JP6928923B2 - Polyolefin resin molded product - Google Patents

Description

The present invention relates to a polyolefin-based resin molded body having improved mechanical properties such as rigidity and impact resistance in a well-balanced manner and a method for producing the same. A mechanical resin such as rigidity and impact resistance, which is characterized by blending a specific amide-based compound with an alloy-based polyolefin-based resin composed of a polyolefin-based resin molded body, mainly a polypropylene-based resin and a polybutene-1 resin. The present invention relates to a polyolefin-based resin molded body having improved properties in a well-balanced manner and a method for producing the same, a method for improving the mechanical properties of the polyolefin-based resin molded body, the molded body thereof, and a polyolefin-based resin composition used in the manufacturing method. ..

Polyolefin-based resins are currently the most widely used resins as inexpensive resins with excellent mechanical and optical properties. There are various types of polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene depending on their structure. Polyethylene and polypropylene have well-balanced properties and are widely used as general-purpose plastics. Polybutene and polymethyl Penten is mainly used for applications requiring heat resistance and the like. Further, in order to make the best use of each characteristic, a plurality of types of polyolefin resins are combined and often used as a so-called alloy resin.

As a typical alloy resin of such a polyolefin-based material, a general-purpose polypropylene-based resin and an alloy resin containing polybutene-1 resin as a main component are known. For example, improvement of impact resistance and improvement of film elongation by adding a polybutene-1 resin to a polypropylene resin have been studied and put into practical use (Patent Document 1). It is also known that by adding a polypropylene-based resin to a polybutene-1 resin having slow crystallinity, the crystallinity can be improved, and the heat resistance and mechanical properties can be improved. In addition, studies are underway to improve heat resistance and rigidity by adding highly crystalline polybutene-1 resin to polypropylene-based resin.

Japanese Unexamined Patent Publication No. 7-90140

On the other hand, in recent years, due to environmental problems, there is an increasing demand for recycling of used plastics in various applications and energy saving by reducing the weight of automatic parts, and replacement of other resins such as ABS with polyolefin resins is becoming more and more intense. It is attracting attention and is being actively considered. However, in such applications, it is difficult for individual polyolefin resins to cope with the performance, and the performance improvement effect of using the alloy resin as described above has attracted attention and is being studied. Further, recently, even such an alloy resin is required to be further improved in mechanical properties and the like.

The present invention relates to a polyolefin-based resin molded article having improved mechanical properties such as rigidity and impact resistance in a well-balanced manner and a method for producing the same, a method for improving the mechanical properties of the polyolefin-based resin molded article, and further, the molded article thereof. An object of the present invention is to provide a polyolefin-based resin composition which is a raw material used for production and improvement.

The applicant for this patent has also made it possible to improve the rigidity, heat resistance and impact resistance of the polypropylene resin in a well-balanced manner by blending a specific amide compound with the polypropylene resin in Japanese Patent Application No. 6-234929. In Ganpei 7-158473, it was reported that the crystallinity of the polybutene-1 resin can be improved by blending a specific amide compound with the polybutene-1 resin. Further, the present inventor or the applicant of the present patent, in Japanese Patent Application No. 2010-530906, molded a polypropylene-based resin containing the above-mentioned amide-based compound under specific molding conditions to form a molded product having a unique laminated structure. It was reported that the mechanical properties such as impact resistance and rigidity can be further improved in a well-balanced manner.

In view of the above situation, the present inventors have diligently studied to achieve the above-mentioned problems, and as a result, blend the above-mentioned amide compound with the polyolefin resin containing the polypropylene resin and the polybutene-1 resin as main components. As a result, it has been found that a polyolefin-based resin molded product containing components oriented in different directions can be easily obtained, and the present invention has been completed.

That is, the present invention relates to the following polyolefin-based resin molded article and a method for producing the same, a method for improving the mechanical properties of the polyolefin-based resin molded article, and the polyolefin-based resin composition provided for the molded article and the manufacturing method. It provides things.

[Item 1] A polyolefin-based resin molded product containing a polypropylene-based resin and a polybutene-1 resin as main components, and the two-color ratio of the absorption spectrum obtained by measuring the polarization infrared absorption spectrum of the polypropylene-based resin and the polybutene-1 resin. Polyolefin-based resin molded products in which the respective orientation functions calculated from are different from each other and have positive or negative values.

[Item 2] The molecular chain of the polypropylene-based resin is oriented in a direction perpendicular to the flow direction of the resin when molding, and the molecular chain of the polybutene-1 resin is oriented in a direction parallel to the flow direction of the resin when molding. Item 2. The polyolefin-based resin molded article according to [Item 1], which is oriented.

［式中、ｎは、２〜６の整数を表す。Ｒ^１は、炭素数２〜１８の飽和若しくは不飽和の脂肪族ポリカルボン酸残基、炭素数３〜１８の脂環族ポリカルボン酸残基又は炭素数６〜１８の芳香族ポリカルボン酸残基を表す。２〜６個のＲ^２は、同一又は異なって、それぞれ、炭素数５〜３０の飽和若しくは不飽和の脂肪族アミン残基、炭素数５〜３０の脂環族アミン残基又は炭素数６〜３０の芳香族アミン残基を表す。］
一般式（２）

［式中、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、同一又は異なって、それぞれ、水素原子、炭素数１〜２０のアルキル基、炭素数５〜２０の置換基を有してもよいシクロアルキル基、又は炭素数６〜２０の置換基を有してもよいアリール基を表す。なお、Ｒ^３とＲ^４、及びＲ^５とＲ^６は、それぞれ同時に水素原子を表すことはない。また、Ｒ^３とＲ^４と、又はＲ^５とＲ^６とが、それぞれ、互いに結合してアルキレン基を形成してもよい。］ [Item 3] From the group consisting of (A) polypropylene-based resin, (B) polybutene-1 resin, and (C) amide-based compound represented by the following general formula (1) and amide-based compound represented by the general formula (2). A polyolefin-based resin molded product containing at least one selected amide-based compound.
General formula (1)

[In the formula, n represents an integer of 2 to 6. R ¹ is a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 18 carbon atoms, an alicyclic polycarboxylic acid residue having 3 to 18 carbon atoms, or an aromatic polycarboxylic acid residue having 6 to 18 carbon atoms. Represents a group. 2-6 ^{R 2} are the same or different, respectively, saturated or unsaturated aliphatic amine residue having 5 to 30 carbon atoms, 6 to alicyclic amine residue or carbon atoms of 5 to 30 carbon atoms Represents 30 aromatic amine residues. ]
General formula (2)

[In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ may have the same or different hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a substituent having 5 to 20 carbon atoms, respectively. Represents a cycloalkyl group or an aryl group which may have a substituent having 6 to 20 carbon atoms. Note that R ³ and R ⁴ and R ⁵ and R ⁶ do not represent hydrogen atoms at the same time, respectively. Further, R ³ and R ⁴ or R ⁵ and R ⁶ may be bonded to each other to form an alkylene group. ]

[Item 4] The component (C) is an integer of 2 to 3 in n in the general formula (1), R ¹ is an aromatic polycarboxylic acid residue having 6 to 12 carbon atoms, and 2 to 3 R ² are. Item 3. The polyolefin-based resin molded product according to [Item 3], which is the same or different, and is an amide-based compound represented by a saturated alicyclic amine residue having 6 to 10 carbon atoms, respectively.

[Item 5] The polyolefin-based resin molded article according to [Item 3] or [Item 4], wherein the amide compound of the component (C) is an amide compound that forms β crystals with respect to a polypropylene resin.

[Item 6] The content of the component (C) is 0.001 to 5 parts by weight with respect to a total of 100 parts by weight of the contents of the component (A) and the component (B). Item 5. The polyolefin-based resin molded product according to any one of Items 5].

[Item 7] Any of [Item 3] to [Item 6], wherein the ratio of the component (A) to the component (B) is in the range of (A) component / (B) component = 30/70 to 70/30. The polyolefin-based resin molded article described in Crab.

[Item 8] The polyolefin-based resin molding according to [Item 7], wherein the ratio of the component (A) to the component (B) is in the range of (A) component / (B) component = 40/60 to 60/40. body.

［式中、ｎは、２〜６の整数を表す。Ｒ^１は、炭素数２〜１８の飽和若しくは不飽和の脂肪族ポリカルボン酸残基、炭素数３〜１８の脂環族ポリカルボン酸残基又は炭素数６〜１８の芳香族ポリカルボン酸残基を表す。２〜６個のＲ^２は、同一又は異なって、それぞれ、炭素数５〜３０の飽和若しくは不飽和の脂肪族アミン残基、炭素数５〜３０の脂環族アミン残基又は炭素数６〜３０の芳香族アミン残基を表す。］
一般式（２）

［式中、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、同一又は異なって、それぞれ、水素原子、炭素数１〜２０のアルキル基、炭素数５〜２０の置換基を有してもよいシクロアルキル基、又は炭素数６〜２０の置換基を有してもよいアリール基を表す。なお、Ｒ^３とＲ^４、及びＲ^５とＲ^６は、それぞれ同時に水素原子を表すことはない。また、Ｒ^３とＲ^４と、又はＲ^５とＲ^６とが、それぞれ、互いに結合してアルキレン基を形成してもよい。］ [Item 9] (i) At least one selected from the group consisting of a polypropylene resin, a polybutene-1 resin, an amide compound represented by the following general formula (1), and an amide compound represented by the general formula (2). A step of heating the above-mentioned amide-based compound to dissolve at least one of the above-mentioned amide-based compounds to obtain a melted polyolefin-based resin composition.
(Ii) The step of cooling the melted polyolefin-based resin composition obtained in the step (i) to precipitate crystals of the amide-based compound, and (iii) the step of (iii) the cooled polyolefin-based resin of the step (ii). A polyolefin-based resin molded article having an excellent balance of rigidity and impact resistance, comprising a step of melting the composition in a temperature range above the melting point of the polyolefin-based resin and a temperature at which the amide-based compound does not melt by heating. Production method.
General formula (1)

[In the formula, n represents an integer of 2 to 6. R ¹ is a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 18 carbon atoms, an alicyclic polycarboxylic acid residue having 3 to 18 carbon atoms, or an aromatic polycarboxylic acid residue having 6 to 18 carbon atoms. Represents a group. 2-6 ^{R 2} are the same or different, respectively, saturated or unsaturated aliphatic amine residue having 5 to 30 carbon atoms, 6 to alicyclic amine residue or carbon atoms of 5 to 30 carbon atoms Represents 30 aromatic amine residues. ]
General formula (2)

[In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ may have the same or different hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a substituent having 5 to 20 carbon atoms, respectively. Represents a cycloalkyl group or an aryl group which may have a substituent having 6 to 20 carbon atoms. Note that R ³ and R ⁴ and R ⁵ and R ⁶ do not represent hydrogen atoms at the same time, respectively. Further, R ³ and R ⁴ or R ⁵ and R ⁶ may be bonded to each other to form an alkylene group. ]

[Item 10] The production method according to [Item 9], wherein the crystals of the amide compound precipitated in the step (ii) are fine needle-like crystals.

[Item 11] The orientation functions calculated from the two-color ratio of the absorption spectra obtained by measuring the polarization infrared absorption spectra of the polypropylene-based resin and the polybutene-1 resin, which are the main components of the polyolefin-based resin molded product, are different from each other. A method for improving the rigidity and impact resistance of a polyolefin resin molded product in a well-balanced manner, which is characterized by having a positive or negative value.

［式中、ｎは、２〜６の整数を表す。Ｒ^１は、炭素数２〜１８の飽和若しくは不飽和の脂肪族ポリカルボン酸残基、炭素数３〜１８の脂環族ポリカルボン酸残基又は炭素数６〜１８の芳香族ポリカルボン酸残基を表す。２〜６個のＲ^２は、同一又は異なって、それぞれ、炭素数５〜３０の飽和若しくは不飽和の脂肪族アミン残基、炭素数５〜３０の脂環族アミン残基又は炭素数６〜３０の芳香族アミン残基を表す。］
一般式（２）

［式中、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、同一又は異なって、それぞれ、水素原子、炭素数１〜２０のアルキル基、炭素数５〜２０の置換基を有してもよいシクロアルキル基、又は炭素数６〜２０の置換基を有してもよいアリール基を表す。なお、Ｒ^３とＲ^４、及びＲ^５とＲ^６は、それぞれ同時に水素原子を表すことはない。また、Ｒ^３とＲ^４と、又はＲ^５とＲ^６とが、それぞれ、互いに結合してアルキレン基を形成してもよい。］ [Item 12] From the group consisting of (A) polypropylene-based resin, (B) polybutene-1 resin, and (C) amide-based compound represented by the following general formula (1) and amide-based compound represented by the general formula (2). A polyolefin-based resin composition used for obtaining a polyolefin-based resin molded product having an excellent balance of rigidity and impact resistance, which comprises at least one selected amide-based compound.
General formula (1)

[In the formula, n represents an integer of 2 to 6. R ¹ is a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 18 carbon atoms, an alicyclic polycarboxylic acid residue having 3 to 18 carbon atoms, or an aromatic polycarboxylic acid residue having 6 to 18 carbon atoms. Represents a group. 2-6 ^{R 2} are the same or different, respectively, saturated or unsaturated aliphatic amine residue having 5 to 30 carbon atoms, 6 to alicyclic amine residue or carbon atoms of 5 to 30 carbon atoms Represents 30 aromatic amine residues. ]
General formula (2)

[In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ may have the same or different hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a substituent having 5 to 20 carbon atoms, respectively. Represents a cycloalkyl group or an aryl group which may have a substituent having 6 to 20 carbon atoms. Note that R ³ and R ⁴ and R ⁵ and R ⁶ do not represent hydrogen atoms at the same time, respectively. Further, R ³ and R ⁴ or R ⁵ and R ⁶ may be bonded to each other to form an alkylene group. ]

By orienting the molecular chains of the polypropylene-based resin and the polybutene-1 resin in different directions, it is possible to improve the mechanical properties such as impact resistance and rigidity of the polyolefin-based resin molded product in a well-balanced manner.

Further, by blending a specific amide-based compound with a polyolefin-based resin containing polypropylene-based resin and polybutene-1 resin as main components, a polyolefin-based resin molded product containing components oriented in different directions can be easily obtained. As a result, the mechanical properties such as impact resistance and rigidity of the resulting polyolefin resin molded product can be improved in a well-balanced manner.

FIG. 1 is an X-ray diffraction pattern of the sheet obtained in Example 1. FIG. 2 is an X-ray diffraction pattern of the sheet obtained in Comparative Example 1.

<Polyolefin-based resin molded product>
The polyolefin-based resin molded product of the present invention is a polyolefin-based resin molded product containing polypropylene-based resin and polybutene-1 resin as main components, and all or one of the molecular chains of polypropylene-based resin and polybutene-1 resin. The portions are characterized in that they are oriented in different directions from each other, and by having such a structure, it is possible to improve the rigidity and impact resistance of the obtained polyolefin resin molded product in a well-balanced manner. ..
The description of the polyolefin-based resin molded product is also a description of the polyolefin-based resin composition of the present invention, and also a description of a method for improving the rigidity and impact resistance of the polyolefin-based resin molded product of the present invention in a well-balanced manner.

The "main component" means that the total ratio of the polypropylene resin and the polybutene-1 resin in the polyolefin resin molded product is 60% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more. It means that there is.

The above "all or part" means that 50% or more, preferably 70% or more, more preferably 80% or more of the total molecular chains in the polypropylene resin and the polybutene-1 resin are oriented in the above direction. Means.

The ratio of the polypropylene-based resin to the polybutene-1 resin contained in the polyolefin-based resin molded body varies depending on the use thereof, and is not particularly limited as long as the effect of the present invention is exhibited, but the polypropylene-based resin is preferable. / The ratio (weight ratio) of the polybutene-1 resin is in the range of 30/70 to 70 to 30, more preferably in the range of 40/60 to 60/40, and particularly preferably in the range of 40/60 to 50/50. It is recommended that there be.

Polypropylene resin (component (A))
The polypropylene-based resin contained in the polyolefin-based resin molded product of the present invention is a polymer containing propylene as a main constituent component, and is, for example, a polypropylene homopolymer, propylene mainly composed of propylene, and other α-olefins ( Random copolymer with preferably 2 or 4 to 20 carbon atoms, particularly preferably α-olefin having 2 or 4 to 8 carbon atoms, propylene mainly composed of propylene and other α-olefins (preferably 2 carbon atoms). Alternatively, a block copolymer with 4 to 20, particularly preferably an α-olefin having 2 or 4 to 8 carbon atoms, or a propylene-ethylene-diene multi-component copolymer mainly composed of propylene (5-ethylidene-2 as a diene). -Norbornene, 5-methylene-2-norbornene, 1,4-hexadien, etc.), a copolymer of propylene-based propylene and a small amount of styrene, comonomer such as maleic anhydride or (meth) acrylic acid, or Examples thereof include a blend polymer of the polypropylene-based resin and a small amount of thermoplastic resin.

The above-mentioned "mainly propylene" means that the propylene unit is present in the copolymer at least 50% by weight or more, preferably 70% by weight or more and less than 100% by weight, more preferably 80% by weight. More than 100% by weight is recommended.

More specifically, it is a polypropylene homopolymer or a copolymer mainly composed of propylene, and is a propylene-ethylene random copolymer, a propylene-ethylene block copolymer, a propylene-ethylene-butene-1 random copolymer, and a propylene-ethylene-butene-. 1-block copolymer, propylene-ethylene-1-pentene random copolymer, propylene-ethylene-1-pentene block copolymer, propylene-hexene-1 random copolymer, propylene-hexene-1 block copolymer, propylene-ethylene-hexene-1 random copolymer, Propylene-ethylene-4-methylpentene-1 random copolymer, propylene-ethylene-5-ethylidene-2-norbornene copolymer, propylene-ethylene-5-methylene-2-norbornene copolymer, propylene-ethylene-1,4-hexadien copolymer, Examples thereof include propylene-styrene copolymer, propylene-maleic anhydride copolymer, and propylene / (meth) acrylic acid copolymer. The above polypropylene resins can be used alone or in combination of two or more as appropriate.

Among these, polypropylene homopolymers, propylene-ethylene random copolymers mainly composed of propylene, and propylene-ethylene block copolymers are preferably recommended. The propylene unit in the copolymer is preferably 70% by weight or more and less than 100% by weight, more preferably 80% by weight or more and less than 100% by weight.

The polypropylene resin can be obtained by a conventionally known production method. As the production method, various known methods such as a slurry polymerization method using a hydrocarbon such as hexane and heptane as a solvent, a massive polymerization method using liquid propylene as a solvent, and a vapor phase method can be used. Further, as the catalyst used in such a production method, a commonly used Ziegler-Natta type catalyst, a transition metal compound (for example, a halide of titanium such as titanium trichloride and titanium tetrachloride) is used as a halogen such as magnesium chloride. Examples thereof include a catalyst system formed by combining a catalyst supported on a carrier containing magnesium oxide as a main component and an alkylaluminum compound (triethylaluminum, diethylaluminum chloride, etc.), a metallocene-based catalyst called a Kaminsky catalyst, and the like. ..

The melt flow rate of the polypropylene resin (hereinafter abbreviated as "MFR"; JIS K 6758-1981) is appropriately selected depending on the molding method and application to which it is applied, but is preferably 0.1 to 200 g / 10 minutes. More preferably, 0.3 to 150 g / 10 minutes, particularly 0.5 to 100 g / 10 minutes is recommended.

Polybutene-1 resin (component (B))
The polybutene-1 resin according to the present invention is a polymer containing butene-1 as a main constituent, and specifically, polybutene-1 homopolymer and butene-1-ethylene mainly composed of butene-1. Examples thereof include copolymers, butene-1-propylene copolymers, and blend polymers of the polybutene-1 resin with a small amount of thermoplastic resin or elastomer, such as polyethylene, polyisobutylene, and poly-4-methylpentene-1. Isotactics and syndiotactics are recommended as the stereoregularity.

The polybutene-1 resin can be obtained by a conventionally known production method. As the production method, various known methods such as a slurry polymerization method using a hydrocarbon such as hexane or heptane as a solvent can be used. Further, as the catalyst used in such a production method, not only a commonly used Ziegler-Natta type catalyst but also a transition metal compound (for example, a halide of titanium such as titanium trichloride and titanium tetrachloride) is used as magnesium chloride or the like. In addition to a catalyst system in which a catalyst supported on a carrier containing magnesium halide as a main component and an alkylaluminum compound (triethylaluminum, diethylaluminum chloride, etc.) are combined, a so-called Kaminsky catalyst can also be used.

The melt flow rate of the polybutene-1 resin (hereinafter abbreviated as "MFR"; JIS K7210 (190 ° C., 2.16 kgf)) is appropriately selected depending on the molding method to which it is applied, and is usually 0.01 to 50 g / 10. About minutes, preferably about 0.03 to 20 g / 10 minutes.

In addition to the polypropylene-based resin and polybutene-1 resin, which are the main components, the polyolefin-based resin molded body includes, for example, low-pressure polyethylene, medium-pressure polyethylene, high-pressure polyethylene, linear low-density polyethylene, and ethylene-propylene. Polyolefin-based resins exemplified by polymers, poly-4-methylpentene-1, and the like can be contained within the range in which the effects of the present invention are exhibited.

［式中、ｎは、２〜６の整数を表す。Ｒ^１は、炭素数２〜１８の飽和若しくは不飽和の脂肪族ポリカルボン酸残基、炭素数３〜１８の脂環族ポリカルボン酸残基又は炭素数６〜１８の芳香族ポリカルボン酸残基を表す。２〜６個のＲ^２は、同一又は異なって、それぞれ、炭素数５〜３０の飽和若しくは不飽和の脂肪族アミン残基、炭素数５〜３０の脂環族アミン残基又は炭素数６〜３０の芳香族アミン残基を表す。］
一般式（２）

［式中、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、同一又は異なって、それぞれ、水素原子、炭素数１〜２０のアルキル基、炭素数５〜２０の置換基を有してもよいシクロアルキル基、又は炭素数６〜２０の置換基を有してもよいアリール基を表す。なお、Ｒ^３とＲ^４、及びＲ^５とＲ^６は、それぞれ同時に水素原子を表すことはない。また、Ｒ^３とＲ^４と、又はＲ^５とＲ^６とが、それぞれ、互いに結合してアルキレン基を形成してもよい。］ Amide compound (component (C))
The amide compound of the present invention is at least one amide compound selected from the group consisting of the amide compound represented by the following general formula (1) and the amide compound represented by the general formula (2). Is recommended.
General formula (1)

[In the formula, n represents an integer of 2 to 6. R ¹ is a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 18 carbon atoms, an alicyclic polycarboxylic acid residue having 3 to 18 carbon atoms, or an aromatic polycarboxylic acid residue having 6 to 18 carbon atoms. Represents a group. 2-6 ^{R 2} are the same or different, respectively, saturated or unsaturated aliphatic amine residue having 5 to 30 carbon atoms, 6 to alicyclic amine residue or carbon atoms of 5 to 30 carbon atoms Represents 30 aromatic amine residues. ]
General formula (2)

[In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ may have the same or different hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a substituent having 5 to 20 carbon atoms, respectively. Represents a cycloalkyl group or an aryl group which may have a substituent having 6 to 20 carbon atoms. Note that R ³ and R ⁴ and R ⁵ and R ⁶ do not represent hydrogen atoms at the same time, respectively. Further, R ³ and R ⁴ or R ⁵ and R ⁶ may be bonded to each other to form an alkylene group. ]

Preferably, n in the general formula (1) is an integer of 2 to 4, R ¹ is a saturated aliphatic polycarboxylic acid residue having 3 to 6 carbon atoms, and an alicyclic polycarboxylic acid residue having 5 to 7 carbon atoms. group, aromatic polycarboxylic acid residue having 6 to 12 carbon atoms, and 2-4 R ^2, same or different, respectively, saturated aliphatic having 6 to 10 carbon atoms, alicyclic or aromatic Amide compounds represented by amine residues are recommended.

The "polycarboxylic acid residue" means a group remaining after removing all the carboxyl groups from the polycarboxylic acid, and the number of carbon atoms thereof represents the total number of carbon atoms of the polycarboxylic acid residue. The polycarboxylic acid is a carboxylic acid having a valence of 2 to 6, and the valence thereof is the same as that of n in the general formula (1). Further, the "amine residue" means a group remaining except for all amino groups, and the carbon number thereof represents the total carbon number of the amine residue.

More preferably, n in the general formula (1) is an integer of 2 to 3, R ¹ is an aromatic polycarboxylic acid residue having 6 to 12 carbon atoms, and 2 to 3 R ² are the same or different. An amide compound represented by a saturated alicyclic amine residue having 6 to 10 carbon atoms is recommended.

［式中、ｐは、１〜８の整数を表す。ｑは、０〜２の整数を表す。Ｒ^７は、炭素数１〜４のアルキル基を表す。］ As ^{a preferable combination of R 1} and R ^2, a combination in which R ¹ is the formula (a) to the formula (d) and R ² is the formula (e) is recommended in order to exert the effect of the present invention. .. Further, a combination in which R ¹ is the formula (a) to the formula (c) and R ² is the formula (e) is particularly preferable.

[In the formula, p represents an integer of 1-8. q represents an integer of 0 to 2. R ⁷ represents an alkyl group having 1 to 4 carbon atoms. ]

Specific examples of the amide compound represented by the general formula (1) include N, N'-dicyclohexyl-1,4-cyclohexanedicarboxyamide and N, N'-di (2-methylcyclohexyl) -1. , 4-Cyclohexanedicarboxyamide, N, N'-di (4-methylcyclohexyl) -1,4-cyclohexanedicarboxyamide, N, N'-di (2,3-dimethylcyclohexyl) -1,4-cyclohexane Dicarboxyamide, N, N'-dicyclohexyl-terephthalamide, N, N'-di (2-methylcyclohexyl) -terephthalamide, N, N'-di (3-methylcyclohexyl) -terephthalamide, N, N' -Di (4-methylcyclohexyl) -terephthalamide, N, N'-di (2,3-dimethylcyclohexyl) -terephthalamide, N, N'-di (cyclooctyl) -terephthalamide, N, N'-dicyclohexyl -2,6-naphthalenedicarboxyamide, N, N'-dicyclopentyl-2,6-naphthalenedicarboxyamide, N, N'-dicyclooctyl-2,6-naphthalenedicarboxyamide, N, N'- Dicyclododecyl-2,6-naphthalenedicarboxyamide, N, N'-di (2-methylcyclohexyl) -2,6-naphthalenedicarboxyamide, N, N'-di (3-methylcyclohexyl) -2, 6-naphthalenedicarboxyamide, N, N'-di (4-methylcyclohexyl) -2,6-naphthalenedicarboxyamide, N, N'-di (2,3-dimethylcyclohexyl) -2,6-naphthalenedi Carboxamide, N, N'-di (cyclooctyl) -2,6-naphthalenedicarboxyamide, N, N'-dicyclohexyl-2,7-naphthalenedicarboxyamide, N, N'-di (2,3-di) Dicyclohexyl) -2,7-naphthalenedicarboxyamide, N, N'-dicyclohexyl-4,4'-biphenyldicarboxyamide, N, N'-dicyclopentyl-4,4'-biphenyldicarboxyamide, N, N ´-Dicyclooctyl-4,4′-biphenyldicarboxyamide, N, N′-dicyclododecyl-4,4′-biphenyldicarboxyamide, N, N′-di (2-methylcyclohexyl) -4, 4'-biphenyldicarboxyamide, N, N'-di (3-methylcyclohexyl) -4,4'-biphenyldicarboxyamide, N, N'-di (4-methylcyclo) Hexil) -4,4'-biphenyldicarboxyamide, N, N'-di (2,3-dimethylcyclohexyl) -4,4'-biphenyldicarboxyamide, N, N'-di (cyclooctyl) -4 , 4'-biphenyldicarboxyamide, N, N'-dicyclohexyl-2,2'-biphenyldicarboxyamide, N, N'-diphenylhexanediamide, N, N'-bis (p-methylphenyl) hexanediamide, N, N'-bis (p-ethylphenyl) hexanediamide, N, N'-bis (4-cyclohexylphenyl) hexanediamide, adipate dianilide, suberic acid dianilide, trimesic acid tri (cyclohexylamide), trimesic acid tri- t-Butyl amide, Trimethic acid tri (2-methylcyclohexylamide), Trimethic acid tri (4-methylcyclohexylamide), Trimethic acid tri (2-ethylcyclohexylamide), Trimethicate tri (4-ethylcyclohexylamide), Trimethic acid Tri (4-n-propylcyclohexylamide), trimesic acid tri (4-isopropylcyclohexylamide), trimesic acid tri (4-n-butylcyclohexylamide), trimesic acid tri (4-isobutylcyclohexylamide), trimesic acid tri (4-isobutylcyclohexylamide) 4-t-Butylcyclohexylamide), trimesic acid tri (4-sec-butylcyclohexylamide), trimesic acid tri (2,3-dimethylcyclohexylamide), trimesic acid tri (2,4-dimethylcyclohexylamide), trimesic acid Tri (benzylamide), Trimethicate tri (cycloheptyl), Trimethicate tri (3-methylcyclohexylamide), Trimethicate tri (cyclododecylamide), Trimethicate tri (1,1,3,3-tetramethylbutyl) Amide), trimesic acid tri (S (+)-1-cyclohexylethylamide), trimesic acid tri (R (+)-1-cyclohexylethylamide), trimesic acid tri (cyclooctylamide) and the like are exemplified.

Among them, N, N'-dicyclohexyl-terephthalamide, N, N'-di (2-methylcyclohexyl) -terephthalamide, N, N'-di (3-methylcyclohexyl) -terephthalamide, N, N'- Di (4-methylcyclohexyl) -terephthalamide, N, N'-di (2,3-dimethylcyclohexyl) -terephthalamide, N, N'-di (cyclooctyl) -terephthalamide, N, N'-dicyclohexyl- 2,6-naphthalenedicarboxyamide, N, N'-di (2-methylcyclohexyl) -2,6-naphthalenedicarboxyamide, N, N'-di (3-methylcyclohexyl) -2,6-naphthalenedi Carboxamide, N, N'-di (4-methylcyclohexyl) -2,6-naphthalenedicarboxyamide, N, N'-di (2,3-dimethylcyclohexyl) -2,6-naphthalenedicarboxyamide, N , N'-di (cyclooctyl) -2,6-naphthalenedicarboxyamide, N, N'-dicyclohexyl-4,4'-biphenyldicarboxyamide, N, N'-di (2-methylcyclohexyl) -4 , 4'-biphenyldicarboxyamide, N, N'-di (3-methylcyclohexyl) -4,4'-biphenyldicarboxyamide, N, N'-di (4-methylcyclohexyl) -4,4'- Biphenyldicarboxyamide, N, N'-di (2,3-dimethylcyclohexyl) -4,4'-biphenyldicarboxyamide, N, N'-di (cyclooctyl) -4,4'-biphenyldicarboxyamide Trimesic acid tri (cyclohexylamide), trimesic acid tri (2-methylcyclohexylamide), trimesic acid tri (3-methylcyclohexylamide), trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (2,3-) Dimethylcyclohexylamide) and trimethicate tri (cyclooctylamide) are recommended because they are particularly superior in the effects of the present invention.

Further, as the alkyl group of the general formula (2), an alkyl group having 1 to 20 carbon atoms, particularly an alkyl group having 1 to 18 carbon atoms is preferable. Specifically, there are a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, an octadecyl group and the like. As the cycloalkyl group, a cycloalkyl group having 5 to 20 carbon atoms, particularly a cycloalkyl group having 5 to 14 carbon atoms is preferable. Specifically, there are a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a 4-t-butylcyclohexyl group, a 2,4-di-t-butylcyclohexyl group, a 1-adamantyl group and the like. As the aryl group, an aryl group having 6 to 20 carbon atoms, particularly an aryl group having 6 to 14 carbon atoms is recommended. Specifically, there are a phenyl group, a 1-naphthyl group, a 4-t-butylphenyl group, a 2,4-di (t-butyl) phenyl group and the like. When R ³ and R ⁴ or R ⁵ and R ⁶ are bonded to each other at the ω-end to jointly represent an alkylene group, the nitrogen atom to which ^{R 3} and R ⁴ or R ⁵ and R ^{6 are bonded.} The nitrogen-containing ring has a ring size of 5 to 8, that is, ^{an alkylene group derived from R 3} and R ⁴ or an alkylene group derived from R ⁵ and R ⁶ is carbon. Those of the number 4 to 7 are preferable. Specifically, pyrrolidine, piperidine, hexamethyleneimine and the like can be exemplified.

Specific examples of the amide compound represented by the general formula (2) include 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [ 5.5] Undecane, 3,9-bis {4- [N- (4-t-butylcyclohexyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3, 9-bis {4- [N- (2,4-di-t-butylcyclohexyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis { 4- [N- (1-adamantyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (N-phenylcarbamoyl) phenyl]- 2,4,8,10-Tetraoxaspiro [5.5] undecane, 3,9-bis {4- [N- (4-t-butylphenyl) carbamoyl] phenyl} -2,4,8,10- Tetraoxaspiro [5.5] undecane, 3,9-bis {4- [N- (2,4-di-t-butylphenyl) carbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [ 5.5] Undecane, 3,9-bis {4- [N- (1-naphthyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-butylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-hexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-dodecylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [ 5.5] Undecane, 3,9-bis [4- (Nn-octadecylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] Undecane, 3,9-bis (4) -Carbamoylphenyl) -2,4,8,10-Tetraoxaspiro [5.5] undecane, 3,9-bis [4- (N, N-dicyclohexylcarbamoyl) phenyl] -2,4,8,10- Tetraoxaspiro [5.5] undecane, 3,9-bis [4- (N, N-diphenylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9 -Bis [4- (Nn-butyl-N-cyclohexy) Lucarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-butyl-N-phenylcarbamoyl) phenyl] -2,4 8,10-Tetraoxaspiro [5.5] undecane, 3,9-bis [4- (1-pyrrolidinylcarbonyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane , 3,9-bis [4- (1-piperidinylcarbonyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, and the like.

Among them, 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis {4- [N-( 1-adamantyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (N-phenylcarbamoyl) phenyl] -2,4,8, 10-Tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-octadecylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3 , 9-Bis (4-carbamoylphenyl) -2,4,8,10-tetraoxaspiro [5.5] undecane is recommended because it is particularly advantageous in the effects of the present invention.

Further, among the above-mentioned amide compounds, the amide compound that forms β crystals with respect to the polypropylene resin contains a plurality of components whose molecular chains are oriented in different directions, which is a feature of the present invention. It is superior in forming a peculiar structure of a polyolefin-based resin molded product characterized by the above, and is particularly recommended.

The content of the amide compound is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 1 part by weight, based on 100 parts by weight of the total content of the polypropylene resin and the polybutene-1 resin. In particular, 0.01 to 0.7 parts by weight is recommended. In this range, the effect of the present invention is particularly superior.

When the polyolefin-based resin composition is used as a masterbatch by using the above-mentioned amide-based compound in a high content, it is useful even if it is used beyond the above-mentioned range. Even in that case, in order to obtain the molded article of the present invention, it is recommended to dilute the masterbatch so as to be within the range of the above-mentioned content of the amide compound.

Further, as a method of making a master batch as described above, a method of making a master batch of a mixture of a polypropylene resin and a polybutene-1 resin, a method of making a master batch of a polypropylene resin alone, and then mixing with a polybutene-1 resin, There is a method of making a master batch of the polybutene-1 resin alone and then mixing it with a polypropylene-based resin, and any method may be used as long as it is within the range in which the effect of the present invention is exhibited.

The polyolefin-based resin molded product according to the present invention may further contain a conventionally known modifier for polyolefins within a range that exhibits the effects of the present invention, as appropriate according to the purpose of use and its use.

Examples of such modifiers for fatty acids include various additives described in "Handbook of Additives on Positive List" (October 1990) edited by the Sanitary Council for Fatty Acids, etc., and more specifically, they are stable. Agents (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), antioxidants (phenolic compounds, phosphite ester compounds, sulfur) (Compounds, etc.), surfactants, lubricants (aliphatic hydrocarbons such as paraffin and wax, higher fatty acids with 8 to 22 carbon atoms, higher fatty acid metal (Al, Ca, Mg, Zn) salts with 8 to 22 carbon atoms, etc. Fatty acid with 8 to 18 carbon atoms, aliphatic alcohol with 8 to 22 carbon atoms, polyglycol, ester of higher fatty acid with 4 to 22 carbon atoms and aliphatic monovalent alcohol with 4 to 18 carbon atoms, 8 to 22 carbon atoms Higher fatty acid amide, silicone oil, rosin derivative, etc.), filler (talc, hydrotalcite, mica, zeolite, pearlite, diatomaceous soil, calcium carbonate, glass fiber, etc.), neutralizing agent, antioxidant, foaming agent, foaming Auxiliary agent, polymer additive, fluorescent whitening agent, plasticizer, molecular weight modifier (radical generator), cross-linking agent, cross-linking accelerator, antistatic agent, antifogging agent, polymer alloy component (block SBR or random SBR and them) Various modifications such as hydrides and other rubbers and polystyrenes), flame retardants, dispersants, organic / inorganic pigments, dyes, processing aids, antiblocking agents, organic crystal nucleating agents other than the above amide compounds, etc. Agents are exemplified. These modifiers can be used alone or in combination of two or more as appropriate.

Structure of Polyolefin-Based Resin Molded Body The polyolefin-based resin molded product according to the present invention is characterized by containing a plurality of components whose molecular chains are oriented in different directions from each other. That is, the molecular chains of the polypropylene-based resin and the polybutene-1 resin, which are the main components of the alloy resin, are oriented in different directions.

The orientation direction of the molecular chain can be easily confirmed from the diffraction pattern obtained by the wide-angle X-ray diffraction measurement. Specifically, using a general-purpose wide-angle X-ray diffractometer, the test piece cut out from the molded body is subjected to throughh view (flow direction (MD direction) -direction perpendicular to the flow direction (TD direction) plane) and From the direction in which the characteristic diffraction peaks of each resin on the X-ray diffraction pattern obtained by the transmission method are concentrated by irradiating X-rays from the edge view (MD direction-thickness direction (ND direction) plane) at room temperature. The direction in which the molecular chains of each resin are oriented can be confirmed.

Further, the strength of each orientation can be easily obtained by the orientation function calculated from the infrared two-color ratio. Specifically, the polarization infrared absorption spectrum of the test piece cut out from the molded body was measured using a general-purpose infrared spectroscope incorporating a polarizer, and the characteristic absorption band for each resin on the obtained chart. From the intensity of, the two-color ratio D (1 formula) of the absorption spectrum was obtained using the following (1 formula), and the orientation function F was calculated from the obtained D value using the following (2 formula). As the characteristic absorption band, the polypropylene-based resin is assigned to ^{the absorption band of 998 cm -1} which is attributed to CC expansion and contraction, and the polybutene-1 resin is _{attributed to CH 2-} CH ₃ variable vibration. The absorption band of 924 cm ^-1 was defined as each characteristic absorption band. The coefficient c in (Equation 2) was calculated as c = 1 in the case of polypropylene-based resin and c = -2 in the case of polybutene-1 resin.

<Manufacturing method of polyolefin resin molded product>
The method for producing a polyolefin-based resin molded product of the present invention comprises, for example, the following steps (i) to (iii), and the effects of the present invention can be more effectively achieved by satisfying such conditions. It is possible to obtain a molded product that can be used.
The description of the production method described later is also a description of the method for molding the polyolefin-based resin composition according to the present invention.

Step (i): A amide-based compound is completely added to a polypropylene-based resin, a polybutene-1 resin, or a polyolefin-based resin containing a mixture of a polypropylene-based resin and a polybutene-1 resin as a main component, and the resin in which the amide-based compound is dissolved is completely dissolved. A step of obtaining a melted polyolefin resin composition by melting at a temperature higher than the melting temperature.
Step (ii); A step of cooling the melted polyolefin resin composition to a temperature below the temperature at which crystals of the amide compound are precipitated.
Step (iii); After melting the cooled polyolefin resin composition in a temperature range equal to or higher than the melting point of the polyolefin resin and lower than the dissolution temperature of the amide compound in the polypropylene resin, the temperature is usually 125 ° C. or lower, preferably 20 to 20 to. A step of molding in a temperature range of 125 ° C., more preferably 50 to 120 ° C., particularly preferably 80 to 120 ° C.

When the resin in the step (i) is a polypropylene-based resin or a polybutene-1 resin, the polypropylene-based resin may be a polybutene-1 resin, and the polybutene-1 resin may be a polypropylene-based resin, which may be melt-mixed in the step (i). , It may be melt-mixed in the step (iii).

In the step (i), it is important to dissolve the amide compound (preferably at least one amide compound represented by the general formula (1) or the general formula (2)) in the polyolefin resin. Yes, it can be done using a known device. The step (i) comprises an operation of dissolving the amide compound and an operation of putting the polyolefin resin composition in a molten state.

"The amide compound is dissolved by heating" means that substantially the entire amount of the amide compound is dissolved within the scope of the present specification and claims. In this operation, if the amide compound is not sufficiently dissolved, the effect of the present invention may not be sufficiently exhibited. When the amide compound is melted by heating, when the melted polyolefin resin composition is visually observed, the undissolved amide compound is substantially not observed, and the melted polyolefin resin composition is transparent. be. By this method, it can be confirmed that substantially the entire amount is dissolved.

The "melting point of the polyolefin resin" in the step (ii) means the temperature at which all the resins contained in the polyolefin resin composition are completely melted, and when measured by a differential scanning calorimeter (DSC), for example. This is the temperature corresponding to the melting peak temperature that appears on the hottest side of the chart.

Specifically, the step (i) will be described. For example, (1) a mixer such as a Henschel mixer, a ribbon blender, a drum mixer, or the like, (1) the polyolefin-based resin, the amide-based compound, and, if necessary, the modifier for polyolefin. After dry-blending with Then, the amide-based compound is dissolved in the polypropylene-based resin at a predetermined resin temperature, the melted state is maintained as it is, and the process proceeds to the next step (ii), and (2) the predetermined resin temperature using a melt-kneader. An amide compound and, if necessary, a polyolefin modifier, if necessary, are directly added to the melted polyolefin resin in the above in a solid form or a liquid form to dissolve the resin, and the melted state is maintained as it is, and the next step is performed. Method of shifting to (ii), (3) The polyolefin-based resin melted at a predetermined resin temperature using a melt-kneader contains an amide-based compound and, if necessary, a polyolefin modifier at a high concentration. Examples thereof include a method of adding and dissolving using a master batch, maintaining the molten state as it is, and shifting to the next step (ii).

Examples of the above (1) to (3) are methods in which the amide compound is dissolved, the melted state is maintained as it is, and the process proceeds to the next step (ii). It is also possible to adopt a procedure in which the amide compound is once cooled and pelletized, the amide compound is dissolved in the polyolefin resin again at a predetermined treatment temperature, the molten state is maintained as it is, and the process proceeds to the next step (ii). ..

Further, as a device for sufficiently dissolving the amide compound, in addition to raising the resin temperature in the step (i) while paying attention to the thermal decomposition temperature of the polyolefin resin, the treatment time (residence time) in the step (i) and heating It is preferable to appropriately adjust the screw rotation speed and shape of the mixing device.

Usually, the melting point of the amide-based compound according to the present invention is 270 ° C. or higher, and the melting temperature range of the polyolefin-based resin is 80 to 180 ° C. Therefore, in the above step (i), the polyolefin-based resin is first melted, and then the polyolefin-based resin is melted. The amide compound (solid) dissolves in the melted polyolefin resin. That is, the melting temperature is higher than the melting point of the polyolefin resin. Therefore, the resin temperature in step (i) is equal to or higher than the dissolution temperature of the amide compound in the polyolefin resin, preferably in the range of the dissolution temperature to (dissolution temperature + 40 ° C.), and more preferably (the dissolution temperature + 5 ° C.). ) ~ (Melting temperature + 40 ° C) is recommended.

In the above step (ii), the melted polyolefin resin composition is cooled to a temperature below the temperature at which crystals of the amide compound are precipitated. That is, the resin temperature at the time of cooling in the step (ii) is not more than the temperature at which the amide compound is precipitated from the polyolefin resin composition, preferably (the precipitation temperature −150 ° C.) or less, and more preferably (the precipitation temperature). -200 ° C) or less is recommended. More specifically, 80 ° C. or lower, more preferably 40 ° C. or lower is recommended.

Further, the cooling method in the step (ii) is not particularly limited, and a known cooling method can be adopted. Specifically, a method of immersing in a refrigerant such as water or air-cooling using a forced air-cooling device can be used. At this time, it is best that the amide compound is recrystallized in the polyolefin resin and precipitated as needle-like crystals. The acicular crystals of such an amide compound can be easily observed with a polarizing microscope.

In order to exert the effect of the present invention more effectively, it is important that the crystals of the amide compound (particularly needle-like crystals) are uniformly and finely dispersed in the polyolefin resin. Therefore, the steps (i) and (ii) are the simplest and most efficient methods for achieving the above state.

However, if the amide compound is easily available as microcrystals or acicular crystals, the step (iii) can be performed immediately, but the amide compound obtained as a pretreatment before the step (iii) is once obtained. It is preferable to disperse it uniformly in the polyolefin resin.

The temperature control in the step (iii) is usually 125 ° C. or lower, preferably 125 ° C. or lower, after the polyolefin-based resin composition is once melted in a temperature range equal to or higher than the melting point of the polyolefin-based resin and lower than the melting temperature of the amide-based compound in the polypropylene-based resin. Is molded in a temperature range of 20 to 125 ° C., more preferably 50 to 120 ° C., particularly preferably 80 to 120 ° C.

The above-mentioned "molding" means, as appropriate, pneumatic molding, provided that the temperature can be controlled so as to have the desired shape and shape (film, sheet, bottle, case, etc.) of the polyolefin-based resin molded body. It means that molding is performed by adopting a molding method such as vacuum molding, compression molding, extrusion thermoform molding, extrusion molding, or injection molding.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The evaluation methods in Examples and Comparative Examples are as follows.

[Crystal orientation in molded product]
Sample Preparation Using a uniaxial fully meshing twin-screw extruder ULT15TWnano-15MG-NH (-700) -HKU manufactured by Technobel Co., Ltd., extrusion molding was performed under the following conditions to prepare a sheet. A test piece having a predetermined size was cut out from the obtained sheet and used as a sample for each test.
<Extrusion conditions>
Set temperature barrel C1 117 ℃, C2 200 ℃,
Head 200 ° C,
Dice 200 ℃
Screw shape D = 15mm, L / D = 15 (biaxial)
Screw rotation speed 25 rpm
Die shape Slit die (opening length) 35 mm,
Die gap 0.5mm
Discharge rate 0.42 kg / h (using a weight feeder)
Air gap 20mm
Chill roll diameter 72mm
Chill roll rotation speed 2 rpm

Wide-angle X-ray diffraction (2D-XRD)
In order to evaluate the crystal orientation, X-ray diffraction was measured by a transmission method using a wide-angle X-ray diffractometer (R-AxisIIc, manufactured by Rigaku Co., Ltd.). The tube current and tube voltage were set to 100 mA and 40 kV, respectively. Each sample was cut out so as to have a length x width of about 10 mm × 10 mm, and was laminated and bonded to a thickness of about 1.0 mm using a solution of toluene and polystyrene. X-rays were emitted from two directions, the MD-TD surface (throwh view: hereinafter referred to as "TV") and the MD-ND surface (edge view: hereinafter referred to as "EV").

In order to evaluate the infrared dichroic crystal orientation, the polarization infrared absorption spectrum was measured using a Fourier transform infrared spectroscope (FT-IR6100, manufactured by JASCO Corporation). The two-color ratio D (1 equation) of the obtained absorption spectrum was obtained, and the orientation function F (2 equations) was calculated. The absorption band of the spectrum was focused on ^{998 cm -1} for polypropylene-based resin and 924 cm ^-1 for polybutene-1 resin. In (formula 2), c = 1 for the polypropylene-based resin and c = -2 for the polybutene-1 resin.

[Mechanical characteristics]
Tensile Elastic Modulus Using a tensile tester DVE-3 S1000 manufactured by UBM, a sample cut into a dumbbell shape with a test portion width of 2 mm from the sheet obtained in the above "Sample preparation" has a chuck-to-chuck distance of 4 mm. The tensile test was performed at a tensile speed of 0.065 mm / s at room temperature. The slope of the stress when the tensile elongation value changes from 0.03 to 0.06 is obtained, and assuming that this slope is the same even when the elongation = 0.1 mm, the stress of elongation = 0.1 mm is obtained. The tensile elastic modulus was used. The larger the tensile elastic modulus, the better the rigidity.

Impact resistance: DuPont impact strength Using a DuPont type impact tester (manufactured by Yasuda Seiki Co., Ltd.), the DuPont impact value was measured by a method according to JIS K 5400 (1990). As the evaluation sample, a test piece of 50 mm × 50 mm cut out from the polyolefin resin sheet obtained in each Example / Comparative Example was used, and the condition was that the falling weight was 100 g or 300 g and the tip size of the striking core was 3/16 inch. It was carried out 20 times, and the average value thereof was taken as the DuPont impact value (J). The larger the value, the better the impact resistance.

<Example 1>
40 parts by weight of polypropylene resin (polypropylene homopolymer, MFR = 7.5, melting point; 168 ° C), 60 parts by weight of polybutene-1 resin (polybutene-α-olefin-polyolefin, MFR = 1.8, melting point; 110 ° C) , N, N'-dicyclohexyl-2,6-naphthalenedicarboxyamide as an amide compound (trade name; NJester NU-100, manufactured by Shin Nihon Rika Co., Ltd.) 0.04 parts by weight, tetrakis as a modifier for polyolefin [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (manufactured by Ciba Specialty Chemicals, trade name "IRGANOX1010") 0.05 parts by weight, Tris (2,4- Di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals, trade name "IRGAFOS168") 0.05 weight, and calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name "CP-S") 0.05 The weight was dry blended with a Henschel mixer. The dry blend was melted with N, N'-dicyclohexyl-2,6-naphthalenedicarboxyamide at a resin temperature of 260 ° C. to obtain a melted polyolefin resin composition (step (i)). The melted polyolefin resin composition was water-aged and cut with a pelletizer to obtain a pellet-shaped polyolefin resin composition (step (ii)). The pellet was sheet-molded at a resin temperature of 200 ° C. and a chill roll temperature of 80 ° C. to prepare a polyolefin-based resin sheet of the present invention having a thickness of 0.3 mm (step (iii)).
A 10 mm × 10 mm test piece was cut out from the obtained sheet, and X-ray diffraction measurement was performed after a predetermined treatment. FIG. 1 shows 2D-XRD diffraction patterns on TV (left) and EV (right).
Next, the polarized infrared absorption spectrum was measured using the above sheet, and the orientation function was obtained using (Equation 1) and (Equation 2), and is shown in Table 1.
Subsequently, a dumbbell test piece was cut out from the above sheet and subjected to a tensile test to determine the tensile elastic modulus. Similarly, a 50 mm × 50 mm test piece was cut out from the above sheet and subjected to an impact resistance test to determine the DuPont impact strength. The results obtained are summarized in Table 2.

<Example 2>
A polyolefin-based resin sheet was prepared by carrying out the same procedure as in Example 1 except that the chill roll temperature was changed to 50 ° C.
A dumbbell test piece was cut out from the obtained sheet and subjected to a tensile test to determine the tensile elastic modulus. Similarly, a 50 mm × 50 mm test piece was cut out from the above sheet and subjected to an impact resistance test to determine the DuPont impact strength. The results obtained are summarized in Table 2.

<Example 3>
The same procedure as in Example 1 was carried out except that the amount of the polypropylene-based resin was changed to 50 parts by weight, the amount of the polybutene-1 resin was changed to 50 parts by weight, and the amount of the amide-based compound was changed to 0.05 parts by weight. To prepare a polyolefin-based resin sheet.
A dumbbell test piece was cut out from the obtained sheet and subjected to a tensile test to determine the tensile elastic modulus. Similarly, a 50 mm × 50 mm test piece was cut out from the above sheet and subjected to an impact resistance test to determine the DuPont impact strength. The results obtained are summarized in Table 2.

<Example 4>
A polyolefin-based resin sheet was prepared by carrying out the same procedure as in Example 3 except that the chill roll temperature was changed to 100 ° C.
A dumbbell test piece was cut out from the obtained sheet and subjected to a tensile test to determine the tensile elastic modulus. Similarly, a 50 mm × 50 mm test piece was cut out from the above sheet and subjected to an impact resistance test to determine the DuPont impact strength. The results obtained are summarized in Table 2.

<Example 5>
The same procedure as in Example 1 was carried out except that the amount of the polypropylene-based resin was changed to 60 parts by weight, the amount of the polybutene-1 resin was changed to 40 parts by weight, and the amount of the amide-based compound was changed to 0.06 parts by weight. To prepare a polyolefin-based resin sheet.
A dumbbell test piece was cut out from the obtained sheet and subjected to a tensile test to determine the tensile elastic modulus. Similarly, a 50 mm × 50 mm test piece was cut out from the above sheet and subjected to an impact resistance test to determine the DuPont impact strength. The results obtained are summarized in Table 2.

<Example 6>
A polyolefin-based resin sheet was prepared by carrying out the same procedure as in Example 5 except that the chill roll temperature was changed to 100 ° C.
A dumbbell test piece was cut out from the obtained sheet and subjected to a tensile test to determine the tensile elastic modulus. Similarly, a 50 mm × 50 mm test piece was cut out from the above sheet and subjected to an impact resistance test to determine the DuPont impact strength. The results obtained are summarized in Table 2.

<Comparative example 1>
A polyolefin-based resin sheet was prepared by carrying out the same procedure as in Example 3 except that the amide-based compound was not blended.
A 10 mm × 10 mm test piece was cut out from the obtained sheet, and X-ray diffraction measurement was performed after a predetermined treatment. FIG. 2 shows 2D-XRD diffraction patterns on TV (left) and EV (right).
Next, the polarized infrared absorption spectrum was measured using the above sheet, and the orientation function was obtained using (Equation 1) and (Equation 2), and is shown in Table 1.
Subsequently, a dumbbell test piece was cut out from the above sheet and subjected to a tensile test to determine the tensile elastic modulus. Similarly, a 50 mm × 50 mm test piece was cut out from the above sheet and subjected to an impact resistance test to determine the DuPont impact strength. The results obtained are summarized in Table 2.

<Reference example 1>
A polypropylene resin sheet was prepared by carrying out the same procedure as in Comparative Example 1 except that polybutene-1 was not blended, the polypropylene resin was 100 parts by weight, and the chill roll temperature was 100 ° C.
A dumbbell test piece was cut out from the obtained sheet and subjected to a tensile test to determine the tensile elastic modulus. Similarly, a 50 mm × 50 mm test piece was cut out from the above sheet and subjected to an impact resistance test to determine the DuPont impact strength. The results obtained are summarized in Table 2.

<Reference example 2>
A polybutene-1 resin sheet was prepared by carrying out the same procedure as in Comparative Example 1 except that the polypropylene-based resin was not blended, the polybutene-1 resin was 100 parts by weight, and the chill roll temperature was 25 ° C.
A dumbbell test piece was cut out from the obtained sheet and subjected to a tensile test to determine the tensile elastic modulus. Similarly, a 50 mm × 50 mm test piece was cut out from the above sheet and subjected to an impact resistance test to determine the DuPont impact strength. The results obtained are summarized in Table 2.

From the X-ray diffraction pattern of FIG. 2 (Comparative Example 1), in the case of a mixture of a polypropylene resin and a polybutene-1 resin not containing an amide compound, φ = 90 ° in the TV image and the EV image. From the strong diffraction peaks of the (110) plane and the (300) plane derived from the polybutene-1 resin, it can be seen that the molecular chains of the polybutene-1 resin are oriented in the flow direction. Further, in the TV image, a weak diffraction peak on the (040) plane derived from the polypropylene resin is confirmed on the low angle side of the (300) plane, so that the molecular chain of the polypropylene resin is the same as that of the polybutene-1 resin. It can be seen that it is oriented in the flow direction.

On the other hand, from the X-ray diffraction pattern of FIG. 1 (Example 1), the positions of the diffraction peaks on the (110) plane and the (300) plane derived from the polypropylene-1 resin fluctuate due to the addition of the amide compound. However, the diffraction peak of the (110) plane derived from the polypropylene resin appears strongly at φ = 30 °, φ = 90 ° and φ = 150 °, and the molecular chain of the polypropylene resin clearly appears with respect to the flow direction. It can be seen that they are oriented in the vertical direction. The diffraction surface of the polypropylene-based resin changes its crystal morphology from α-crystal to β-crystal due to the action of the amide-based compound as a β-crystal nucleating agent. In the plane, FIG. 1, the diffraction peak of the (110) plane of the β crystal was confirmed.

From the results in Table 1, in the system not containing the amide-based compound of Comparative Example 1, the orientation functions of the polypropylene-based resin and the polybutene-1 resin both showed the same positive value, whereas the amide-based resin showed the same positive value. In the result of Example 1 in which the compound was blended, the orientation function of the polybutene-1 resin did not change, whereas the orientation function of the polypropylene-based resin changed from a positive value to a negative value, and this result also shows that polypropylene. The orientation direction of the molecular chains of the based resin changes from the flow direction to the direction perpendicular to the flow direction, that is, the molecular chains of the polypropylene resin and the polybutene-1 resin are oriented in different directions. It is clear that there is.

Further, from the results in Table 2, a blend of the polypropylene-based resin and the polybutene-1 resin of the comparative example, in which the balance between rigidity and impact resistance is improved as compared with the polypropylene-based resin alone or the polybutene-1 resin alone system of the reference example. It can be seen that both the rigidity and the impact resistance are further improved by blending the amide-based compound as compared with the system. That is, by blending an amide-based compound with a polyolefin-based alloy resin containing a polypropylene-based resin and a polybutene-1 resin as main components, a further improvement in the balance between rigidity and impact resistance has been achieved, and so far, a polyolefin-based resin has been achieved. It can be said that the possibility of using polyolefin-based resins has expanded even in applications that could not be handled by resins.

The polyolefin-based resin molded product of the present invention has an excellent balance of rigidity and impact resistance, and has particularly high impact strength. Therefore, it should be used as a molded product for automobile parts, mechanical engineering parts, chemical industry parts, home appliance parts, etc. Can be done.

Claims (4)

A polyolefin-based resin molded product containing polypropylene-based resin and polybutene-1 resin as main components.
Polyolefin-based resin molded article in which the orientation functions calculated from the two-color ratio of the absorption spectrum obtained by the polarization infrared absorption spectrum measurement of the polypropylene-based resin and the polybutene-1 resin are different from each other and have positive or negative values. .. The molecular chain of the polypropylene resin is oriented in a direction perpendicular to the flow direction of the resin when molding, and the molecular chain of the polybutene-1 resin is oriented in a direction parallel to the flow direction of the resin when molding. , The polyolefin-based resin molded product according to claim 1. (I) a polypropylene resin and polybutene-1 resin and the following formula by heating the amide compound represented by (1) by heating and dissolving the above A phagemid based compound, a polyolefin resin composition in a molten state The process of getting
(Ii) A step of cooling the melted polyolefin resin composition obtained in the step (i) to precipitate fine acicular amide-based compound crystals, and (iii) the step of the step (ii). Rigidity and impact resistance, comprising a step of melting the cooled polyolefin-based resin composition to a temperature range above the melting point of the polyolefin-based resin and a temperature at which the amide-based compound of fine acicular crystals does not melt by heating, and then molding. The method for producing a polyolefin-based resin molded product according to claim 1 or 2, which has an excellent balance of properties.
General formula (1)

[In the formula, n represents an integer of 2 to 6. R ¹ is a saturated or unsaturated aliphatic polycarboxylic acid residue having 2 to 18 carbon atoms, an alicyclic polycarboxylic acid residue having 3 to 18 carbon atoms, or an aromatic polycarboxylic acid residue having 6 to 18 carbon atoms. Represents a group. 2-6 ^{R 2} are the same or different, respectively, saturated or unsaturated aliphatic amine residue having 5 to 30 carbon atoms, 6 to alicyclic amine residue or carbon atoms of 5 to 30 carbon atoms Represents 30 aromatic amine residues. ] The orientation functions calculated from the two-color ratio of the absorption spectrum obtained by measuring the polarization infrared absorption spectrum of the polypropylene-based resin and the polybutene-1 resin, which are the main components of the polyolefin-based resin molded product, are positive or different from each other. A method for improving the rigidity and impact resistance of a polyolefin resin molded product in a well-balanced manner, which is characterized by having a negative value.

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