阅读说明：本技术 树脂组合物和树脂成型品 (Resin composition and resin molded article ) 是由 八百健二 宫崎佳奈 田中凉 于 2019-03-08 设计创作，主要内容包括：本发明提供了一种树脂组合物和树脂成型品。所述树脂组合物包含具有源自生物质的碳原子的树脂,其中,弯曲蠕变弹性模量F<Sup>7</Sup>与弯曲蠕变弹性模量F<Sup>14</Sup>之比(F<Sup>7</Sup>/F<Sup>14</Sup>)为1.9至6.0。根据ISO 899-2:1993中规定的方法,在60℃的温度和7MPa的负载的条件下经1000小时测得F<Sup>7</Sup>,并且在60℃的温度和14MPa的负载的条件下经1000小时测得F<Sup>14</Sup>。(The invention provides a resin composition and a resin molded product. The resin composition comprises a resin having biomass-derived carbon atoms, wherein the flexural creep elastic modulus F 7 Flexural creep modulus of elasticity F 14 Ratio of (F) 7 /F 14 ) Is 1.9 to 6.0. F is measured according to the method specified in ISO899-2:1993 at a temperature of 60 ℃ and a load of 7MPa over a period of 1000 hours 7 And F is measured at a temperature of 60 ℃ and a load of 14MPa for 1000 hours 14 。)

1. A resin composition comprising a resin having a biomass-derived carbon atom, wherein the flexural creep elastic modulus F⁷Flexural creep modulus of elasticity F¹⁴Ratio F⁷/F¹⁴1.9 to 6.0; according to the method specified in ISO899-2:1993, said F⁷Measured at a temperature of 60 ℃ and a load of 7MPa over a period of 1000 hours, and the F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours.

2. The resin composition according to claim 1, wherein the content of biomass-derived carbon atoms in the resin composition as defined in ASTM D6866:2012 is 30% or more based on the total amount of carbon atoms in the resin composition.

3. The resin composition according to claim 1 or 2, wherein F⁷Is 1,200MPa to 1,800 MPa.

4. The resin composition according to any one of claims 1 to 3, wherein F¹⁴Is 200MPa to 800 MPa.

5. The resin composition according to any one of claims 1 to 4, wherein the resin having a carbon atom derived from biomass contains cellulose acylate (A).

6. The resin composition according to any one of claims 1 to 5, wherein the cellulose acylate (A) is at least one compound selected from the group consisting of Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB).

7. The resin composition according to any one of claims 1 to 6, wherein a content of the cellulose acylate (A) is 50% by mass or more with respect to the resin composition.

8. The resin composition according to any one of claims 1 to 7, further comprising at least one ester compound (B) selected from the group consisting of: a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), and a compound represented by the following general formula (5),

wherein, in the general formula (1), R¹¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, and R¹²Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms;

in the general formula (2), R²¹And R²²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms;

in the general formula (3), R³¹And R³²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms;

in the general formula (4), R⁴¹、R⁴²And R⁴³Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms; and is

In the general formula (5), R⁵¹、R⁵²、R⁵³And R⁵⁴Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

9. The resin composition according to claim 8 or 9, wherein the resin having a biomass-derived carbon atom contains cellulose acylate (a), and

the mass ratio B/A of the ester compound (B) to the cellulose acylate (A) is from 0.0025 to 0.1.

10. The resin composition according to claim 8 or 9, wherein the ester compound (B) is reacted with the resin (a) having a carbon atom derived from biomass^Bio) Mass ratio of B/A^BioIs 0.005 to 0.05.

11. The resin composition according to any one of claims 1 to 8, further comprising a plasticizer (C).

12. The resin composition according to claim 11, wherein the plasticizer (C) contains at least one selected from the group consisting of a cardanol compound, a dicarboxylic acid diester, a citric acid ester, a polyether compound having at least one unsaturated bond in the molecule, a polyether ester compound, a benzoic acid glycol ester, a compound represented by the following general formula (6), and an epoxidized fatty acid ester,

wherein, in the general formula (6), R⁶¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, and R⁶²Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

13. The resin composition according to claim 11, wherein the plasticizer (C) comprises a cardanol compound.

14. The resin composition according to any one of claims 1 to 13, further comprising a thermoplastic elastomer (D).

15. The resin composition according to claim 14, wherein the thermoplastic elastomer (D) comprises at least one selected from the group consisting of a core-shell structure polymer (D1) and an olefin polymer (D2), the core-shell structure polymer (D1) comprises a core layer and a shell layer containing an alkyl (meth) acrylate polymer on a surface of the core layer, the olefin polymer (D2) is a polymer of α -olefin and alkyl (meth) acrylate and contains 60 mass% or more of a structural unit derived from the α -olefin.

16. A resin molded article comprising the resin composition as defined in any one of claims 1 to 15.

17. The resin molded article according to claim 16, wherein the resin molded article is an injection molded article.

Technical Field

The present invention relates to a resin composition and a resin molded article.

Background

Conventionally, resin compositions have been provided and used for various purposes. In particular, the resin composition is used for various parts and housings of home appliances and automobiles. In addition, thermoplastic resins are also used for parts such as office equipment and housings of electronic and electrical equipment.

In recent years, resins derived from biomass (organic resources derived from living organisms other than fossil resources) are used, and an example of conventionally known resins having carbon atoms derived from biomass includes cellulose acylate.

Examples of conventional resin compositions or molding materials include those described in the following JP-A-2013-079319, JP-A-2011-28438 and JP-A-2006-282950.

JP-A-2013-079319 discloses ｃA resin composition comprising: (A) a cellulose ester, (B) a styrene-based resin, and (C) titanium dioxide, wherein the content of the (A) component is 95 to 50% by mass, the content of the (B) component is 50 to 5% by mass, the content of the (C) component is 0.1 to 10 parts by mass relative to the total amount (100 parts by mass) of the (A) component and the (B) component, and the resin composition does not contain a compatibilizer of the (A) component and the (B) component.

JP-A-2011-132438 discloses ｃA molding material comprising: a cellulose derivative and a polyhydroxyalkanoic acid having a molecular weight of 10000 or more, the cellulose derivative comprising: at least one group obtained by substituting hydrogen atoms of hydroxyl groups contained in cellulose with A) described below, and at least one group substituted with B) described below.

A) Hydrocarbyl group: -R^A

B) Acyl group: -CO-R^B(R^BRepresents a hydrocarbon group)

JP-A-2006-282950 discloses ｃA polyamide resin composition comprising: (A)100 parts by weight of polyundecanamide (polyamide 11) and/or polydodecanamide (polyamide 12) having a terminal amide group concentration of 15(μ eq/1g polymer); and (B)0.05 to 1.0 part by weight of N, N' -carbonylbislactam represented by the following general formula (I) wherein the relative viscosity (polymer concentration 10g/dm in 96% sulfuric acid) is measured in accordance with JIS K-6920³At 25 ℃ from 2.3 to 3.0.

In the formula, each R represents an alkyl group which may be the same as or different from each other.

Disclosure of Invention

The present invention aims to provide a resin composition and a resin composition containing a resin having a biomass-derived carbon atom, in which the flexural creep elastic modulus F is higher⁷Flexural creep modulus of elasticity F¹⁴Ratio of (F)⁷/F¹⁴) A resin molded article having excellent puncture impact strength can be obtained from the resin composition of the present invention as compared with the case of less than 1.9 or more than 6.0; in the resin composition, according to the method specified in ISO899-2:1993, F⁷Measured at a temperature of 60 ℃ and a load of 7MPa for 1000 hours, F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours.

<1>According to an aspect of the present invention, there is provided a resin composition comprising a resin having carbon atoms derived from biomass, wherein a flexural creep elastic modulus F⁷Flexural creep modulus of elasticity F¹⁴Ratio of (F)⁷/F¹⁴) From 1.9 to 6.0, according to the method specified in ISO899-2:1993, said F⁷Measured at a temperature of 60 ℃ and a load of 7MPa for 1000 hours, said F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours.

<2> the resin composition according to <1>, wherein a content of biomass-derived carbon atoms as defined in ASTM D6866:2012 in the resin composition is 30% or more based on a total amount of carbon atoms in the resin composition.

<3>According to<1>Or<2>The resin composition, wherein F⁷Is 1,200MPa to 1,800 MPa.

<4>According to<1>To<3>The resin composition as described in any one of (1), wherein F¹⁴Is 200MPa to 800 MPa.

<5> the resin composition according to any one of <1> to <4>, wherein the resin having a carbon atom derived from a biomass contains a cellulose acylate (a).

<6> the resin composition according to any one of <1> to <5>, wherein the cellulose acylate (a) is at least one selected from the group consisting of Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB).

<7> the resin composition according to any one of <1> to <6>, wherein a content of the cellulose acylate (a) is 50% by mass or more with respect to the resin composition.

<8> the resin composition according to any one of <1> to <7>, further comprising at least one ester compound (B) selected from the group consisting of: a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), and a compound represented by the following general formula (5),

in the general formula (1), R¹¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, and R¹²Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms;

in the general formula (2), R²¹And R²²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms;

in the general formula (3), R³¹And R³²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms;

in the general formula (4), R⁴¹、R⁴²And R⁴³Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms;

in the general formula (5), R⁵¹、R⁵²、R⁵³And R⁵⁴Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

<9> the resin composition <8> or <9>, wherein the resin having a carbon atom derived from a biomass contains a cellulose acylate (A), and

the mass ratio (B/A) of the ester compound (B) to the cellulose acylate (A) is from 0.0025 to 0.1.

<10>According to<8>Or<9>The resin composition of (A), wherein the ester compound (B) is reacted with a resin (A) having a biomass-derived carbon atom^Bio) Mass ratio (B/A) of^Bio) Is 0.005 to 0.05.

<11> the resin composition according to any one of <1> to <8>, further comprising a plasticizer (C).

<12> the resin composition according to <11>, wherein the plasticizer (C) comprises at least one selected from the group consisting of a cardanol compound, a dicarboxylic acid diester, a citric acid ester, a polyether compound having at least one unsaturated bond in the molecule, a polyether ester compound, a glycol benzoate, a compound represented by the following general formula (6), and an epoxidized fatty acid ester,

in the general formula (6), R⁶¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, and R⁶²Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

<13> the resin composition according to <11>, wherein the plasticizer (C) comprises a cardanol compound.

<14> the resin composition according to any one of <1> to <13>, which further comprises a thermoplastic elastomer (D).

<15> the resin composition according to <14>, wherein the thermoplastic elastomer (D) comprises at least one selected from the group consisting of a core-shell structure polymer (D1) and an olefin polymer (D2), the core-shell structure polymer (D1) has a core layer and a shell layer containing an alkyl (meth) acrylate polymer on a surface of the core layer, and the olefin polymer (D2) is a polymer of α -olefin and alkyl (meth) acrylate and contains 60 mass% or more of a structural unit derived from the α -olefin.

<16> a resin molded article comprising the resin composition of any one of <1> to <15 >.

<17> the resin molded article according to <16>, wherein the resin molded article is an injection molded article.

[ advantageous effects of the invention ]

According to the embodiments<1>Or<2>A resin composition and a flexural creep elastic modulus F in a resin composition containing a resin having a biomass-derived carbon atom are provided⁷Flexural creep modulus of elasticity F¹⁴Ratio of (F)⁷/F¹⁴) A resin molded article having superior puncture impact strength (puncutimpact strength) can be obtained from the resin composition of the present invention as compared with the case of less than 1.9 or more than 6.0; in the resin composition, according to the method specified in ISO899-2:1993, F⁷Measured at a temperature of 60 ℃ and a load of 7MPa for 1000 hours, F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours.

According to embodiment <3>, there is provided a resin composition from which a resin molded article having excellent puncture impact strength can be obtained, as compared with the case where only polylactic acid is contained as the resin having a carbon atom derived from a biomass.

According to the embodiments<4>A resin composition is provided, with F⁷A resin molded article having superior puncture impact strength can be obtained from the resin composition of the present invention as compared with the case of less than 1,200MPa or more than 1,700 MPa.

According to the embodiments<5>A resin composition is provided, with F¹⁴The resin composition of the present invention can provide a resin molded article having superior puncture impact strength as compared with the case of less than 200MPa or more than 800 MPa.

According to embodiment <6>, there is provided a resin composition from which a resin molded article having excellent puncture impact strength can be obtained, as compared with the case where the cellulose acylate (a) is cellulose acetate.

According to embodiment <7>, there is provided a resin composition from which a resin molded article having excellent puncture impact strength can be obtained, as compared with a case where the content of the cellulose acylate (a) is less than 50% by mass relative to the resin composition.

According to the embodiments<8>Also disclosed is a resin composition which enables to obtain a resin molded article having excellent puncture impact strength, as compared with a case where the resin composition contains only a resin having a biomass-derived carbon atom or a case where the resin composition contains an ester compound (B) having an aliphatic hydrocarbon group in which R is present¹¹、R²¹、R²²、R³¹、R³²、R⁴¹、R⁴²、R⁴³、R⁵¹、R⁵²、R⁵³And R⁵⁴Has less than 7 carbon atoms or more than 28 carbon atoms or R¹²Having less than 9 carbon atoms or more than 28 carbon atoms.

According to embodiment <9>, there is provided a resin composition from which a resin molded article excellent in puncture impact strength can be obtained, as compared with a case where a resin having a biomass-derived carbon atom contains cellulose acylate (a) and the mass ratio (B/a) of ester compound (B) to cellulose acylate (a) is less than 0.0025 or more than 0.1.

According to the embodiments<10>A resin composition comprising an ester compound (B) and a resin (A) having a biomass-derived carbon atom^Bio) Mass ratio (B/A) of^Bio) When the amount of the crosslinking agent is less than 0.005 or more than 0.05, a resin molded article having excellent puncture impact strength can be obtained from the resin composition of the present invention.

According to embodiment <11> or <12>, there is provided a resin composition from which a resin molded article excellent in puncture impact strength can be obtained, as compared with a resin composition containing only a resin having a carbon atom derived from a biomass.

According to embodiment <13>, there is provided a resin composition from which a resin molded article excellent in puncture impact strength can be obtained, as compared with a case where only at least one selected from the group consisting of a dicarboxylic acid diester compound, a citric acid ester, a polyether compound having one or more unsaturated bonds in the molecule, a polyether ester compound, an ethyl benzoate, a compound represented by the general formula (6), and an epoxidized fatty acid ester is contained as the plasticizer (C).

According to embodiment <14>, there is provided a resin composition from which a resin molded article excellent in puncture impact strength can be obtained as compared with a resin composition containing only a resin having a carbon atom derived from a biomass.

According to embodiment <15>, there is provided a resin composition from which a resin molded article excellent in puncture impact strength can be obtained as compared with the case where the thermoplastic elastomer (D) does not contain at least one selected from the group consisting of the core-shell structure polymer (D1) and the olefin polymer (D2) described below, wherein the core-shell structure polymer (D1) has a core layer and a shell layer of a polymer containing an alkyl (meth) acrylate ester on the surface of the core layer, and the olefin polymer (D2) is a polymer of α -olefin and an alkyl (meth) acrylate ester and contains 60 mass% or more of a structural unit derived from the α -olefin.

According to the embodiments<16>And a flexural creep elastic modulus F in a resin composition containing a resin having a biomass-derived carbon atom⁷Flexural creep modulus of elasticity F¹⁴Ratio of (F)⁷/F¹⁴) A resin molded article excellent in puncture impact strength is provided as compared with the case of less than 1.9 or more than 6.0; in the resin composition, according to the method specified in ISO899-2:1993, F⁷Measured at a temperature of 60 ℃ and a load of 7MPa for 1000 hours, F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours.

According to the embodiments<17>And a flexural creep elastic modulus F in a resin composition containing a resin having a biomass-derived carbon atom⁷Flexural creep modulus of elasticity F¹⁴Ratio of (F)⁷/F¹⁴) An injection-molded article having excellent puncture impact strength as a resin-molded article compared with the case of less than 1.9 or more than 6.0; in the resin composition, according to the method specified in ISO899-2:1993, F⁷Measured at a temperature of 60 ℃ and a load of 7MPa for 1000 hours, F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours.

Drawings

Exemplary embodiments of the present invention will be described in detail based on the following drawings, in which:

FIG. 1A is a schematic view of a tubular test piece A, which is a resin molded article molded using the resin compositions of examples and comparative examples;

FIG. 1B is a schematic view of a cylindrical test piece B, which is a resin molded article molded using the resin compositions of examples and comparative examples; and

fig. 2 is a schematic view showing an example of assembling and disassembling a molded article of a tubular test piece a and a cylindrical test piece B molded using the resin compositions of examples and comparative examples.

Description of the reference numerals

A: a tubular test piece is provided with a test tube,

b: a cylindrical test piece was used,

f: the separating force.

Detailed Description

Hereinafter, exemplary embodiments will be described as examples of the present invention. These descriptions and examples are illustrative of exemplary embodiments and do not limit the scope of the exemplary embodiments.

In the numerical ranges described in a stepwise manner, an upper limit value or a lower limit value described in one numerical range may be replaced with an upper limit value or a lower limit value of another numerical range. In addition, in the numerical ranges described in the exemplary embodiments, the upper limit value or the lower limit value of the numerical range may be replaced with the values described in the examples.

In exemplary embodiments, the term "step" is not only an independent step, but also included in the terms of the present disclosure as long as the intended purpose of the step is achieved, even if it cannot be clearly distinguished from other steps.

In exemplary embodiments, each component may comprise a plurality of respective substances. In an exemplary embodiment, where reference is made to the amount of each component in the composition, if there are multiple substances corresponding to each component in the composition, it refers to the total amount of the multiple substances, unless otherwise specified.

In exemplary embodiments, "(meth) acrylic" refers to at least one of acrylic and methacrylic, and "(meth) acrylate" refers to at least one of acrylate and methacrylate.

In the exemplary embodiment, the cellulose acylate (a), the ester compound (B), the plasticizer (C) and the thermoplastic elastomer (D) are also referred to as a component (a), a component (B), a component (C) and a component (D), respectively.

< resin composition >

The resin composition of the exemplary embodiment contains a resin having biomass-derived carbon atoms, in which bending occursModulus of creep elasticity F⁷Flexural creep modulus of elasticity F¹⁴Ratio of (F)⁷/F¹⁴) From 1.9 to 6.0, according to the method specified in ISO899-2:1993, said F⁷Measured at a temperature of 60 ℃ and a load of 7MPa over a period of 1000 hours, and the F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours.

The resin composition of the exemplary embodiment may include other components such as an ester compound (B), a plasticizer (C), and a thermoplastic elastomer (D), which are described in detail below.

Unlike resin compositions derived from fossil resources such as petroleum, it is difficult for resin compositions containing conventional biomass-derived components to freely design a molecular structure and impart desired properties, and therefore the puncture impact strength of resin molded articles may be insufficient.

In this regard, the resin composition of the exemplary embodiment includes a resin having carbon atoms derived from biomass, in which the flexural creep elastic modulus F⁷Flexural creep modulus of elasticity F¹⁴Ratio of (F)⁷/F¹⁴) From 1.9 to 6.0, according to the method specified in ISO899-2:1993, said F⁷Measured at a temperature of 60 ℃ and a load of 7MPa over a period of 1000 hours, and the F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours. Therefore, a resin molded article having excellent puncture impact strength can be obtained. The reason for this is presumed as follows.

It is presumed that the flexural creep elastic modulus F of 1.9 or more⁷Flexural creep modulus of elasticity F¹⁴Ratio of (F)⁷/F¹⁴) Indicating that the intermolecular force in the resin composition in which F is specified according to the method of ISO899-2:1993 is weak, molecules are pulled apart and the resin molded article may be broken when an external force is applied due to a high-speed collision⁷Measured at a temperature of 60 ℃ and a load of 7MPa for 1000 hours, F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours.

Further, it is presumed that F is 6.0 or less⁷/F¹⁴Indicates that the modulus of elasticity is high even when a load is applied for a certain period of time; and the resin deforms under the action of external force, may not sufficiently absorb energy, and is therefore susceptible to puncture impact. In addition, it is presumed that F is⁷/F¹⁴1.9 to 6.0, the load dependence is considered a slightly larger design that supports rapid acceleration energy absorption; within this value range, the puncture impact strength is improved without excessive deformation, and the energy absorption is not reduced.

For the above reasons, it is considered that the resin molded article obtained from the resin composition of the exemplary embodiment has excellent puncture impact strength.

[ flexural creep modulus of elasticity ]

Flexural creep elastic modulus F of resin composition of exemplary embodiment⁷Flexural creep modulus of elasticity F¹⁴Ratio of (F)⁷/F¹⁴) From 1.9 to 6.0, according to the method specified in ISO899-2:1993, said F⁷Measured at a temperature of 60 ℃ and a load of 7MPa over a period of 1000 hours, and the F¹⁴Measured at a temperature of 60 ℃ and a load of 14MPa over a period of 1000 hours. From the viewpoint of obtaining puncture impact strength in the obtained resin molded article, the ratio is preferably 1.9 to 5.0, more preferably 2.0 to 4.0, still more preferably 2.1 to 3.0, and particularly preferably 2.2 to 2.8.

F⁷And F¹⁴The value of (B) is adjusted based on, for example, the kind and content of the resin contained in the resin composition, the kind and content of the ester compound (B) described below, and the kind and content of the plasticizer (C) described below.

The flexural creep elastic modulus of the resin composition of the exemplary embodiment is measured by the following method.

Using an injection molding machine (NEX500, manufactured by NISSEI PLASTIC input ring co., ltd., the test part has a thickness of 4mm and a width of 10mm corresponding to ISO 527 tensile test and ISO 178 bending test), ISO multi-purpose dumbbell test pieces were molded using the resin composition of the exemplary embodiment at a cylinder temperature such that the injection peak pressure did not exceed 180 MPa.

The obtained ISO multi-purpose dumbbell test pieces were subjected to a test of ISO899-2:1993 for 1000 hours under the conditions of a temperature of 60 ℃ and a load of 7MPa or 14MPa using a universal tester (manufactured by Autograph AG-X plus, Shimadzu Corporation), thereby determining the flexural creep elastic modulus.

In the resin composition of the exemplary embodiment, from the viewpoint of obtaining puncture impact strength in the obtained resin molded article, the flexural creep elastic modulus F measured for 1000 hours under the conditions of a temperature of 60 ℃ and a load of 7MPa according to the method specified in ISO899-2:1993⁷Preferably 1,200MPa to 1,800MPa, more preferably 1,300MPa to 1,750MPa, and further preferably 1,350MPa to 1,650 MPa.

In the resin composition of the exemplary embodiment, from the viewpoint of obtaining puncture impact strength in the obtained resin molded article, the flexural creep elastic modulus F measured for 1000 hours under the conditions of a temperature of 60 ℃ and a load of 14MPa according to the method specified in ISO899-2:1993¹⁴Preferably from 200MPa to 800MPa, more preferably from 300MPa to 750MPa, and still more preferably from 450MPa to 700 MPa.

Hereinafter, each component of the resin composition of the exemplary embodiment will be described in detail.

[ resin having Biomass-derived carbon atoms ]

The resin composition of the exemplary embodiment includes a resin having carbon atoms derived from biomass.

The resin having a carbon atom derived from biomass is not particularly limited, and known resins having a carbon atom derived from biomass are used.

Further, the resin having a carbon atom derived from biomass may not necessarily be completely derived from biomass as long as at least a part thereof has a structure derived from biomass. Specifically, for example, as cellulose acylate described below, the cellulose structure may be derived from biomass, and the acylate structure may be derived from petroleum.

In an exemplary embodiment, the "resin having a biomass-derived carbon atom" is a resin having at least carbon derived from an organic resource derived from an organism other than a fossil resourceAtomic resin, and as described below, the presence of carbon atoms derived from biomass as specified by ASTM D6866:2012¹⁴Abundance of C indicates.

From the viewpoint of obtaining puncture impact strength in the obtained resin molded article, in the resin composition of the exemplary embodiment, the content of the biomass-derived carbon atoms defined by ASTM D6866:2012 is preferably 20% or more, more preferably 30% or more, further preferably 35% or more, and particularly preferably 40% to 100% relative to the total amount of carbon atoms in the resin composition.

In an exemplary embodiment, a method of measuring biomass-derived carbon atom content in a resin composition comprises: measurement of the total amount of carbon atoms in the resin composition based on the specification of ASTM D686: 2012¹⁴C content and calculating the content of carbon atoms derived from the biomass.

Examples of resins having biomass-derived carbon atoms include: cellulose acylate, polylactic acid, polyolefin derived from biomass, polyethylene terephthalate derived from biomass, polyamide derived from biomass, poly (3-hydroxybutyric acid), polytrimethylene terephthalate (PTT), polybutylene succinate (PBS), Phosphatidylglycerol (PG), isosorbide polymer, acrylic modified rosin, and the like.

Among these, the resin having a carbon atom derived from biomass preferably contains cellulose acylate (a), and more preferably cellulose acylate (a), from the viewpoint of obtaining puncture impact strength in the obtained resin molded article.

Cellulose acylate (A): component (A) —

The cellulose acylate (a) is a cellulose derivative in which at least a part of the hydroxyl groups in the cellulose are substituted (acylated) with acyl groups. Acyl is of the formula-CO-R^ACGroup of the structure (R)^ACRepresents a hydrogen atom or a hydrocarbon group).

The cellulose acylate (a) is, for example, a cellulose derivative represented by the following general formula (CA).

In the general formula (CA), A¹、A²And A³Independently represents a hydrogen atom or an acyl group, and n represents an integer of 2 or more. However, n is A¹N number of A²And n is A³At least a part of (a) represents an acyl group. All n A's in the molecule¹May be the same, partially the same or different from each other. Similarly, all n A's in a molecule²And n is A³May be the same, partially the same or different from each other.

In the reaction of A¹、A²And A³In the acyl groups represented, the hydrocarbon group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.

In the reaction of A¹、A²And A³In the acyl group represented, the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and is more preferably a saturated hydrocarbon group.

From A¹、A²And A³The acyl group represented is preferably an acyl group having 1 to 6 carbon atoms. That is, the cellulose acylate (a) is preferably an acyl group having 1 to 6 carbon atoms. The resin molded article excellent in puncture impact strength can be obtained more easily with the cellulose acylate (a) having an acyl group of 1 to 6 carbon atoms than with the cellulose acylate (a) having an acyl group of 7 or more carbon atoms.

From A¹、A²And A³The acyl group represented may be a group in which a hydrogen atom in the acyl group is substituted with a halogen atom (for example, a fluorine atom, a bromine atom and an iodine atom), an oxygen atom, a nitrogen atom or the like, and is preferably an unsubstituted group.

From A¹、A²And A³Examples of the acyl group represented include formyl, acetyl, propionyl, butyryl (butyryl group), acryloyl and hexanoyl. Among them, the acyl group is preferably an acyl group having 2 to 4 carbon atoms, more preferably an acyl group having 2 or 3 carbon atoms, from the viewpoint of moldability of obtaining the resin composition and puncture impact strength of obtaining the resin molded article.

Examples of the cellulose acylate (a) include cellulose acetates (mono-, di-and tri-acetates), Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB).

The cellulose acylate (a) is preferably Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB), more preferably Cellulose Acetate Propionate (CAP), from the viewpoint of obtaining puncture impact strength in the obtained resin molded article.

The cellulose acylate (a) may be used alone, or two or more thereof may be used in combination.

The weight-average degree of polymerization of the cellulose acylate (a) is preferably 200 to 1000, more preferably 600 to 1000, from the viewpoint of moldability of obtaining the resin composition and puncture impact strength in the obtained resin molded article.

The weight-average degree of polymerization of the cellulose acylate (a) is determined from the weight-average molecular weight (Mw) by the following procedure.

First, the weight average molecular weight (Mw) of the cellulose acylate (A) was measured with reference to polystyrene using a gel permeation chromatography apparatus (GPC apparatus: HLC-8320GPC manufactured by TOSOH CORPORATION, column: TSK gel α -M) using tetrahydrofuran.

Next, this is divided by the molecular weight of the structural unit of the cellulose acylate (a) to determine the degree of polymerization of the cellulose acylate (a). For example, in the case where the substituent of the cellulose acylate is an acetyl group, the molecular weight of the structural unit is 263 when the substitution degree is 2.4, and 284 when the substitution degree is 2.9.

The weight average molecular weight (Mw) of the resin in the exemplary embodiment is also measured by the same method as the method of measuring the weight average molecular weight of the cellulose acylate (a).

The substitution degree of the cellulose acylate (a) is preferably 2.1 to 2.9, more preferably 2.2 to 2.9, further preferably 2.3 to 2.9, particularly preferably 2.6 to 2.9, from the viewpoint of moldability of obtaining the resin composition and obtaining puncture impact strength in the obtained resin molded article.

From the viewpoint of moldability into which the resin composition is obtained and puncture impact strength in the obtained resin molded article, in Cellulose Acetate Propionate (CAP), the ratio of the substitution degree of acetyl group to propionyl group (acetyl group/propionyl group) is preferably 0.01 to 1, more preferably 0.05 to 0.1.

CAP preferably satisfies at least one of the following (1), (2), (3) and (4), more preferably satisfies the following (1), (3) and (4), further preferably satisfies the following (2), (3) and (4). (1) when measured by a GPC method using tetrahydrofuran as a solvent, the weight average molecular weight (Mw) of the reference polystyrene is 160000 to 250000, and the ratio Mn/Mz of the number average molecular weight (Mn) of the reference polystyrene to the Z average molecular weight (Mz) of the reference polystyrene is 0.14 to 0.21. (2) when measured by a GPC method using tetrahydrofuran as a solvent, the weight average molecular weight (Mw) of the reference polystyrene is 160000 to 250000, the ratio Mn/Mz of the number average molecular weight (Mn) of the reference polystyrene to the Z average molecular weight (Mz) of the reference polystyrene is 0.14 to 0.21, and the ratio Mn/Mz of the weight (Mw) of the reference polystyrene to the Z average molecular weight (Mz) of the reference polystyrene is 0.3 to 0.7.21, and the ratio of the weight (Mz/Mz) of the weight (Mn) of the reference polystyrene to the Z average molecular weight (Mz) of the polystyrene is 0.7 to 0.7 when measured by a die under a GPC method using a die under a temperature probe (20) and a temperature, the temperature is 36 mm, the temperature is 366, the temperature is 36 mm, the temperature is measured by a perpendicular to the temperature is 366 mm, the temperature is 366 when measured by a perpendicular to the temperature of the perpendicular to the pressure of the molding process is 3619, the molding is 36 mm, the test piece when measured by a perpendicular to the test method, the test method is.

From the viewpoint of moldability of the obtained resin composition and obtaining puncture impact strength in the obtained resin molded article, in Cellulose Acetate Butyrate (CAB), the ratio of the degree of substitution of acetyl group to butyryl group (acetyl/butyryl group) is preferably 0.05 to 3.5.

The degree of substitution of the cellulose acylate (a) is an index indicating the degree of substitution of the hydroxyl group of the cellulose with the acyl group. That is, the degree of substitution is an index indicating the degree of acylation of the cellulose acylate (a). Specifically, the degree of substitution means that three hydroxyl groups in the D-glucopyranose unit of the cellulose acylate are substituted with acyl groupsThe intramolecular average of the number of generations is taken. Degree of substitution is given by¹The ratio of the integral of the peak of a hydrogen atom derived from cellulose to the integral of the peak of a hydrogen atom derived from an acyl group in H-NMR (JMN-ECA, manufactured by JEOL RESONANCE Co., LTd.).

The resin having a carbon atom derived from biomass may be used alone, or two or more kinds thereof may be used in combination.

[ ester compound (B): component (B) ]

From the viewpoint of obtaining puncture impact strength in the obtained resin molded article, the resin composition of the exemplary embodiment further includes at least one ester compound (B) selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), and a compound represented by the following general formula (5).

Among them, from the viewpoint of obtaining puncture impact strength in the obtained resin molded article, the resin composition of the exemplary embodiment contains an ester compound (B), which is preferably one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3), more preferably one selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and particularly preferably a compound represented by the following general formula (1) as the ester compound (B).

In the general formula (1), R¹¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, and R¹²Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms.

In the general formula (2), R²¹And R²²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

In the general formula (3), R³¹And R³²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

In the general formula (4) In, R⁴¹、R⁴²And R⁴³Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

In the general formula (5), R⁵¹、R⁵²、R⁵³And R⁵⁴Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

R¹¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms. From the viewpoint that the group is easy to act as a lubricant for the resin molecular chain, R¹¹The group represented by (a) is preferably an aliphatic hydrocarbon group having 9 or more carbon atoms, more preferably an aliphatic hydrocarbon group having 10 or more carbon atoms, and still more preferably an aliphatic hydrocarbon group having 15 or more carbon atoms. From the viewpoint that such a group easily enters between molecular chains of the resin (particularly, cellulose acylate (A), the same applies hereinafter), R¹¹The group represented by (a) is preferably an aliphatic hydrocarbon group having 24 or less carbon atoms, more preferably an aliphatic hydrocarbon group having 20 or less carbon atoms, and still more preferably an aliphatic hydrocarbon group having 18 or less carbon atoms. R¹¹The radicals indicated are particularly preferably aliphatic hydrocarbon radicals having 17 carbon atoms.

R¹¹The group represented may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. From the viewpoint that the group easily enters between resin molecular chains, R¹¹The group represented is preferably a saturated aliphatic hydrocarbon group.

R¹¹The group represented may be a straight-chain aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing an alicyclic ring. From the viewpoint that the group easily enters between molecular chains of the resin (A), R¹¹The group represented is preferably an aliphatic hydrocarbon group (i.e., a chain aliphatic hydrocarbon group) free of alicyclic group, and more preferably a linear aliphatic hydrocarbon group.

When R is¹¹When the group represented is an unsaturated aliphatic hydrocarbon group, the number of unsaturated bonds in the group is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1, from the viewpoint that the group is easily incorporated between resin molecular chains.

When R is¹¹The radicals indicated are notWhen the aliphatic hydrocarbon group is saturated, from the viewpoint that the group easily enters between resin molecular chains and easily acts as a lubricant for the resin molecular chains, the group preferably contains a straight-chain saturated hydrocarbon chain having 5 to 24 carbon atoms, more preferably contains a straight-chain saturated hydrocarbon chain having 7 to 22 carbon atoms, further preferably contains a straight-chain saturated hydrocarbon chain having 9 to 20 carbon atoms, and particularly preferably contains a straight-chain saturated hydrocarbon chain having 15 to 18 carbon atoms.

When R is¹¹When the group represented is a branched aliphatic hydrocarbon group, the number of branches in the group is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1, from the viewpoint that the group is easily taken into the space between the molecular chains of the resin.

When R is¹¹When the group represented is a branched aliphatic hydrocarbon group, the main chain of the group preferably contains 5 to 24 carbon atoms, more preferably 7 to 22 carbon atoms, further preferably 9 to 20 carbon atoms, and particularly preferably 15 to 18 carbon atoms, from the viewpoint that the group easily enters between resin molecular chains and easily acts as a lubricant for the resin molecular chains.

When R is¹¹When the group represented is an aliphatic hydrocarbon group containing an alicyclic ring, the number of alicyclic rings in the group is preferably 1 or 2, more preferably 1, from the viewpoint that the group is easily incorporated between resin molecular chains.

When R is¹¹When the group represented is an aliphatic hydrocarbon group containing an alicyclic ring, the alicyclic ring in the group is preferably an alicyclic ring having 3 or 4 carbon atoms, more preferably an alicyclic ring having 3 carbon atoms, from the viewpoint that the group is easily taken into the resin molecular chain.

From the viewpoint of further improving the puncture impact strength of the resin molded article, R¹¹The group represented is preferably a straight-chain saturated aliphatic hydrocarbon group, a straight-chain unsaturated aliphatic hydrocarbon group, a branched saturated aliphatic hydrocarbon group or a branched unsaturated aliphatic hydrocarbon group, and particularly preferably a straight-chain saturated aliphatic hydrocarbon group. The number of carbon atoms in these aliphatic hydrocarbon groups is preferably as described above.

R¹¹The group represented may be a group in which a hydrogen atom in the aliphatic hydrocarbon group is replaced with a halogen atom (for example,fluorine atom, bromine atom, and iodine atom), oxygen atom, nitrogen atom, or the like, and is preferably an unsubstituted group.

R¹²Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms. R¹²Examples of radicals represented include the radicals represented by¹¹The same forms as those described. Here, R¹²The number of carbon atoms of the group represented preferably satisfies the following conditions.

From the viewpoint that the group is easy to act as a lubricant for the resin molecular chain, R¹²The group represented by (a) is preferably an aliphatic hydrocarbon group having 10 or more carbon atoms, more preferably an aliphatic hydrocarbon group having 11 or more carbon atoms, and still more preferably an aliphatic hydrocarbon group having 16 or more carbon atoms. From the viewpoint that the group easily enters between resin molecular chains, R¹²The group represented by (a) is preferably an aliphatic hydrocarbon group having 24 or less carbon atoms, more preferably an aliphatic hydrocarbon group having 20 or less carbon atoms, and still more preferably an aliphatic hydrocarbon group having 18 or less carbon atoms. R¹²The radicals indicated are particularly preferably aliphatic hydrocarbon radicals having 18 carbon atoms.

From the viewpoint of further improving the puncture impact strength of the resin molded article, R¹²The group represented is preferably a straight-chain saturated aliphatic hydrocarbon group, a straight-chain unsaturated aliphatic hydrocarbon group, a branched saturated aliphatic hydrocarbon group or a branched unsaturated aliphatic hydrocarbon group, and particularly preferably a straight-chain saturated aliphatic hydrocarbon group. The number of carbon atoms in these aliphatic hydrocarbon groups is preferably as described above.

R²¹、R²²、R³¹、R³²、R⁴¹、R⁴²、R⁴³、R⁵¹、R⁵²、R⁵³And R⁵⁴The particular and preferred forms of the radicals indicated and for R¹¹Those described are the same.

Hereinafter, the compound represented by R will be described¹¹、R²¹、R²²、R³¹、R³²、R⁴¹、R⁴²、R⁴³、R⁵¹、R⁵²、R⁵³And R⁵⁴Having 7 to 28 carbon atomsAnd a specific example of an aliphatic hydrocarbon group represented by R¹²Specific examples of the aliphatic hydrocarbon group having 9 to 28 carbon atoms are shown, but the exemplary embodiments are not limited thereto.

The ester compound (B) may be used alone, or two or more thereof may be used in combination.

[ plasticizer (C): component (C) ]

The resin composition of the exemplary embodiment preferably further contains a plasticizer (C) from the viewpoint of obtaining puncture impact strength in the obtained resin molded article.

Examples of the plasticizer (C) include cardanol compound, ester compound other than the ester compound (B), camphor, metal soap, polyhydric alcohol, polyalkylene oxide, or the like. The plasticizer (C) is preferably a cardanol compound from the viewpoint of obtaining puncture impact strength of the resin molded article.

The plasticizer (C) may be used alone, or two or more thereof may be used in combination.

The plasticizer (C) is preferably a cardanol compound or an ester compound other than the ester compound (B) from the viewpoint that the puncture impact strength is easily improved by adding the ester compound (B). Hereinafter, cardanol compounds and ester compounds suitable as the plasticizer (C) will be specifically described.

-anacardol compounds

The cardanol compound refers to a component contained in a compound naturally derived from a cashew nut (for example, a compound represented by the following formulae (c-1) to (c-4)) or a derivative of the above component.

The cardanol compound may be used alone, or two or more thereof may be used in combination.

The resin composition of the exemplary embodiment may include a mixture of compounds naturally derived from cashew nuts as a cardanol compound (hereinafter, also referred to as "cashew-derived mixture").

The resin composition of the exemplary embodiment may include a derivative from a cashew source mixture as a cardanol compound. Examples of derivatives from mixtures of cashew sources include the following mixtures or pure substances.

Mixtures prepared by adjusting the composition ratio of the components in the cashew source mixture

Pure substances obtained by separating only specific components from a mixture of cashew sources

Mixtures containing modified products obtained by modifying the components of the cashew source mixture

Mixtures comprising polymers obtained by polymerising components of cashew source mixtures

A mixture comprising a modified polymer obtained by modifying and polymerizing components of the cashew source mixture

A mixture comprising a modified product obtained by: after the composition ratio of the mixture is adjusted, the components in the mixture are further modified

A mixture comprising a polymer obtained by the following process: adjusting the composition ratio of the mixture, and further polymerizing the components in the mixture

A mixture comprising a modified polymer obtained by the following process: after adjusting the composition ratio of the mixture, the components in the mixture are further modified and polymerized

Modified products obtained by further modification of the isolated pure substances

Polymers obtained by further polymerizing the isolated pure substances

Modified polymers obtained by further modifying the isolated monomers and polymerizing them

Here, pure substances include multimers, such as dimers and trimers.

The cardanol compound is preferably at least one compound selected from the group consisting of a compound represented by general formula (CDN1) and a polymer obtained by polymerizing a compound represented by general formula (CDN1), from the viewpoint of obtaining puncture impact strength of a resin molded article.

In the general formula (CDN1), R¹Represents an alkyl group optionally having a substituent, or an unsaturated aliphatic group optionally having a double bond and a substituent. R²Represents a hydroxyl group, a carboxyl group, an alkyl group optionally having a substituent, or an unsaturated aliphatic group optionally having a double bond and a substituent. P2 represents an integer of 0 to 4. When P2 is 2 or more, plural R' s²Each may be the same group or different groups.

In the general formula (CDN1), R¹The alkyl group optionally having a substituent represented by (a) is preferably an alkyl group having 3 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms, and further preferably an alkyl group having 8 to 20 carbon atoms.

Examples of the substituent include: a hydroxyl group; a substituent group having an ether bond such as an epoxy group or a methoxy group; substituents containing ester bonds, such as acetyl or propionyl; and so on.

Examples of the alkyl group which may be substituted include pentadecn-1-yl, hept-1-yl, oct-1-yl, non-1-yl, decan-1-yl, undecane-1-yl, dodecane-1-yl or tetradecan-1-yl and the like.

In the general formula (CDN1), R¹The unsaturated aliphatic group optionally having a double bond and a substituent represented by (A) is preferablyAn unsaturated aliphatic group having 3 to 30 carbon atoms, more preferably an unsaturated aliphatic group having 5 to 25 carbon atoms, and further preferably an unsaturated aliphatic group having 8 to 20 carbon atoms.

The number of double bonds contained in the unsaturated aliphatic group is preferably 1 to 3.

Examples of the substituent include those listed as substituents for alkyl groups.

Examples of unsaturated aliphatic groups optionally having double bonds and substituents include pentadec-8-en-1-yl, pentadec-8, 11-dien-1-yl, pentadec-8, 11, 14-trien-1-yl, pentadec-7-en-1-yl, pentadec-7, 10-dien-1-yl, pentadec-7, 10, 14-trien-1-yl, and the like.

In the general formula (CDN1), R¹Preference is given to pentadec-8-en-1-yl, pentadec-8, 11-dien-1-yl, pentadec-8, 11, 14-trien-1-yl, pentadec-7-en-1-yl, pentadec-7, 10-dien-1-yl and pentadec-7, 10, 14-trien-1-yl.

In the general formula (CDN1), R is represented by²Preferred examples of the optionally substituted alkyl group and the optionally double-bonded and substituted unsaturated aliphatic group represented by (A) are included as represented by R¹The alkyl group optionally having a substituent and the unsaturated aliphatic group optionally having a double bond and a substituent are listed.

The compound represented by the general formula (CDN1) may be further modified. For example, the compound may be epoxidized. Specifically, the compound may be a compound having the following structure: wherein the hydroxyl group of the compound represented by the general formula (CDN1) is replaced with the following group (EP), that is, a compound represented by the following general formula (CDN 1-e).

In the group (EP) and the formula (CDN1-e), L_EPRepresents a single bond or a divalent linking group. In the general formula (CDN1-e), R¹、R²And P2 each independently of R in formula (CDN1)¹、R²As in P2。

In the group (EP) and the formula (CDN1-e), L_EPExamples of the divalent linking group represented include an alkylene group (preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 carbon atom) or-CH optionally having a substituent₂CH₂OCH₂CH₂-and the like.

Examples of substituents include R as general formula (CDN1)¹The substituents of (a) are listed.

L_EPMethylene is preferred.

The polymer obtained by polymerizing the compound represented by the general formula (CDN1) means a polymer obtained by polymerizing at least two compounds represented by the general formula (CDN1) with or without a linking group.

Examples of the polymer obtained by polymerizing the compound represented by the general formula (CDN1) include a compound represented by the following general formula (CDN 2).

In the general formula (CDN2), R¹¹、R¹²And R¹³Each independently represents an alkyl group optionally having a substituent or an unsaturated aliphatic group optionally having a double bond and a substituent. R²¹、R²²And R²³Each independently represents a hydroxyl group, a carboxyl group, an alkyl group optionally having a substituent, or an unsaturated aliphatic group optionally having a double bond and a substituent. P21 and P23 each independently represent an integer of 0 to 3, and P22 represents an integer of 0 to 2. L is¹And L²Each independently represents a divalent linking group. n represents an integer of 0 to 10. When P21 is 2 or more, plural R' s²¹May be the same group or different groups; when P22 is 2 or more, plural R' s²²May be the same group or different groups; when P23 is 2 or more, plural R' s²³May be the same group or different groups. When n is 2 or more, plural R¹²A plurality of R²²And a plurality of L¹Each may be the same group or different groups; and inWhen n is 2 or more, P22 s may be the same number or different numbers.

In the general formula (CDN2), R is represented by¹¹、R¹²、R¹³、R²¹、R²²And R²³Preferred examples of the alkyl group optionally having a substituent or the unsaturated aliphatic group optionally having a double bond and a substituent represented include R for the general formula (CDN1)¹Those listed.

In the general formula (CDN2), L¹And L²Examples of the divalent linking group represented include an alkylene group optionally having a substituent (preferably an alkylene group having 2 to 30 carbon atoms, more preferably an alkylene group having 5 to 20 carbon atoms) and the like.

Examples of substituents include R as general formula (CDN1)¹The substituents of (a) are those listed.

In the general formula (CDN2), n is preferably 1 to 10, more preferably 1 to 5.

The compound represented by the general formula (CDN2) may be further modified. For example, the compound may be epoxidized. Specifically, the compound may be a compound having the following structure: wherein the hydroxyl group of the compound represented by the general formula (CDN2) is replaced with a group (EP), that is, a compound represented by the following general formula (CDN 2-e).

In the general formula (CDN2-e), R¹¹、R¹²、R¹³、R²¹、R²²、R²³、P21、P22、P23、L¹、L²And n each have the same general formula as R in (CDN2)¹¹、R¹²、R¹³、R²¹、R²²、R²³、P21、P22、P23、L¹、L²And n have the same meaning.

In the general formula (CDN2-e), L_EP1、L_EP2And L_EP3Each independently represents a single bond or a divalent linking group. When n is 2 or more, plural L_EP2May be the same group or differentA group.

In the general formula (CDN2-e), the formula is represented by L_EP1、L_EP2And L_EP3Preferred examples of the divalent linking group represented include those represented by L in the general formula (CDN1-e)_EPThe divalent linking groups represented are those listed.

The polymer obtained by polymerizing the compound represented by the general formula (CDN1) may be, for example, a polymer obtained by three-dimensionally crosslinking and polymerizing at least three compounds represented by the general formula (CDN1) with or without a linking group. Examples of the polymer obtained by three-dimensionally crosslinking and polymerizing the compound represented by the general formula (CDN1) include compounds represented by the following structural formulae.

In the above structural formula, R¹⁰、R²⁰And P20 each independently has the same general formula (CDN1) as R¹、R²The same meaning as P2. L is¹⁰Represents a single bond or a divalent linking group. Plural R¹⁰A plurality of R²⁰And a plurality of L¹⁰Each may be the same group or different groups. P20 may be the same number or different numbers.

In the above structural formula, L¹⁰Examples of the divalent linking group represented include optionally substituted alkylene groups (preferably alkylene groups having 2 to 30 carbon atoms, more preferably alkylene groups having 5 to 20 carbon atoms) and the like.

Examples of substituents include R for general formula (CDN1)¹The substituents of (a) are those listed.

The compounds represented by the above structural formula may be further modified. For example, the compound may be epoxidized. Specifically, the compound may be a compound having the following structure: wherein the hydroxyl group of the compound represented by the above structural formula is replaced with a group (EP), for example, a polymer represented by the following structural formula, that is, a polymer obtained by three-dimensionally crosslinking and polymerizing a compound represented by the general formula (CDN 1-e).

In the above structural formula, R¹⁰、R²⁰And P20 each independently has the same general formula (CDN1-e) as R¹、R²The same meaning as P2. L is¹⁰Represents a single bond or a divalent linking group. Plural R¹⁰A plurality of R²⁰And a plurality of L¹⁰Each may be the same group or different groups. P20 may be the same number or different numbers.

In the above formula, from L¹⁰Examples of the divalent linking group represented include an alkylene group optionally having a substituent (preferably an alkylene group having 2 to 30 carbon atoms, and more preferably an alkylene group having 5 to 20 carbon atoms), and the like.

Examples of substituents include R for general formula (CDN1)¹The substituents of (a) are those listed.

The cardanol compound preferably contains a cardanol compound having an epoxy group, and more preferably a cardanol compound having an epoxy group, from the viewpoint of improving puncture impact strength of a resin molded article.

As the cardanol compound, a commercially available product may be used. Examples of commercially available products include NX-2024, Ultra LITE 2023, NX-2026, GX-2503, NC-510, LITE 2020, NX-9001, NX-9004, NX-9007, NX-9008, NX-9201, and NX-9203, prepared by Cardolite corporation, and LB-7000, LB-7250, and CD-5L, prepared by Tohoku Chemical IndustryuCo., Ltd.; and so on.

Examples of commercially available products of cardanol compounds with epoxy groups include NC-513, NC-514S, NC-547, LITE513E, and Ultra LTE 513, which are manufactured by Cardolite Corporation.

From the viewpoint of obtaining puncture impact strength of the resin molded article, the hydroxyl value of the cardanol compound is preferably 100mgKOH/g or more, more preferably 120mgKOH/g or more, and still more preferably 150mgKOH/g or more. The hydroxyl value of the cardanol compound was measured according to method a of ISO 14900.

When a cardanol compound having an epoxy group is used as the cardanol compound, the epoxy equivalent weight is preferably 300 to 500, more preferably 350 to 480, and even more preferably 400 to 470, from the viewpoint of improving the puncture impact strength of the resin molded article. The epoxy equivalent of the cardanol compound having an epoxy group is measured according to ISO 3001.

-ester compound-

The ester compound as the plasticizer (C) contained in the resin composition of the exemplary embodiment is not particularly limited as long as it is an ester compound other than the compounds represented by the general formulae (1) to (5).

Examples of the ester compound as the plasticizer (C) include dicarboxylic acid diesters, citric acid esters, polyether ester compounds, benzoic acid glycol esters, compounds represented by the following general formula (6), epoxidized fatty acid esters, and the like. Examples of the above esters include monoesters, diesters, triesters, and polyesters.

In the general formula (6), R⁶¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, R⁶²Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

From R⁶¹Specific forms and preferred forms of the group include those represented by the formula (1) wherein R is¹¹The groups shown are in the same form.

R⁶²The group represented may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group. R⁶²The group represented may be a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing an alicyclic ring, and is preferably a linear aliphatic hydrocarbon group. R⁶²The group represented may be a group in which a hydrogen atom in the aliphatic hydrocarbon group is substituted with a halogen atom (e.g., a fluorine atom, a bromine atom, and an iodine atom), an oxygen atom, a nitrogen atom, or the like, and is preferably an unsubstituted group. R⁶²The group represented preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and further preferably 4 or more carbon atoms.

Specific examples of the ester compound contained as the plasticizer (C) include adipates, citrates, sebacates, azelates, phthalates, acetates, dibasic esters, phosphates, condensed phosphates, glycol esters (e.g., benzoic acid glycol esters) or modified products of fatty acid esters (e.g., epoxidized fatty acid esters), and the like. Examples of the above esters include monoesters, diesters, triesters, and polyesters. Among them, dicarboxylic acid diesters (e.g., adipic acid diester, sebacic acid diester, azelaic acid diester, and phthalic acid diester) are preferable.

The plasticizer (C) is preferably an adipate. The adipate ester has high affinity with the resin, particularly the cellulose acylate (a), and is dispersed in a state close to uniformity with the resin, particularly the cellulose acylate (a), and thus the heat fluidity is further improved as compared with other plasticizers.

The ester compound as the plasticizer (C) contained in the resin composition of the exemplary embodiment preferably has a molecular weight (or weight average molecular weight) of 200 to 2,000, more preferably 250 to 1,500, and further preferably 280 to 1,000. The weight average molecular weight of the ester compound is not particularly limited, and is a value measured according to the method of measuring the weight average molecular weight of the cellulose acylate (a).

Examples of adipates include adipic diesters and adipate polyesters. Specifically, examples include adipic acid diesters represented by the following general formula (AE) and adipate polyesters represented by the following general formula (APE).

In the general formula (AE), R^AE1And R^AE2Each independently represents an alkyl group or a polyoxyalkyl [ - (C)_xH_2x-O)_y-R^A1](Here, R is^A1Represents an alkyl group, x represents an integer of 1 to 10, and y represents an integer of 1 to 10).

In the general formula (APE), R^AE1And R^AE2Each independently represents an alkyl group or a polyoxyalkyl [ - (C)_xH_2x-O)_y-R^A1](here, the number of the first and second electrodes,R^A1represents an alkyl group, x represents an integer of 1 to 10, y represents an integer of 1 to 10), R^AE3Represents an alkylene group. m1 represents an integer of 1 to 10, and m2 represents an integer of 1 to 20.

In the general formula (AE) and the general formula (APE), R^AE1And R^AE2The alkyl group represented is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and further preferably an alkyl group having 8 carbon atoms. R^AE1And R^AE2The alkyl groups represented may be linear, branched or cyclic, and are preferably linear or branched.

In the general formula (AE) and the general formula (APE), in R^AE1And R^AE2Polyoxyalkyl [ - (C) of_xH_2x-O)_y-R^A1]In, R^A1The alkyl group represented is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. R^A1The alkyl groups represented may be linear, branched or cyclic, and are preferably linear or branched.

In the general formula (APE), R^AE3The alkylene group represented is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear, branched or cyclic, and is preferably linear or branched.

In the general formula (APE), m1 is preferably an integer of 1 to 5, and m2 is preferably an integer of 1 to 10.

In the general formula (AE) and the general formula (APE), the group represented by each symbol may be substituted with a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, or the like.

The molecular weight (weight average molecular weight) of the adipate is preferably 250 to 2000, more preferably 280 to 1500, and further preferably 300 to 1000. The weight average molecular weight of adipate is a value measured according to the method of measuring the weight average molecular weight of cellulose acylate (a).

Mixtures of adipates and other components may be used as the adipate. Examples of commercially available products of this mixture include daicatty 101 manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.

The hydrocarbon group at the terminal of the fatty acid ester (e.g., citrate, sebacate, azelate, phthalate, and acetate) is preferably an aliphatic hydrocarbon group, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and further preferably an alkyl group having 8 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.

Examples of fatty acid esters (e.g., citrate, sebacate, azelate, phthalate, and acetate) include esters of fatty acids and alcohols. Examples of alcohols include: monohydric alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol; polyhydric alcohols such as glycerin, polyglycerin (diglycerin and the like), pentaerythritol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, trimethylolpropane, trimethylolethane, and sugar alcohols; and so on.

Examples of diols in the glycol benzoate include ethylene glycol, diethylene glycol, or propylene glycol, and the like.

The epoxidized fatty acid ester is an ester compound having a structure in which the unsaturated carbon-carbon bond of the unsaturated fatty acid ester is epoxidized (i.e., oxetane). Examples of epoxidized fatty acid esters include esters of fatty acids and alcohols in which some or all of the unsaturated carbon-carbon bonds in unsaturated fatty acids (e.g., oleic acid, palmitoleic acid, vaccenic acid, linoleic acid, linolenic acid, and nervonic acid) are epoxidized. Examples of alcohols include: monohydric alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol; polyhydric alcohols such as glycerin, polyglycerin (diglycerin and the like), pentaerythritol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, trimethylolpropane, trimethylolethane, and sugar alcohols; and so on.

Examples of commercially available products of epoxidized fatty acid esters include ADK CIZER D-32, D-55, O-130P and O-180A (manufactured by ADEKA) and SANSO CIZER E-PS, nE-PS, E-PO, E-4030, E-6000, E-2000H and E-9000H (manufactured by New Japan Chemical Co., Ltd.).

The polyetherester compound may be a polyester unit or a polyether unit, and each of these two units may be aromatic or aliphatic (including alicyclic). The mass ratio of the polyester unit to the polyether unit is, for example, 20:80 to 80: 20. The molecular weight (weight average molecular weight) of the polyetherester compound is preferably 250 to 2000, more preferably 280 to 1500, and further preferably 300 to 1000. An example of a commercially available product of the polyether ester compound includes ADK CIZER RS-1000 (manufactured by ADEKA).

Examples of the polyether compound having at least one unsaturated bond in the molecule include polyether compounds having an allyl group at the terminal, and polyalkylene glycol allyl ethers are preferable. The molecular weight (weight average molecular weight) of the polyether compound having at least one unsaturated bond in the molecule is preferably 250 to 2000, more preferably 280 to 1500, and further preferably 300 to 1000. Examples of commercially available products of polyether compounds having at least one unsaturated bond in the molecule include polyalkylene glycol allyl ethers such as UNIOX PKA-5006, UNIOX PKA-5008, UNIOL PKA-5014 and UNIOL PKA-5017 (manufactured by NOF CORPORATION).

[ thermoplastic elastomer (D): component (D) ]

The resin composition of the exemplary embodiment preferably further contains a thermoplastic elastomer (D) from the viewpoint of obtaining puncture impact strength in the obtained resin molded article.

The thermoplastic elastomer (D) is at least one thermoplastic elastomer selected from the group consisting of:

a core-shell structure polymer (d1) having a core layer comprising a butadiene polymer and a shell layer comprising a polymer selected from the group consisting of a styrene polymer and an acrylonitrile-styrene polymer on the surface of the core layer;

a core-shell structure polymer (d2) having a core layer and a shell layer containing an alkyl (meth) acrylate polymer on the surface of the core layer;

an olefin polymer (d3) which is a polymer of α -olefin and alkyl (meth) acrylate and contains 60 mass% or more of a structural unit derived from the α -olefin;

styrene-ethylene-butadiene-styrene copolymer (d 4);

polyurethane (d 5); and

polyester (d 6).

Component (D) is, for example, a thermoplastic elastomer having elasticity at normal temperature (25 ℃) and softening like a thermoplastic resin at high temperature.

From the viewpoint of obtaining puncture impact strength in the obtained resin molded article, the thermoplastic elastomer (D) preferably contains at least one thermoplastic elastomer selected from the group consisting of a core-shell structure polymer (D1), a core-shell structure polymer (D2), a styrene-ethylene-butadiene-styrene copolymer (D4), polyurethane (D5) and polyester (D6), wherein the polymer (D1) has a core layer containing a butadiene polymer and a shell layer containing a polymer selected from a styrene polymer and an acrylonitrile-styrene polymer on the surface of the core layer, and the polymer (D2) has a core layer and a shell layer containing an alkyl (meth) acrylate polymer on the surface of the core layer; the thermoplastic elastomer (D) more preferably contains at least one thermoplastic elastomer selected from the group consisting of a core-shell structure polymer (D1) and a core-shell structure polymer (D2), wherein the polymer (D1) has a core layer comprising a butadiene polymer and a shell layer comprising a polymer selected from a styrene polymer and an acrylonitrile-styrene polymer on the surface of the core layer, and the polymer (D2) has a core layer and a shell layer comprising an alkyl (meth) acrylate polymer on the surface of the core layer; the thermoplastic elastomer (D) further preferably contains a core-shell structure polymer (D2) having a core layer and a shell layer containing an alkyl (meth) acrylate polymer on the surface of the core layer.

The thermoplastic elastomer (D) is preferably a particulate thermoplastic elastomer from the viewpoint of obtaining puncture impact strength in the obtained resin molded article. That is, the resin composition of the exemplary embodiment preferably contains thermoplastic elastomer particles as the thermoplastic elastomer (D) from the viewpoint of obtaining puncture impact strength in the obtained resin molded article.

(core-Shell structured Polymer (d 1): component (d1))

The core-shell structure polymer (d1) is a polymer having a core-shell structure having a core layer and a shell layer located on the surface of the core layer.

The core-shell structure polymer (d1) is a polymer having a core layer as the innermost layer and a shell layer as the outermost layer (specifically, a shell layer polymer obtained by graft polymerizing an alkyl (meth) acrylate polymer onto the core layer polymer).

One or more other layers (e.g., 1 to 6 other layers) may be provided between the core layer and the shell layer. When other layers are provided between the core layer and the shell layer, the core-shell structure polymer (d1) is a multilayered polymer obtained by graft polymerizing a plurality of polymers onto the core layer polymer.

Examples of the rubber layer include a (meth) acrylic rubber layer, a silicone rubber layer, a styrene rubber layer, a conjugated diene rubber layer, an α -olefin rubber layer, a nitrile rubber layer, a polyurethane rubber layer, a polyester rubber layer, a polyamide rubber layer, and two or more copolymer rubber layers of these rubbers, wherein the rubber layer is preferably a (meth) acrylic rubber layer, a silicone rubber layer, a styrene rubber layer, a conjugated diene rubber layer, a α -olefin rubber layer, and two or more copolymer rubber layers of these rubbers.

Examples of the (meth) acrylic rubber include polymer rubbers obtained by polymerizing a (meth) acrylic component (alkyl (meth) acrylate having 2 to 8 carbon atoms).

Examples of the silicone rubber include rubbers containing a silicone component (polydimethylsiloxane, polyphenylsiloxane or the like).

Examples of the styrene rubber include polymer rubbers obtained by polymerizing styrene components (styrene or α -methylstyrene or the like).

Examples of the conjugated diene rubber include polymer rubbers obtained by polymerizing a conjugated diene component (butadiene or isoprene or the like).

α -olefin rubber examples include polymer rubbers obtained by polymerizing α -olefin components (ethylene, propylene and 2-methylpropene).

Examples of the copolymer rubber include: a copolymer rubber obtained by polymerizing two or more (meth) acrylic components, a copolymer of a (meth) acrylic component, a conjugated diene component, and a styrene component, and the like.

Examples of the alkyl (meth) acrylate among the polymers constituting the shell layer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octadecyl (meth) acrylate, and the like. In the alkyl (meth) acrylate, at least a part of hydrogen of the alkyl chain may be substituted. Examples of the substituent include amino, hydroxyl, or halogen groups and the like.

Among them, from the viewpoint that the toughness-improving effect is easily obtained by adding component (B), the alkyl (meth) acrylate polymer is preferably an alkyl (meth) acrylate polymer having an alkyl chain of 1 to 8 carbon atoms, more preferably an alkyl (meth) acrylate polymer having an alkyl chain of 1 or 2 carbon atoms, and still more preferably an alkyl (meth) acrylate polymer having an alkyl chain of 1 carbon atom.

The polymer constituting the shell layer may be a polymer obtained by polymerizing at least one selected from the group consisting of a glycidyl group-containing vinyl compound and an unsaturated dicarboxylic anhydride, in addition to the alkyl (meth) acrylate.

Examples of the glycidyl group-containing vinyl compound include glycidyl (meth) acrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, 4-glycidylstyrene, or the like.

Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride or aconitic anhydride, and the like. Among them, maleic anhydride is preferable.

When other layers are provided between the core layer and the shell layer, examples of the other layers are polymer layers described for the shell layer.

The mass percentage of the shell layer is preferably 1 to 40 mass%, more preferably 3 to 30 mass%, and further preferably 5 to 15 mass% with respect to the entire core-shell structure.

From the viewpoint that the toughness-improving effect is easily obtained by adding component (B), the average primary particle diameter of the core-shell structure polymer is not particularly limited, and it is preferably from 50nm to 500nm, more preferably from 50nm to 400nm, further preferably from 100nm to 300nm, particularly preferably from 150nm to 250 nm.

The average primary particle diameter refers to a value measured by the following method. The particles were observed with a scanning electron microscope, the maximum diameter of the primary particles was taken as the primary particle diameter, and the primary particle diameters of 100 particles were measured and averaged to obtain an average primary particle diameter. Specifically, the core-shell structured polymer in a dispersed form in the resin composition was observed with a scanning electron microscope, whereby an average primary particle diameter was obtained.

The core-shell structured polymer (d1) can be prepared by known methods.

Examples of known methods include emulsion polymerization methods. Specifically, the following method is exemplified as the preparation method. First, a monomer mixture is emulsion-polymerized to prepare a core particle (core layer), and then a mixture of other monomers is emulsion-polymerized in the presence of the core particle (core layer) to form a core-shell structure polymer, thereby forming a shell layer around the core particle (core layer). The emulsion polymerization of the mixture of other monomers is repeated while forming other layers between the core layer and the shell layer to obtain a desired core-shell structure polymer including the core layer, the other layers, and the shell layer.

Examples of commercially available products of the core-shell structured polymer (d1) include "METABLEN" (registered trademark) manufactured by Mitsubishi Chemical Corporation, "Kane Ace" (registered trademark) manufactured by Kaneka Corporation, "PARALOID" (registered trademark) manufactured by Dow Chemical Japan, "STAPHYLOID" (registered trademark) manufactured by Aica Kogyo company Limited, and "Parafacace" (registered trademark) manufactured by KURAY Co., Ltd.

(core-Shell structured Polymer (d 2): component (d2))

The core-shell structure polymer (d2) is a polymer having a core-shell structure having a core layer and a shell layer located on the surface of the core layer.

The core-shell structure polymer (d2) is a polymer having a core layer as an innermost layer and a shell layer as an outermost layer (specifically, a shell layer polymer obtained by graft polymerizing a styrene polymer or an acrylonitrile-styrene polymer to a core layer containing a butadiene polymer).

One or more other layers (e.g., 1 to 6 other layers) may be provided between the core layer and the shell layer. When other layers are provided between the core layer and the shell layer, the core-shell structure polymer (d2) is a multilayered polymer obtained by graft polymerizing a plurality of polymers onto the core layer polymer.

The core layer containing a butadiene polymer is not particularly limited as long as it is a polymer obtained by polymerizing a butadiene-containing component, and may be a core layer containing a butadiene homopolymer, but also a core layer containing a copolymer of butadiene and other monomers, examples of the other monomers include vinyl aromatic compounds, among vinyl aromatic compounds, preferred are styrene components (e.g., styrene, alkyl-substituted styrene (e.g., α -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, and 4-ethylstyrene)) and halogen-substituted styrene (e.g., 2-chlorostyrene, 3-chlorostyrene, and 4-chlorostyrene)), styrene components may be used alone, or two or more in combination.

In particular, the core layer containing a butadiene polymer may be, for example, a homopolymer of butadiene, may be a copolymer of butadiene and styrene, or may be a terpolymer of butadiene, styrene and divinylbenzene.

The butadiene polymer contained in the core layer includes: 60 to 100 mass% (preferably 70 to 100 mass%) of a structural unit derived from butadiene, and 0 to 40 mass% (preferably 0 to 30 mass%) of a structural unit derived from other monomer (preferably styrene component). For example, the proportions of the structural units derived from the respective monomers constituting the butadiene polymer are: 60 to 100 mass% for butadiene and 0 to 40 mass% for styrene. For divinylbenzene, the proportion is preferably 0 to 5 mass% of the total amount of styrene and divinylbenzene.

The shell layer containing a styrene polymer is not particularly limited as long as it is a shell layer containing a polymer obtained by polymerizing a styrene component, and may be a shell layer containing a styrene homopolymer or a shell layer containing a copolymer of styrene and other monomers. Examples of the styrene component include the styrene components exemplified for the core layer. Examples of the other monomers include alkyl (meth) acrylates (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and octadecyl (meth) acrylate), and the like. In the alkyl (meth) acrylate, at least a part of hydrogen of the alkyl chain may be substituted. Examples of the substituent include amino, hydroxyl, or halogen groups and the like. The alkyl (meth) acrylate may be used alone or in combination of two or more. As other monomers, polyfunctional monomers such as allyl (meth) acrylate, triallyl isocyanurate, and divinylbenzene may be used. The styrene polymer contained in the shell layer is preferably a copolymer of 85 to 100% by mass of a styrene component and 0 to 15% by mass of other monomer component (preferably, alkyl (meth) acrylate).

Among them, the styrene polymer contained in the shell layer is preferably a copolymer of styrene and an alkyl (meth) acrylate from the viewpoint that the toughness-improving effect is easily obtained by adding the component (B). From the same viewpoint, a copolymer of styrene and an alkyl (meth) acrylate having an alkyl chain of 1 to 8 carbon atoms is preferable, and an alkyl (meth) acrylate polymer having an alkyl chain of 1 to 4 carbon atoms is more preferable.

The shell layer containing the acrylonitrile-styrene polymer is a shell layer containing a copolymer of an acrylonitrile component and a styrene component. The acrylonitrile-styrene polymer is not particularly limited, and examples thereof include known acrylonitrile-styrene polymers. Examples of the acrylonitrile-styrene polymer include a copolymer of 10% by mass to 80% by mass of an acrylonitrile component and 20% by mass to 90% by mass of a styrene component. Examples of the styrene component copolymerized with the acrylonitrile component include the styrene components exemplified for the core layer. As the acrylonitrile-styrene polymer contained in the shell layer, polyfunctional monomers such as allyl (meth) acrylate, triallyl isocyanurate, and divinylbenzene can be used.

When other layers are provided between the core layer and the shell layer, examples of the other layers are polymer layers described for the shell layer.

The mass ratio of the shell layer is preferably 1 to 40 mass%, more preferably 3 to 30 mass%, and further preferably 5 to 15 mass% with respect to the entire core-shell structure.

Among the components (d2), examples of commercially available products of the core-shell structured polymer (d2) having a core layer comprising a butadiene polymer and a shell layer containing a styrene polymer on the surface of the core layer include "metabelen" (registered trademark) manufactured by Mitsubishi Chemical Corporation, "Kane Ace" (registered trademark) manufactured by Kaneka Corporation, "cleartrength" (registered trademark) manufactured by Arkema s.a., and "PARALOID" (registered trademark) manufactured by Dow Chemical Japan.

Among the component (d2), examples of commercially available products of the core-shell structured polymer (d2) having a core layer comprising a butadiene polymer and a shell layer containing an acrylonitrile-styrene polymer on the surface of the core layer include "Blendex" (registered trademark) made by Galata Chemicals or "ELIX" made by ELIX POLYMERS, and the like.

(olefin Polymer (d 3): component (d3))

The olefin polymer (d3) is a polymer of α -olefin and alkyl (meth) acrylate, and preferably contains 60% by mass or more of a structural unit derived from α -olefin.

Among the olefin polymers, α -olefin examples include ethylene, propylene, 2-methylpropene or the like from the viewpoint that the toughness-improving effect is easily obtained by adding component (B), α -olefin having 2 to 8 carbon atoms is preferable, α -olefin having 2 to 3 carbon atoms is more preferable, of which ethylene is more preferable.

Examples of the alkyl (meth) acrylate to be polymerized with α -olefin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octadecyl (meth) acrylate, and the like from the viewpoint that the toughness-improving effect is easily obtained by adding component (B), preferred is an alkyl (meth) acrylate having an alkyl chain with a carbon number of 1 to 8, more preferred is an alkyl (meth) acrylate having an alkyl chain with a carbon number of 1 to 4, and further preferred is an alkyl (meth) acrylate having an alkyl chain with a carbon number of 1 to 2.

The olefin polymer is preferably a polymer of ethylene and methyl acrylate from the viewpoint that the toughness-improving effect is easily obtained by adding the component (B).

From the viewpoint that the toughness-improving effect is easily obtained by adding the component (B), the olefin polymer preferably contains from 60 to 97 mass%, more preferably from 70 to 85 mass% of structural units derived from α -olefin.

The olefin polymer may contain a structural unit derived from α -olefin and another structural unit derived from alkyl (meth) acrylate, however, the other structural unit is preferably 10% by mass or less based on all the structural units in the olefin polymer.

(styrene-ethylene-butadiene-styrene copolymer (d 4): component (d4))

The copolymer (d4) is not particularly limited as long as it is a thermoplastic elastomer, and examples thereof include styrene-ethylene-butadiene-styrene copolymers. The copolymer (d4) may be a styrene-ethylene-butadiene-styrene copolymer and a hydrogenated product thereof.

From the viewpoint that the toughness-improving effect is easily obtained by adding component (B), copolymer (d4) is preferably a hydrogenated product of a styrene-ethylene-butadiene-styrene copolymer. From the same viewpoint, the copolymer (d4) is preferably a block copolymer, for example, a copolymer having styrene block portions at both ends and having an ethylene/butene-containing block portion in the middle due to hydrogenation of at least a part of the double bonds of the butadiene portion (a triblock copolymer of styrene-ethylene/butene-styrene) is preferable. The ethylene/butylene block portion of the styrene-ethylene/butylene-styrene copolymer may be a random copolymer.

The copolymer (d4) is obtained by known methods. When the copolymer (d4) is a hydrogenated product of a styrene-ethylene-butadiene-styrene copolymer, for example, the copolymer can be obtained by hydrogenating the butadiene moiety of a styrene-butadiene-styrene block copolymer in which the conjugated diene moiety contains 1,4 bonds.

Examples of commercially available products of the copolymer (d4) include "Kraton" (registered trademark) manufactured by Kraton Corporation and "Septon" (registered trademark) manufactured by KURARAY co.

(polyurethane (d 5): component (d5))

The polyurethane (d5) is not particularly limited as long as it is a thermoplastic elastomer, and examples thereof include known polyurethanes. The polyurethane (d5) is preferably a linear polyurethane. The polyurethane (d5) is obtained by, for example, reacting a polyol component (polyether polyol, polyester polyol, polycarbonate polyol, etc.), an organic isocyanate component (aromatic diisocyanate, aliphatic (including alicyclic) diisocyanate, etc.), and, if necessary, a chain extender (aliphatic (including alicyclic) diol, etc.). The polyol component and the organic isocyanate component may each be used alone or in combination of two or more.

From the viewpoint that the toughness-improving effect is easily obtained by adding component (B), polyurethane (d5) is preferably an aliphatic polyurethane. The aliphatic polyurethane is preferably obtained by reacting a polyol component containing a polycarbonate polyol with an isocyanate component containing an aliphatic diisocyanate.

The polyurethane (d5) can be obtained by the following process: the polyol component is reacted with the organic isocyanate component in such a manner that the NCO/OH ratio in the raw materials when synthesizing the polyurethane is in the range of 0.90 to 1.5. The polyurethane (d5) is obtained by a known method such as a one shot method or a prepolymerization method, etc.

Examples of commercially available products of polyurethane (d5) include "Estane" (registered trademark) manufactured by Lubrizol Corporation and "Elastollan" (registered trademark) manufactured by BASF, and the like. Examples also include "Desmopan" (registered trademark) manufactured by Bayer corporation and the like.

(polyester (d 6): component (d6))

The polyester (d6) is not particularly limited as long as it is a thermoplastic elastomer, and examples thereof include known polyesters. The polyester (d6) is preferably an aromatic polyester from the viewpoint that the toughness-improving effect is easily obtained by adding the component (B). In an exemplary embodiment, the aromatic polyester means a polyester having an aromatic ring in its structure.

Examples of the polyester (d6) include polyester copolymers (polyetheresters, polyesteresters, etc.). Specific examples thereof include: a polyester copolymer having a hard segment comprising a polyester unit and a soft segment comprising a polyester unit; a polyester copolymer having a hard segment comprising polyester units and a soft segment comprising polyether units; and a polyester copolymer having a hard segment comprising polyester units and a soft segment comprising polyether units and polyester units. The mass ratio of the hard segment to the soft segment (hard segment/soft segment) in the polyester copolymer is preferably, for example, 20/80 to 80/20. The polyester units constituting the hard segment and the polyester units and polyether units constituting the soft segment may be aromatic or aliphatic (including alicyclic).

The polyester copolymer as the polyester (d6) can be obtained by a known method. The polyester copolymer is preferably a linear polyester copolymer. The polyester copolymer is obtained, for example, by the following method: subjecting a dicarboxylic acid component having 4 to 20 carbon atoms, a diol component having 2 to 20 carbon atoms, and a polyalkylene glycol component having a number average molecular weight of 300 to 20000 (including alkylene oxide adducts of polyalkylene glycols) to esterification or transesterification (esterification or transesterification method) to produce an oligomer; and then polycondensing the oligomer (polycondensation method). Further, examples of the method of esterification or transesterification include a method using a dicarboxylic acid component having 4 to 20 carbon atoms, a diol component having 2 to 20 carbon atoms, and an aliphatic polyester component having a number average molecular weight of 300 to 20000. The dicarboxylic acid component is an aromatic or aliphatic dicarboxylic acid or an ester derivative thereof, the diol component is an aromatic or aliphatic diol, and the polyalkylene glycol component is an aromatic or aliphatic polyalkylene glycol.

Among them, from the viewpoint that the toughness-improving effect is easily obtained by adding the component (B), it is preferable to use a dicarboxylic acid component having an aromatic ring as the dicarboxylic acid component of the polyester copolymer. It is preferable to use an aliphatic diol component and an aliphatic polyalkylene glycol component as the diol component and the polyalkylene glycol component, respectively.

Examples of commercially available products of the polyester (d6) include "PELPRENE" (registered trademark) manufactured by Toyobo co., ltd., and "Hytrel" (registered trademark) manufactured by DU PONT-TORAY co., ltd., respectively.

The thermoplastic elastomer (D) may be used alone, or two or more thereof may be used in combination.

[ content or content ratio of respective Components ]

The resin composition of the exemplary embodiment contains a resin having a carbon atom derived from biomass (e.g., component (a)), and optionally contains component (B), component (C), and component (D), and may contain other component (E) described below. From the viewpoint of obtaining puncture impact strength in the resulting resin molded article, the content or content ratio (both based on mass) of each component in the resin composition of the exemplary embodiment is preferably within the following range.

Abbreviations for the respective components are as follows.

Component (A) ═ cellulose acylate (A)

Component (B) ═ ester compound (B)

Component (C) is plasticizer (C)

Component (D) ═ thermoplastic elastomer (D)

In the resin composition of the exemplary embodiment, the content of the resin having carbon atoms derived from biomass is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, with respect to the total mass of the resin composition.

In the resin composition of the exemplary embodiment, the content of the component (a) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, with respect to the total mass of the resin composition.

In the resin composition of the exemplary embodiment, the content of the component (a) is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and further preferably 95 to 100 parts by mass, relative to 100 parts by mass of the content of the resin having a carbon atom derived from biomass.

In the resin composition of the exemplary embodiment, the content of the component (B) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass, relative to the total mass of the resin composition.

In the resin composition of the exemplary embodiment, the content of the component (C) is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, and further preferably 5 to 15% by mass, relative to the total mass of the resin composition.

In the resin composition of the exemplary embodiment, the content of the component (D) is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and further preferably 5 to 10% by mass, relative to the total mass of the resin composition.

Component (C) with resin (A) having biomass-derived carbon atoms^Bio) Content ratio of (C/A)^Bio) Preferably 0.03. ltoreq. (C/A)^Bio) 0.3 or less, more preferably 0.05 or less (C/A)^Bio) 0.2 or less, preferably 0.07 or less (C/A)^Bio)≤0.15。

Further, the content ratio (C/A) of the component (C) to the component (A) is preferably 0.05. ltoreq. C/A.ltoreq.0.3, more preferably 0.05. ltoreq. C/A.ltoreq.0.2, further preferably 0.07. ltoreq. C/A.ltoreq.0.3.

Component (D) and resin (A) having biomass-derived carbon atoms^Bio) Content ratio (D/A)^Bio) Superior foodIs selected to be less than or equal to 0.025 (D/A)^Bio) 0.3 or less, more preferably 0.05 or less (D/A)^Bio) 0.2 or less, preferably 0.07 or less (D/A)^Bio)≤0.1。

Further, the content ratio (D/A) of the component (D) to the component (A) is preferably 0.025. ltoreq. D/A.ltoreq.0.3, more preferably 0.05. ltoreq. D/A.ltoreq.0.2, further preferably 0.07. ltoreq. D/A.ltoreq.0.1.

[ other component (E) ]

The resin composition of the exemplary embodiment may include other component (E) (component (E)). In the case where the other component (E) is contained, the total content of the other component (E) as a whole is preferably 15% by mass or less, more preferably 10% by mass or less, with respect to the total amount of the resin composition.

Examples of the other component (E) include: flame retardants, compatibilizers, oxidation inhibitors, stabilizers, antiblocking agents, light stabilizers, weathering agents, colorants, pigments, modifiers, drip inhibitors, antistatic agents, hydrolysis inhibitors, fillers, reinforcing agents (e.g., glass fibers, carbon fibers, talc, clay, mica, glass flakes, ground glass, glass beads, crystalline silica, alumina, silicon nitride, aluminum nitride, and boron nitride), acid acceptors to prevent acetic acid release (oxides such as magnesium oxide and alumina, metal hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and magnesium aluminocarbonate; calcium carbonate; talc; etc.), reactive trapping agents (e.g., epoxy compounds, anhydride compounds, and carbodiimides), and the like.

The content of the other components is preferably 0 to 5% by mass with respect to the total amount of the resin composition. Here, "0 mass%" means that no other component is contained.

In addition to the resin having a carbon atom derived from biomass (e.g., component (a)), component (B), component (C), and component (D), the resin composition of the exemplary embodiment may contain other resins as other component (E). However, when other resin is contained, the content of the other resin is preferably 5% by mass or less, and more preferably less than 1% by mass, relative to the total amount of the resin composition. It is particularly preferable that no other resin is contained (i.e., 0 mass%).

Examples of the other resins include thermoplastic resins known in the related art, specifically including: a polycarbonate resin; a polypropylene resin; a polyester resin; a polyolefin resin; a polyester carbonate resin; a polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; polyether sulfone resin; a polyarylene resin; a polyetherimide resin; a polyacetal resin; a polyvinyl acetal resin; a polyketone resin; a polyetherketone resin; polyether ether ketone resin; a polyaryl ketone resin; a polyether nitrile resin; a liquid crystal resin; a polybenzimidazole resin; a polyaspartic acid resin; a vinyl polymer or copolymer obtained by polymerizing or copolymerizing one or more vinyl monomers selected from the group consisting of aromatic alkenyl compounds, methacrylates, acrylates, and vinyl cyanide compounds; a diene-aromatic alkenyl compound copolymer; vinyl cyanide-diene-aromatic alkenyl compound copolymer; aromatic alkenyl-diene-vinyl cyanide-N-phenylmaleimide copolymer; ethylene cyanide- (ethylene-diene-propylene (EPDM)) -aromatic alkenyl compound copolymers; vinyl chloride resin; chlorinated vinyl chloride resin; and so on. These resins may be used alone or in combination of two or more.

The polyester as the other component (E) may contain an aliphatic polyester (E1). Examples of the aliphatic polyester (e1) include a polymer of hydroxyalkanoate (hydroxyalkanoic acid), a polycondensate of a polycarboxylic acid and a polyhydric alcohol, a ring-opening polycondensate of cyclic lactam or a polymer obtained by polymerizing lactic acid with an ester bond, and the like.

Further, it is preferable that the resin composition of the exemplary embodiment contains an oxidation inhibitor or a stabilizer as the other component (E). It is preferable to contain at least one compound (e3) selected from the group consisting of hindered phenol compounds, tocopherol compounds, tocotrienol compounds, phosphite compounds and hydroxylamine compounds as the oxidation inhibitor or stabilizer.

The compound (e3) may be used alone or in combination of two or more, and two or more are preferably used in combination from the viewpoint of obtaining the steel ball drop impact strength in the obtained resin molded article.

Forms in which two or more compounds (e3) are used in combination include: a form in which two or more compounds (e3) in the same group (for example, in a hindered phenol compound) are used in combination, or a form in which two or more compounds (e3) in different groups (for example, a hindered phenol compound and a tocopherol compound) are used in combination.

From the viewpoint of the steel ball drop impact strength of the resulting resin molded article, the form in which two or more compounds (e3) are used in combination is preferably a form in which at least one selected from the group consisting of hindered phenol compounds and hydroxylamine compounds is used in combination with phosphite compounds, and more preferably a form in which hindered phenol compounds and phosphite compounds are used in combination.

In the resin composition of the exemplary embodiment, the content of the compound (e3) is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, and further preferably 0.1 to 1% by mass, relative to the total mass of the resin composition.

Specific examples of the compound (e3) include: hindered phenol compounds such as "Irganox 1010", "Irganox 245" and "Irganox 1076" manufactured by BASF, "ADKSTABAO-80", "ADKSTATAAO-60", "ADK STAB AO-50", "ADK STAB AO-40", "ADK STABAO-30", "ADK STAB AO-20" and "ADK STAB AO-330" manufactured by ADEKA CORPORATION, "Sumilizer GA-80", "Sumilizer GM" and "Sumilizer GS" manufactured by Sumitomo Chemical Co., Ltd.; phosphite compounds such as "Irgafos 38" (bis (2, 4-di-tert-butyl-6-methylphenyl) -ethyl-phosphite), "Irgafos 168", "Irgafos TNPP" and "Irgafos P-EPQ", manufactured by BASF; and hydroxylamine compounds such as "Irgastab FS-042" manufactured by BASF; and so on.

Further, specific examples of the tocopherol compound in the compound (e3) include, for example, the following compounds.

Specific examples of the tocotrienol compound in compound (e3) include, for example, the following compounds.

[ method for producing resin composition ]

Examples of the method of preparing the resin composition of the exemplary embodiment include, for example: a method of mixing and melt-kneading a resin having a carbon atom derived from biomass (e.g., component (a)) and, if necessary, component (B), component (C), component (D), and other component (E); a method of dissolving a resin having a carbon atom derived from biomass (e.g., component (a)) and, if necessary, component (B), component (C), component (D), and other component (E) in a solvent; and so on. Here, the melt kneading means is not particularly limited, and examples thereof include a twin-screw extruder, a HENSCHEL mixer, a BANBURY mixer, a single-screw extruder, a multi-screw extruder, a co-kneader, or the like.

< resin molded article >

The resin molded article of the exemplary embodiment includes the resin composition of the exemplary embodiment. That is, the resin molded article of the exemplary embodiment has the same composition as the resin composition of the exemplary embodiment.

The method of forming the resin molded article of the exemplary embodiment is preferably injection molding from the viewpoint of obtaining a high degree of freedom in shape. Therefore, the resin molded article of the exemplary embodiment is preferably an injection molded article obtained by injection molding from the viewpoint of obtaining a high degree of freedom in shape.

The cylinder temperature at the time of injection molding of the resin molded article of the exemplary embodiment is preferably, for example, 160 ℃ to 280 ℃, more preferably 180 ℃ to 240 ℃. The mold temperature at the time of injection molding of the resin molded article of the exemplary embodiment is preferably, for example, 40 ℃ to 90 ℃, more preferably 40 ℃ to 60 ℃.

Injection molding of the resin molded article of the exemplary embodiment is performed using, for example, commercially available equipment such as NEX500 (manufactured by Nissei Plastic Industrial co., ltd.), NEX 150 (manufactured by Nissei Plastic Industrial co., ltd.), NEX 7000 (manufactured by Nissei Plastic Industrial co., ltd.), PNX 40 (manufactured by Nissei Plastic Industrial co., ltd.), and SE50D (manufactured by Sumitomo HeavyIndustries, ltd.).

The molding method for obtaining the resin molded article of the exemplary embodiment is not limited to the above injection molding, and injection molding, extrusion molding, blow molding, hot press molding, calender molding, coating molding, cast molding, dip molding, vacuum molding, transfer molding, or the like may also be used.

The resin molded article of the exemplary embodiment is suitable for applications such as electronic and electric appliances, office equipment, home appliances, automobile interior materials, toys, or containers. Specific applications of the resin molded article of the exemplary embodiment include: housings for electronic and electrical equipment or household appliances; various components of electronic/electric devices or home appliances; an automotive interior component; assembling the toy; a plastic mold kit; CD-ROM or DVD storage boxes; tableware; beverage bottles; a food tray; a wrapping material; a film; a sheet material; and so on.