mm or less, and needle crystals of the amide compound are present in the molten polypropylene resin at the time of molding. A method for producing a polypropylene-based resin molded product.
General formula (1):

[In the formula (1), R ¹ is a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 24 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 4 to 28 carbon atoms, or carbon. Represents an aromatic dicarboxylic acid residue having a number of 6 to 28, and R ² and R ³ are the same or different and are each a cycloalkyl group having 3 to 18 carbon atoms, the following general formulas (a) and (b): Represents a group represented by general formula (c) or general formula (d)

(In the formulas (a) to (d), R ⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or a phenyl group; ⁵ represents a linear or branched alkyl group having 1 to 12 carbon atoms, R ⁶ represents a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁷ represents a carbon number. 1-4 represents a linear or branched alkylene group). ] A polypropylene resin composition containing needle-like crystals of an amide compound, (i) heating an unkneaded raw material containing the polypropylene resin and the amide compound, and dissolving the amide compound in the molten polypropylene resin; ii) A composition obtained by a production method comprising a step of cooling the molten polypropylene resin composition obtained in the step (i) to precipitate acicular crystals of an amide compound,
The melting temperature of the polypropylene resin composition in the step (i) is in the range of T _dis or more and T _dis + 50 ° C. or less (T _dis represents the temperature at which the amide compound is dissolved in the polypropylene resin), and
In the said process (ii), the diameter of the strand at the time of cooling solidification is adjusted to the range of 0.5 mm or more and 2.0 mm or less, The manufacturing method of the polypropylene resin molding of Claim 1 characterized by the above-mentioned. In General Formula (1), R ¹ is a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 12 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 6 to 10 carbon atoms, or the number of carbon atoms Represents an aromatic dicarboxylic acid residue having 6 to 20 and R ² and R ³ are the same or different and each represents a cycloalkyl group having 3 to 12 carbon atoms, or a general formula (a), a general formula (b), a general formula The manufacturing method of the polypropylene resin molding of Claim 1 or 2 showing group represented by Formula (c) or General formula (d). In the general formula (1), R ¹ is a saturated aliphatic dicarboxylic acid residue having 4 to 8 carbon atoms, a saturated alicyclic dicarboxylic acid residue having 6 to 8 carbon atoms, or an aromatic dicarboxylic acid having 6 to 20 carbon atoms. A residue, wherein R ² and R ³ are the same or different and each is a cyclohexyl group or a phenyl group which may be substituted with one alkyl group having 1 to 4 carbon atoms. A method for producing a polypropylene resin molded article according to claim 1. In the general formula (1), R ¹ represents the general formula (e) or the general formula (f).

And R ² and R ³ are the same or different and each is a cyclohexyl group optionally substituted by one alkyl group having 1 to 4 carbon atoms. The manufacturing method of the polypropylene resin molding in any one of 1-4. The method for producing a polypropylene resin molded article according to any one of claims 1 to 5, wherein the amide compound is N, N'-dicyclohexyl-2,6-naphthalenedicarboxamide. The method for producing a polypropylene resin molded article according to any one of claims 1 to 6, wherein the amide compound is contained in an amount of 0.03 to 0.5 parts by weight with respect to 100 parts by weight of the polypropylene resin. The polypropylene resin according to any one of claims 1 to 7, wherein in the polypropylene resin composition, the amide compound and at least one compound selected from the group consisting of a saturated or unsaturated fatty acid metal salt coexist. Manufacturing method of resin molding. The method for producing a polypropylene resin molded product according to any one of claims 1 to 8, wherein the melt flow rate of the polypropylene resin at 230 ° C and a load of 2160 g is 0.5 to 60.0 g / 10 minutes. The crystallization completion time (Tend) in isothermal crystallization at 135 ° C. measured by a differential scanning calorimeter (DSC) of the polypropylene resin composition is 1.2 minutes or less. A method for producing a polypropylene resin molded body. A method of refining needle-like crystals of at least one amide compound represented by the following general formula (1) contained in a polypropylene resin composition,
(I) a step of heating an unkneaded raw material containing a polypropylene resin and an amide compound to dissolve the amide compound in the molten polypropylene resin, and (ii) a molten polypropylene system obtained in the step (i). A method comprising cooling the resin composition to precipitate amide compound needle crystals; and
In the step (ii), the diameter of the strand at the time of cooling and solidification is adjusted to a range of 0.5 mm or more and 2.0 mm or less.
General formula (1):

[In the formula (1), R ¹ is a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 24 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 4 to 28 carbon atoms, or carbon. Represents an aromatic dicarboxylic acid residue having a number of 6 to 28, and R ² and R ³ are the same or different and are each a cycloalkyl group having 3 to 18 carbon atoms, the following general formulas (a) and (b): Represents a group represented by general formula (c) or general formula (d)

(In the formulas (a) to (d), R ⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or a phenyl group; ⁵ represents a linear or branched alkyl group having 1 to 12 carbon atoms, R ⁶ represents a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁷ represents a carbon number. 1-4 represents a linear or branched alkylene group). ] In General Formula (1), R ¹ is a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 12 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 6 to 10 carbon atoms, or carbon Represents an aromatic dicarboxylic acid residue having a number of 6 to 20, and R ² and R ³ are the same or different and each represents a cycloalkyl group having 3 to 12 carbon atoms, or a general formula (a), a general formula (b), The method according to claim 11, which represents a group represented by the general formula (c) or the general formula (d). In the general formula (1), R ¹ is a saturated aliphatic dicarboxylic acid residue having 4 to 8 carbon atoms, a saturated alicyclic dicarboxylic acid residue having 6 to 8 carbon atoms, or an aromatic dicarboxylic acid having 6 to 20 carbon atoms. 13. The residue according to claim 11, wherein R ² and R ³ are the same or different and each is a cyclohexyl group or a phenyl group which may be substituted with one alkyl group having 1 to 4 carbon atoms. the method of. In General Formula (1), R ¹ is General Formula (e) or General Formula (f)

And R ² and R ³ are the same or different and each is a cyclohexyl group optionally substituted by one alkyl group having 1 to 4 carbon atoms. The method in any one of 11-13. The method according to any one of claims 13 to 14, wherein the amide compound is N, N'-dicyclohexyl-2,6-naphthalenedicarboxamide. (I) a step of heating an unkneaded raw material containing at least one amide compound represented by the following general formula (1), and dissolving the amide compound in the molten polypropylene resin;
(Ii) a step of cooling the molten polypropylene resin composition obtained in the step (i) to precipitate acicular crystals of an amide compound, and (iii) the amide obtained in the step (ii) A polypropylene resin composition in which needle crystals of the compound are precipitated is melted and molded in a temperature range of T _m + 10 ° C. or more and less than T _dis −10 ° C. (T _m represents the melting point of the polypropylene resin). A polypropylene resin molded body obtained by a method for producing a polypropylene resin molded body including a process,
The polypropylene resin composition containing acicular crystals of the amide compound obtained in the step (ii) has a pellet shape, and its minor axis is in the range of 0.5 mm or more and 2.0 mm or less. A polypropylene resin molded product.
General formula (1):

[In Formula (1), R ¹ is General Formula (e) or General Formula (f)

Wherein R ² and R ³ are the same or different and each represents a cyclohexyl group which may be substituted with one alkyl group having 1 to 4 carbon atoms] The polypropylene resin molded article according to claim 16, wherein the amide compound is N, N'-dicyclohexyl-2,6-naphthalenedicarboxamide. The secondary processing molded product obtained by further shape | molding the polypropylene resin molded object of Claim 16 or 17.