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 2019-03-07 设计创作，主要内容包括：本发明涉及树脂组合物和树脂成型品。所述树脂组合物包括具有源自生物质的碳原子的树脂,其中,通过ISO 294-3:2002中定义的方法由所述树脂组合物制成的D2试件与蒸馏水的接触角为65度至85度,所述接触角通过ISO 15989:2004中定义的方法测量。(The present invention relates to a resin composition and a resin molded article. The resin composition includes a resin having a carbon atom derived from a biomass, wherein a contact angle of a D2 test piece made of the resin composition by the method defined in ISO294-3:2002, which is measured by the method defined in ISO15989:2004, with distilled water is 65 to 85 degrees.)

1. A resin composition comprising a resin having carbon atoms derived from biomass, wherein a D2 test piece made from the resin composition by the method defined in ISO294-3:2002 has a contact angle with distilled water of 65 to 85 degrees, the contact angle being measured by the method defined in ISO15989: 2004.

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

3. The resin composition according to claim 1 or claim 2, wherein the resin having a carbon atom derived from biomass contains cellulose acylate (a).

4. The resin composition according to claim 3, 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).

5. The resin composition according to claim 3 or claim 4, wherein the content of the cellulose acylate (A) is 50% by weight or more relative to the resin composition.

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

wherein R is¹¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, and R¹²Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms,

R²¹and R²²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms,

R³¹and R³²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms,

R⁴¹、R⁴²and R⁴³Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms,

R⁵¹、R⁵²、R⁵³and R⁵⁴Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

7. The resin composition according to claim 6, wherein the resin having a carbon atom derived from biomass contains cellulose acylate (A), and a weight ratio (B/A) of the ester compound (B) to the cellulose acylate (A) is from 0.0025 to 0.1.

8. The resin composition according to claim 5 or claim 7, wherein the ester compound (B) is reacted with the resin (A) having a biomass-derived carbon atom^Bio) In weight ratio (B/A)^Bio) Is 0.005 to 0.05.

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

10. The resin composition according to claim 9, 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 a molecule of the polyether compound, a polyether ester compound, a glycol benzoate, a compound represented by formula (6), and an epoxidized fatty acid ester:

wherein R is⁶¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, and R⁶²Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

11. The resin composition according to claim 8 or claim 9, wherein the plasticizer (C) comprises a cardanol compound.

12. The resin composition according to any one of claim 1 to claim 11, further comprising a thermoplastic elastomer (D).

13. The resin composition according to claim 12, 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 comprises 60% by weight or more of a constituent unit derived from the α -olefin.

14. A resin molded article comprising the resin composition as defined in any one of claims 1 to 13.

15. The resin molded article according to claim 14, 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

In the related art, various resin compositions have been provided and used for various purposes. The resin composition is particularly useful for various parts and housings of household appliances and automobiles, and the like. In addition, thermoplastic resins are also used for parts such as housings of office equipment and electronic and electrical equipment. In recent years, resins derived from biomass (organic resources derived from organisms other than fossil resources) have been used, and as one of the resins having carbon atoms derived from biomass known in the related art, cellulose acylate can be exemplified.

As the resin composition in the related art, the following compositions disclosed in JP-A-2013-079319 can be exemplified. JP- ｃA-2013-079319 discloses "ｃA resin composition containing (ｃA) ｃA cellulose ester, (B) ｃA styrene-based resin and (C) titanium dioxide, wherein in the content of each of the (ｃA) component and the (B) component, (ｃA) component is 50 to 95% by weight, (B) component is 5 to 50% by weight, and the content of the (C) component is 0.1 to 10 parts by mass relative to the total content (100 parts by mass) of the (ｃA) component and the (B) component, and the resin composition does not contain ｃA compatibilizer of the (ｃA) component and the (B) component".

In addition, porous resin compositions disclosed in JP-A-2010-260926 are known. JP-A-2010-260926 discloses "ｃA porous polylactic acid resin composition comprising ｃA polylactic acid resin (A) and ｃA polymer (B) having ｃA contact angle with water of 87 degrees or more according to JIS K2398, and having pores with an average pore diameter of 50 μm or less inside".

Disclosure of Invention

An object of the present invention is to provide a resin composition containing a resin having a carbon atom derived from a biomass, which is capable of obtaining a resin molded article excellent in puncture impact strength, as compared with the case where a contact angle with distilled water (measured by a method defined in ISO15989: 2004) of a D2 test piece made of the resin composition by a method defined in ISO294-3:2002 is less than 65 degrees or more than 85 degrees.

This object is achieved by the following means.

<1> according to one aspect of the present disclosure, there is provided a resin composition comprising a resin having carbon atoms derived from biomass, wherein a contact angle of a D2 test piece made of the resin composition by the method defined in ISO294-3:2002, which is measured by the method defined in ISO15989:2004, with distilled water is 65 degrees to 85 degrees.

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

<3> the resin composition <1> or <2>, wherein the resin having a carbon atom derived from a biomass contains a cellulose acylate (a).

<4> the resin composition according to <3>, 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).

<5> the resin composition according to <3> or <4>, wherein the content of the cellulose acylate (a) is 50% by weight or more based on the resin composition.

<6> the resin composition according to any one of <1> to <4>, which further comprises at least one ester compound (B) selected from the group consisting of a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (5).

In the 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 formula (2), R²¹And R²²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms. In the formula (3), R³¹And R³²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms. In the formula (4), R⁴¹、R⁴²And R⁴³Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms. In the formula (5), R⁵¹、R⁵²、R⁵³And R⁵⁴Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

<7> the resin composition according to <6>, wherein the resin having a carbon atom derived from a biomass contains the cellulose acylate (a), and a weight ratio (B/a) of the ester compound (B) to the cellulose acylate (a) is from 0.0025 to 0.1.

<8>According to<5>Or<7>The resin composition described above, wherein the ester compound (B) and the resin (A) having a biomass-derived carbon atom^Bio) In weight ratio (B/A)^Bio) Is 0.005 to 0.05.

<9> the resin composition according to any one of <1> to <8>, which further comprises a plasticizer (C).

<10> the resin composition according to <9>, 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 a molecule of the polyether compound, a polyether ester compound, a glycol benzoate, a compound represented by formula (6), and an epoxidized fatty acid ester.

In the 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.

<11> the resin composition according to <8> or <9>, wherein the plasticizer (C) comprises a cardanol compound.

<12> the resin composition according to any one of <1> to <11>, which further comprises a thermoplastic elastomer (D).

<13> the resin composition according to <12>, 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 comprises 60% by weight or more of a constituent unit derived from the α -olefin.

<14> according to another aspect of the present disclosure, there is provided a resin molded article comprising the resin composition according to any one of <1> to <13 >.

<15> the resin molded article according to <14>, which is an injection molded article.

According to the aspect of <1> or <2>, there is provided a resin composition containing a resin having a carbon atom derived from a biomass, which is capable of obtaining a resin molded article excellent in puncture impact strength as compared with the case where a contact angle with distilled water (measured by the method defined in ISO15989: 2004) of a D2 test piece made of the resin composition by the method defined in ISO294-3:2002 is less than 65 degrees or more than 85 degrees.

According to the aspect of <3>, there is provided a resin composition which can obtain a resin molded article more excellent in puncture impact strength than the case of containing only a resin having other biomass-derived atoms (for example, polylactic acid and polyamide 11 as resins having biomass-derived carbon atoms).

According to the aspect of <4>, there is provided a resin composition which can give a resin molded article having more excellent puncture impact strength than a case where the cellulose acylate (a) is cellulose acetate.

According to the aspect of <5>, there is provided a resin composition which can give a resin molded article having more excellent puncture impact strength than a case where the content of the cellulose acylate (a) is less than 50% by weight with respect to the resin composition.

According to<6>In the case of a resin composition containing only a resin having a carbon atom derived from a biomass or a resin composition containing an ester compound (B) (wherein R is¹¹、R²¹、R²²、R³¹、R³²、R⁴¹、R⁴²、R⁴³、R⁵¹、R⁵²、R⁵³And R⁵⁴Any one ofEach represents an aliphatic hydrocarbon group having less than 7 carbon atoms or more than 28 carbon atoms, or R¹²Representing an aliphatic hydrocarbon group having less than 9 carbon atoms or more than 28 carbon atoms), a resin molded article more excellent in puncture impact strength can be obtained.

According to the aspect of <7>, there is provided a resin composition which can give a resin molded article having more excellent puncture impact strength than a case where the weight ratio (B/a) of the ester compound (B) to the cellulose acylate (a) is less than 0.0025 or more than 0.1.

According to<8>In an aspect of (a), there is provided a resin composition comprising an ester compound (B) and a resin (A) having a carbon atom derived from a biomass^Bio) In weight ratio (B/A)^Bio) When the content is less than 0.005 or more than 0.05, a resin molded article having more excellent puncture impact strength can be obtained.

According to the aspect of <9> or <10>, there is provided a resin composition which can obtain a resin molded article having more excellent puncture impact strength than the case of a resin composition containing only a resin having a carbon atom derived from a biomass.

According to the aspect of <11>, there is provided a resin composition capable of obtaining a resin molded article having more excellent puncture impact strength than a case where the plasticizer (C) contains only at least one selected from the group consisting of a dicarboxylic acid diester, a citric acid ester, a polyether compound having at least one unsaturated bond in the molecule of the polyether compound, a polyether ester compound, a benzoic acid glycol ester, a compound represented by the formula (6), and an epoxidized fatty acid ester with respect to the plasticizer (C).

According to the aspect of <12>, there is provided a resin composition which can obtain a resin molded article having more excellent puncture impact strength than the case of a resin composition containing only a resin having a carbon atom derived from a biomass.

According to the aspect of <13>, there is provided a resin composition capable of obtaining a resin molded article more excellent in puncture impact strength than in the case of a resin composition in which the thermoplastic elastomer (D) does not contain 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) having 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% by weight or more of a constituent unit derived from the α -olefin.

According to the aspect of <14>, there is provided a resin molded article excellent in puncture impact strength as compared with the case of using a resin composition containing a resin having a carbon atom derived from a biomass, which is capable of obtaining a resin molded article excellent in puncture impact strength as compared with the case where a contact angle with distilled water (measured by the method defined in ISO15989: 2004) of a D2 test piece made of a resin composition by the method defined in ISO294-3:2002 is less than 65 degrees or more than 85 degrees.

According to the aspect of <15>, there is provided, as a resin molded article, an injection molded article excellent in puncture impact strength as compared with the case of using a resin composition containing a resin having a carbon atom derived from a biomass, which is capable of obtaining a resin molded article excellent in puncture impact strength as compared with the case where a contact angle with distilled water (measured by a method defined in ISO15989: 2004) of a D2 test piece made of a resin composition by a method defined in ISO294-3:2002 is less than 65 degrees or more than 85 degrees.

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 set forth in a stepwise manner, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value described in another numerical range in a stepwise manner. 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 an exemplary embodiment, the term "step" includes not only a separate step but also a case where an intended purpose of the step can be achieved even if it cannot be clearly distinguished from other steps. In exemplary embodiments, each component may comprise a plurality of respective substances. In exemplary embodiments, where reference is made to the amount of each component in the composition, if there are multiple species corresponding to each component in the composition, it refers to the total amount of the multiple species unless otherwise specified. In exemplary embodiments, "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid, and "(meth) acrylate" means 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 according to an exemplary embodiment includes a resin having a carbon atom derived from a biomass, wherein a D2 test piece made of the resin composition by the method defined in ISO294-3:2002 has a contact angle with distilled water of 65 degrees to 85 degrees, the contact angle being measured by the method defined in ISO15989: 2004. The resin composition according to an exemplary embodiment may include other components such as an ester compound (B), a plasticizer (C), and a thermoplastic elastomer (D) described later.

Unlike resin compositions derived from fossil resources (e.g., petroleum), it is difficult in the related art to freely design a molecular structure in a resin composition containing a biomass-derived component, and to impart desired properties, and therefore the puncture impact strength of a resin molded article obtained from the resin composition may be insufficient.

In contrast, the resin composition according to the exemplary embodiment contains a resin having a carbon atom derived from biomass, wherein a D2 test piece made of the resin composition by the method defined in ISO294-3:2002 has a contact angle with distilled water of 65 degrees to 85 degrees, which is measured by the method defined in ISO15989:2004, and thus, it can obtain a resin molded article excellent in puncture impact strength. The reason is presumed as follows.

It is estimated that the contact angle of distilled water in the resin composition is designed to be 65 degrees or more so that the hydrophilic portion is collected to some extent in the resin molded article when the resin composition is formed. This means that bonding by intermolecular or intramolecular polar groups typified by hydrogen bonds is strengthened, which is considered to improve puncture impact strength. On the other hand, it is estimated that designs with contact angles below 85 degrees are intended to ensure that the intermolecular distances do not come too close to each other. When the molecules are too close to each other, it is considered that the rigidity becomes too strong, and energy absorption by weakening the intermolecular force with respect to the external force (e.g., high-speed collision) is insufficient, and the piercing impact strength deteriorates; however, when the contact angle is 85 degrees or less, it is estimated that the puncture impact strength becomes excellent. For the above reasons, it is considered that the resin molded article obtained from the resin composition in the exemplary embodiment is excellent in puncture impact strength.

[ contact Angle with distilled Water ]

In the resin composition according to the exemplary embodiment, a contact angle of a D2 test piece made of the resin composition by the method defined in ISO294-3:2002, which is measured by the method defined in ISO15989:2004, with distilled water is 65 to 85 degrees, and from the viewpoint of puncture impact strength of the resulting resin molded article, the contact angle is preferably 65 to 80 degrees, more preferably 65 to 75 degrees, and particularly preferably 67 to 72 degrees. The contact angle with distilled water is adjusted by, for example, the kind and content of the resin contained in the resin composition, the kind and content of the ester compound (B) described later, and the kind and content of the plasticizer (C) described later.

In addition, the method of measuring a contact angle with distilled water in the exemplary embodiment is performed in such a manner that: injection molding was performed by the method defined in ISO294-3:2002 using the resin composition according to the exemplary embodiment to obtain a D2 test piece (a rectangular plate having the size of (60 ± 2) mmx (2 ± 0.1) mm), and using the obtained D2 test piece, the contact angle of distilled water in the D2 test piece was measured by the method defined in ISO15989: 2004.

Hereinafter, components of the resin composition according to the exemplary embodiment will be described in detail.

[ resin having Biomass-derived carbon atoms ]

The resin composition according to an exemplary embodiment includes a resin having carbon atoms derived from biomass. The resin having a biomass-derived carbon atom is not particularly limited, and known resins having a biomass-derived carbon atom have been used. In addition, as the resin having a carbon atom derived from biomass, all of the resins do not necessarily have to be derived from biomass, and at least a part thereof may have a structure derived from biomass. Specifically, the cellulose acylate described below may have a cellulose structure derived from biomass and an acylate structure derived from petroleum. Note that in an exemplary embodiment, a "resin having carbon atoms derived from biomass" is a resin having at least carbon atoms derived from organic resources derived from organisms other than fossil resources and, as described below, specified under ASTM D6866:2012, by¹⁴The abundance of C indicates the presence of carbon atoms derived from the biomass.

From the viewpoint of puncture impact strength of the resulting resin molded article, the content of biomass-derived carbon atoms in the resin composition according to the exemplary embodiment as defined in ASTM D6866:2012 is preferably 20% or more, more preferably 30% or more, still more preferably 35% or more, and particularly preferably 40% to 100% relative to the total amount of carbon atoms in the resin composition. Further, in exemplary embodiments, the method of measuring the content of biomass-derived carbon atoms of the resin composition is by measuring all of the carbon atoms in the resin composition based on the specifications of ASTM D6866:2012¹⁴The abundance of C is used to calculate the content of carbon atoms derived from the biomass.

Examples of the resin having a carbon atom derived from biomass 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, and acrylic-modified rosin. Among them, from the viewpoint of puncture impact strength of the obtained resin molded article, the resin having a carbon atom derived from biomass preferably contains cellulose acylate (a), and the resin having a carbon atom derived from biomass is more preferably cellulose acylate (a).

-cellulose acylate (a): component (A)

The cellulose acylate (a) is a cellulose derivative in which at least a part of hydroxyl groups in cellulose is 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 a cellulose derivative represented by the formula (CA).

In the formula (CA), A¹、A²And A³Independently represents a hydrogen atom or an acyl group, and n represents an integer of 2 or more. Here, n are 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 the molecule²May be the same as, partially the same as or different from each other, and all n A's in the molecule³May be the same, partially the same or different from each other.

In the reaction of A¹、A²And A³In the acyl group represented, the hydrocarbon group in the acyl group may be linear, branched or cyclic, but it is preferably linear or branched, and more preferably linear.

In the reaction of A¹、A²And A³In the acyl group represented, the hydrocarbon group in the acyl group may be a saturated hydrocarbon group or may be 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, as the cellulose acylate (a), a cellulose acylate having an acyl group of 1 to 6 carbon atoms is preferable. For fibers having acyl groups of 1 to 6 carbon atomsA cellulose acylate (A) which can easily give a resin molded article having a puncture impact strength superior to that of a cellulose acylate (A) having an acyl group having 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), acryloyl and hexanoyl. Among them, the acyl group is more preferably an acyl group having 2 to 4 carbon atoms, and still more preferably an acyl group having 2 or 3 carbon atoms, from the viewpoint of moldability of the resin composition and puncture impact strength of 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), and more preferably Cellulose Acetate Propionate (CAP) from the viewpoint of puncture impact strength of 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 polymerization degree of the cellulose acylate (a) is preferably from 200 to 1000, and more preferably from 600 to 1000, from the viewpoint of moldability of the resin composition and puncture impact strength of the resulting resin molded article.

The average polymerization degree of the cellulose acylate (a) is measured from the weight average molecular weight (Mw) by the following procedure first, the weight average molecular weight (Mw) of the cellulose acylate (a) is measured in terms of polystyrene by using a gel permeation chromatography device for tetrahydrofuran (GPC device: manufactured by TOSOHCORPORATION, HLC-8320GPC, column: TSKgel α -M) next, the weight average molecular weight (Mw) of the cellulose acylate (a) is divided by the molecular weight of the constituent unit of the cellulose acylate (a) to measure the polymerization degree 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 constituent unit is 263 when the substituent degree is 2.4, and 284 when the substituent degree is 2.9.

The substitution degree of the cellulose acylate (a) is preferably from 1.5 to 2.95, more preferably from 1.8 to 2.9, still more preferably from 2.1 to 2.85, and particularly preferably from 2.3 to 2.85, from the viewpoints of moldability of the resin composition and puncture impact strength of the resin molded article.

In the Cellulose Acetate Propionate (CAP), the ratio of the substitution degree of acetyl group to propionyl group (acetyl/propionyl group) is preferably 0.01 to 1, and more preferably 0.05 to 0.1, from the viewpoints of moldability of the resin composition and puncture impact strength of the resin molded article.

As the CAP, a CAP satisfying at least one of the following (1), (2), (3) and (4) is preferable, and a CAP satisfying the following (1), (3) and (4) is more preferable, and a CAP satisfying the following (2), (3) and (4) is still more preferable (1) when measured by a GPC method with tetrahydrofuran as a solvent, the weight average molecular weight (Mw) in terms of polystyrene is 160000 to 250000, and the ratio Mn/Mz of the number average molecular weight (Mn) in terms of polystyrene to the Z average molecular weight (Mz) in terms of polystyrene is 0.14 to 0.21. (2) when measured by a GPC method with tetrahydrofuran as a solvent, the weight average molecular weight (Mw) in terms of polystyrene is 160000 to 250000, the ratio Mn/Z of the number average molecular weight (Mn) in terms of polystyrene to the Z average molecular weight (Mz) in terms is 0.14 to 0.21, and when measured by a GPC method with tetrahydrofuran as a solvent, the ratio Mn/Z of the number average molecular weight (Mn) in terms of polystyrene to the Z average molecular weight (Mz) in terms of polystyrene is 1602, the polystyrene is 0.7 to 0.21, and when measured by a capillary shear coefficient TD is 36 to 35, ("cd 2) when measured by a temperature of a shear coefficient of a probe is 36 to 60mm 2, (" cd 8, ("cd 2) is smaller than 0.8, (" cd 8, ") when measured by a temperature is measured by a temperature, a temperature is 36, (" cd 8, "/20,") when measured by a temperature, 8, "/20,") when measured by a temperature is smaller than 0.7, "/20," (8, "/sec" ("cd 8.

Here, the MD direction indicates a longitudinal direction of a cavity of a mold for injection molding, and the TD direction indicates a direction perpendicular to the MD direction.

In Cellulose Acetate Butyrate (CAB), the ratio of the degree of substitution of acetyl groups to butyryl groups (acetyl/butyryl groups) is preferably 0.01 to 1, and more preferably 0.05 to 0.1, from the viewpoints of moldability of the resin composition and puncture impact strength of the resin molded article to be obtained.

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. In other words, the degree of substitution is an index indicating the degree of acylation of the cellulose acylate (a). Specifically, the degree of substitution represents the number of substitutions of three hydroxyl groups in the D-glucopyranose unit of the cellulose acylate by acyl groups on the average number within the molecule. Degree of substitution with¹H-NMR (JMN-ECA, produced by JEOL RESONANCE) was determined from the ratio of the peak integrals of the cellulose-derived hydrogen atoms to the peak integrals of the acyl-derived hydrogen atoms.

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

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

From the viewpoint of puncture impact strength of the obtained resin molded article, the resin composition according to the exemplary embodiment preferably further comprises at least one ester compound (B) selected from the group consisting of the compound represented by formula (1), the compound represented by formula (2), the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5). Among them, the resin composition according to the exemplary embodiment more preferably contains, as the ester compound (B), at least one selected from the group consisting of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3), still more preferably contains at least one selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2), and particularly preferably contains the compound represented by formula (1), from the viewpoint of puncture impact strength of the obtained resin molded article.

In the 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 formula (2), R²¹And R²²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms. In the formula (3), R³¹And R³²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms. In the formula (4), R⁴¹、R⁴²And R⁴³Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms. In the 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 R¹¹The group represented may be represented by R with respect to the angle that the molecular chain of the resin acts as a lubricant¹¹The group represented 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 R¹¹From the viewpoint that the group represented may enter between molecular chains of the resin (particularly, cellulose acylate (A), the same applies hereinafter), by R¹¹The group represented is preferably an aliphatic hydrocarbon group having 24 carbon atoms or less, more preferably an aliphatic hydrocarbon group having 20 carbon atoms or less, and still more preferably an aliphatic hydrocarbon group having 18 carbon atoms or less. From R¹¹The radicals indicated are particularly preferably aliphatic hydrocarbon radicals having 17 carbon atoms.

From R¹¹The groups represented may be saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. From R¹¹From the viewpoint that the group represented may enter between molecular chains of the resin, represented by R¹¹The group represented is preferably a saturated aliphatic hydrocarbon group.

From 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 R¹¹From the viewpoint that the group represented may enter between molecular chains of the resin, represented by R¹¹The group represented is preferably an aliphatic hydrocarbon group having no alicyclic ring (i.e., a chain aliphatic hydrocarbon group), and more preferably a linear aliphatic hydrocarbon group.

In the reaction of R¹¹When the group represented is an unsaturated aliphatic hydrocarbon group, the group represented by R¹¹The 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 represented may enter between molecular chains of the resin.

In the reaction of R¹¹When the group represented is an unsaturated aliphatic hydrocarbon group, the group represented by R¹¹The group represented may enter between molecular chains of the resin and is represented by R with respect to the angle that the molecular chains of the resin easily act as a lubricant¹¹The group represented 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, and still more 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.

In the reaction of R¹¹When the group represented is a branched aliphatic hydrocarbon group, the group represented by R¹¹From the viewpoint that the group represented may enter between molecular chains of the resin, represented by R¹¹The number of branches in the group represented is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.

In the reaction of R¹¹When the group represented is a branched aliphatic hydrocarbon group, the group represented by R¹¹The group represented may enter between molecular chains of the resin and is represented by R with respect to the angle that the molecular chains of the resin easily act as a lubricant¹¹The main chain of the group represented preferably contains 5 to 24 carbon atoms, more preferably contains 7 to 22 carbon atoms, and still more preferably contains 9 to 20 carbon atoms, and particularly preferably contains 15To 18 carbon atoms.

In the reaction of R¹¹When the group represented is an alicyclic-containing aliphatic hydrocarbon group, the group represented by R¹¹From the viewpoint that the group represented may enter between molecular chains of the resin, represented by R¹¹The number of alicyclic rings in the group represented is preferably 1 or 2, and more preferably 1.

In the reaction of R¹¹When the group represented is an alicyclic-containing aliphatic hydrocarbon group, the group represented by R¹¹From the viewpoint that the group represented may enter between molecular chains of the resin, represented by R¹¹The alicyclic group in the group represented is preferably an alicyclic group having 3 or 4 carbon atoms, and more preferably an alicyclic group having 3 carbon atoms.

From the viewpoint of further improving the puncture impact strength of the resin molded article, R is¹¹The 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.

From R¹¹The group represented may be a group in which a hydrogen atom in the aliphatic hydrocarbon 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.

R¹²Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms. As a group consisting of R¹²As the group represented, there may be mentioned a group represented by the formula¹¹The same forms as those described. Here, from R¹²The number of carbon atoms of the group represented is preferably as follows.

From R¹²The group represented may be represented by R with respect to the angle that the molecular chain of the resin acts as a lubricant¹²The group represented 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 R¹²From the viewpoint that the group represented may enter between molecular chains of the resin, represented by R¹²The group represented is preferably an aliphatic hydrocarbon group having 24 carbon atoms or less, more preferably an aliphatic hydrocarbon group having 20 carbon atoms or less, and still more preferably an aliphatic hydrocarbon group having 18 carbon atoms or less. From 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, R is¹²The 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.

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

Hereinafter, the compound represented by R will be described¹¹、R²¹、R²²、R³¹、R³²、R⁴¹、R⁴²、R⁴³、R⁵¹、R⁵²、R⁵³And R⁵⁴Specific examples of the aliphatic hydrocarbon group having 7 to 28 carbon atoms represented, and¹²specific 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 according to the exemplary embodiment preferably further includes a plasticizer (C) from the viewpoint of puncture impact strength of the obtained resin molded article. Examples of the plasticizer (C) include cardanol compounds, ester compounds other than the ester compound (B), camphor, metal soaps, polyhydric alcohols, and polyalkylene oxides. The plasticizer (C) is preferably a cardanol compound in view of 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 effect of improving puncture impact strength is easily obtained 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 (for example, a compound represented by formulae (c-1) to (c-4)) contained in a compound derived from a natural source of cashew nuts 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 according to an exemplary embodiment may include a mixture of compounds derived from natural sources of cashew nuts as a cardanol compound (hereinafter, also referred to as "cashew nut-derived mixture").

The resin composition according to this exemplary embodiment may include a derivative of a mixture derived from cashew nuts as a cardanol compound. As the derivative of the mixture derived from cashew nuts, for example, the following mixture and pure substance can be exemplified.

A mixture prepared by adjusting the composition ratio of each component in the cashew nut-derived mixture

As pure substance to separate specific components from cashew nut derived mixture

Mixture containing modified product obtained by modifying component in mixture derived from cashew nut

Mixture containing polymer obtained by polymerizing components in cashew nut-derived mixture

Mixture containing modified polymer obtained by modifying and polymerizing components in cashew nut-derived mixture

A mixture containing a modified product obtained by further modifying the components in the mixture prepared by adjusting the composition ratio of each component in the mixture derived from cashew nuts

A mixture containing a polymer obtained by further polymerizing components in a mixture prepared by adjusting the composition ratio of each component in the mixture derived from cashew nuts

A mixture containing a modified polymer obtained by further modifying and polymerizing components in a mixture prepared by adjusting the composition ratio of each component in the mixture derived from cashew nuts

Modified products obtained by further modification of the pure substances

Polymers obtained by further polymerizing the pure substances

Modified polymers obtained by further modification and polymerization of the pure substances

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 polymer obtained by polymerizing a compound represented by formula (CDN1) and a compound represented by formula (CDN1), from the viewpoint of puncture impact strength of a resin molded article.

In formula (CDN1), R¹Represents an alkyl group which may have a substituent or an unsaturated aliphatic group which has a double bond and may have a substituent. R²Represents a hydroxyl group, a carboxyl group, an alkyl group which may have a substituent, or an unsaturated aliphatic group which may have a double bond and may have a substituent. P2 represents an integer of 0 to 4. When P2 is 2 or more, each R exists in plural form²May be the same group or different groups.

In formula (CDN1), represented by R¹The alkyl group which may have a substituent(s) represented is preferably an alkyl group having 3 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms, and still more preferably an alkyl group having 8 to 20 carbon atoms. Examples of the substituent include hydroxyl; ether bond-containing substituents such as epoxy and methoxy; and ester bond-containing substituents such as acetyl and propionyl. Examples of the alkyl group which may have a substituent include pentadecan-1-yl, heptane-1-yl, octane-1-yl, nonane-1-yl, decan-1-yl, undecane-1-yl, dodecane-1-yl and tetradecan-1-yl.

In formula (CDN1), represented by R¹The unsaturated aliphatic group having a double bond and which may have a substituent represented is preferably an unsaturated aliphatic group having 3 to 30 carbon atoms, more preferably an unsaturated aliphatic group having 5 to 25 carbon atoms, and still more 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 the same substituents as those of the alkyl group. Examples of the unsaturated aliphatic group which has a double bond and may have a substituent 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 and pentadec-7, 10, 14-trien-1-yl.

In formula (CDN1), as R1, 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 are preferable.

In formula (CDN1), represented by R²Preferred examples of the alkyl group which may have a substituent and the unsaturated aliphatic group which has a double bond and has a substituent represented by R¹The alkyl group which may have a substituent and the unsaturated aliphatic group which has a double bond and may have a substituent are the same as those represented.

The compound represented by formula (CDN1) may be further modified. For example, it may be epoxidized, and in particular, the compound represented by formula (CDN1) may be a compound having a structure in which a hydroxyl group of the compound represented by formula (CDN1) is substituted with the following group (EP), that is, a compound represented by the following formula (CDN 1-e).

In the radicals (EP) and formula (CDN1-e), L_EPRepresents a single bond or a divalent linking group. In formula (CDN1-e), each R¹、R²And P2 with R in formula (CDN1) respectively¹、R²As with P2.

In the radicals (EP) and formula (CDN1-e), from L_EPExamples of the divalent linking group represented include an alkylene group (preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 1 carbon atom) which may have a substituent, and-CH₂CH₂OCH₂CH₂-a group. Examples of substituents include R with formula (CDN1)¹The same as those in (1).

As L_EPPreferably a methylene group.

The polymer in which the compound represented by formula (CDN1) is polymerized is a polymer in which at least two or more compounds represented by formula (CDN1) are polymerized with or without a linking group.

As the polymer obtained by polymerizing the compound represented by the formula (CDN1), for example, a compound represented by the formula (CDN2) may be mentioned.

In formula (CDN2), R¹¹、R¹²And R¹³Each independently represents an alkyl group which may have a substituent or an unsaturated aliphatic group which has a double bond and may have a substituent. R²¹、R²²And R²³Each independently represents a hydroxyl group, a carboxyl group, an alkyl group which may have a substituent, or an unsaturated aliphatic group which may have a double bond and may have 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, R is present in plural form²¹R may be the same group or different groups, and when P22 is 2 or more, R is present in plural form²²R which may be the same group or different groups and is present in plural form in the case where P23 is 2 or more²³May be the same group or different groups. R in the form of a complex number when n is 2 or more¹²R which may be the same group or different groups and may be present in plural when n is 2 or more₂₂L which may be the same group or different groups and which is present in plural form in the case where n is 2 or more¹May be the same group or different groups, and in the case where n is 2 or more, P22 present in plural form may be the same number or different numbers.

In the formula (CDN2), as represented by R¹¹、R¹²、R¹³、R²¹、R²²And R²³The alkyl group which may have a substituent and the unsaturated aliphatic group which may have a double bond and may have a substituent are represented by the following preferable examples and R in the formula (CDN1)¹The same groups are exemplified.

In formula (CDN2), the result is represented by L¹And L²Examples of the divalent linking group represented include alkylene groups (preferably alkylene groups having 2 to 30 carbon atoms, and more preferably alkylene groups having 5 to 20 carbon atoms) which may have a substituent. Examples of substituents includeR of formula (CDN1)¹The same as those in (1).

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

The compound represented by formula (CDN2) may be further modified. For example, it may be epoxidized, specifically, a compound having a structure in which a hydroxyl group of a compound represented by formula (CDN2) is substituted with the following group (EP), that is, a compound represented by the following formula (CDN 2-e).

In formula (CDN2-e), each R¹¹、R¹²、R¹³、R²¹、R²²、R²³、P21、P22、P23、L¹、L²And n is respectively related to R in the formula (CDN2)¹¹、R¹²、R¹³、R²¹、R²²、R²³、P21、P22、P23、L¹And L²And n is the same. In the formula (CDN2-e), L_EP1、L_EP2And L_EP3Each independently represents a single bond or a divalent linking group. In the case where n is 2 or more, each L in the form of a complex number_EP2May be the same group or different groups.

In the formula (CDN2-e), as represented by L_EP1、L_EP2And L_EP3The divalent linking group represented is preferably exemplified and exemplified by L in the formula (CDN1-e)_EPThe same groups of the divalent linking groups indicated.

The polymer in which the compound represented by the formula (CDN1) is polymerized may be, for example, a polymer in which at least three or more compounds represented by the formula (CDN1) are three-dimensionally crosslinked and polymerized with or without a linking group. Examples of the polymer in which the compound represented by the formula (CDN1) is three-dimensionally crosslinked and polymerized include a compound represented by the following formula.

In the formula, each R¹⁰、R²⁰And P20 with R in formula (CDN1) respectively¹、R²As with P2. L is¹⁰Represents a single bond or a divalent linking group. R in the form of a plurality¹⁰R, which may be identical or different, in the form of a plurality²⁰L, which may be identical or different, and which is present in plural form¹⁰May be the same group or different groups. P20 in plural form may be the same number or different numbers.

In the formula, from L¹⁰Examples of the divalent linking group represented include alkylene groups (preferably alkylene groups having 2 to 30 carbon atoms, and more preferably alkylene groups having 5 to 20 carbon atoms) which may have a substituent. Examples of substituents include R with formula (CDN1)¹The same as those in (1).

The compound represented by formula (iv) may be further modified, for example, it may be epoxidized. Specifically, it may be a compound having a structure in which a hydroxyl group of the compound represented by formula (la) is substituted with a group (EP), and examples thereof include a compound represented by the following formula, i.e., a polymer in which the compound represented by formula (CDN1-e) is three-dimensionally crosslinked and polymerized.

In the formula, each R¹⁰、R²⁰And P²⁰Respectively with R in formula (CDN1-e)¹、R²As with P2. L is¹⁰Represents a single bond or a divalent linking group. R in the form of a plurality¹⁰R, which may be identical or different, in the form of a plurality²⁰L, which may be identical or different, and which is present in plural form¹⁰May be the same group or different groups. P20 in plural form may be the same number or different numbers.

In the formula, from L¹⁰Examples of the divalent linking groups includeA substituted alkylene group (preferably an alkylene group having 2 to 30 carbon atoms, and more preferably an alkylene group having 5 to 20 carbon atoms). Examples of substituents include R with formula (CDN1)¹The same as those in (1).

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 the puncture impact strength of the resin molded article.

As the cardanol compound, a commercially available product can 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, and LB-7000, LB-7250, and CD-5L, prepared by Tohoku Chemical Industries, Ltd.

Examples of commercially available products of cardanol compounds with epoxy groups include Nc-513, Nc-514S, Nc-547, LITE513E and Ultra LTE 513 prepared from Cardolite.

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

In the case of using a cardanol compound having an epoxy group as the cardanol compound, the epoxy equivalent weight is preferably 300 to 500, more preferably 350 to 480, and still 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 compounds

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

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

In the formula (6), R⁶¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, R⁶²Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms. As a group consisting of R⁶¹Specific forms and preferred forms of the group represented are exemplified by R in the formula (1)¹¹The representation is in the same form. From R⁶²The group represented may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group. From R⁶²The group represented may be a linear aliphatic hydrocarbon group, may be a branched aliphatic hydrocarbon group, may be an aliphatic hydrocarbon group containing an alicyclic ring, and is preferably a linear aliphatic hydrocarbon group. From R⁶²The group represented may be a group in which a hydrogen atom in the aliphatic hydrocarbon 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, and is preferably an unsubstituted group. From R⁶²The group represented preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and still more 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), and modified products of fatty acid esters (e.g., epoxidized fatty acid esters). Examples of the above esters include monoesters, diesters, triesters, and polyesters. Among them, dicarboxylic acid diesters (adipic acid diester, sebacic acid diester, azelaic acid diester, phthalic acid diester, etc.) are preferable.

As the plasticizer (C), adipate is preferable. The adipate ester has high affinity with the resin (particularly, cellulose acylate (a)) and is dispersed in a state almost uniform with the resin (particularly, cellulose acylate (a)), so that the thermal fluidity is more improved than other plasticizers.

In the ester compound as the plasticizer (C) included in the resin composition according to the exemplary embodiment, the molecular weight (or weight average molecular weight) is preferably 200 to 2000, more preferably 250 to 1500, and still more preferably 280 to 1000. The weight average molecular weight of the ester compound is a value measured according to the method for measuring the weight average molecular weight of the cellulose acylate (a), unless otherwise specified.

Examples of adipic acid esters include adipic acid diesters and adipic acid polyesters. Specific examples thereof include adipic acid diesters represented by the formula (AE) and adipic acid polyesters represented by the formula (APE).

In formula (AE), R^AE1And R^AE2Each independently represents an alkyl group or a polyoxyalkyl group [ - (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 formula (APE), R^AE1And R^AE2Each independently being alkyl or 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), R^AE3Represents an alkylene group.

m1 represents an integer of 1 to 10, and m2 represents an integer of 1 to 20.

In the formulae (AE) and (APE), from 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 still more preferably an alkyl group having 8 carbon atoms. From R^AE1And R^AE2The alkyl group represented may be any of a straight-chain alkyl group, a branched alkyl group and a cyclic alkyl group, and is preferably a straight-chain alkyl group or a branched alkyl group.

In the formulae (AE) and (APE), in the reaction of R^AE1And R^AE2Polyoxyalkyl [ - (C) of_xH_2x-O)_y-R^A1]In the middle, byR^A1The alkyl group represented is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. From R^A1The alkyl group represented may be any of a straight-chain alkyl group, a branched alkyl group and a cyclic alkyl group, and is preferably a straight-chain alkyl group or a branched alkyl group.

In formula (APE), from R^AE3The alkylene group represented is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. The alkylene group may be any of a straight-chain alkyl group, a branched alkyl group and a cyclic alkyl group, and is preferably a straight-chain alkyl group or a branched alkyl group.

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

In the formulae (AE) and (APE), the groups represented by each code may be substituted with a substituent. Examples of the substituent include an alkyl group, an aryl group and a hydroxyl group.

The molecular weight (or weight average molecular weight) of the adipate is preferably 250 to 2000, more preferably 280 to 1500, and still more 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).

As the adipate ester, a mixture of the adipate ester and other components may be used. As a commercially available product of the mixture, daibatt 101 prepared by Daihachi Chemical Industry co., ltd., and the like can be exemplified.

As the hydrocarbon group at the terminal of the fatty acid ester (for example, citrate ester, sebacate ester, azelate ester, phthalate ester, and acetate ester), an aliphatic hydrocarbon group is preferable, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 4 to 10 carbon atoms is more preferable, and an alkyl group having 8 carbon atoms is still more preferable. The alkyl group may be any of a straight-chain alkyl group, a branched alkyl group and a cyclic alkyl group, and is preferably a straight-chain alkyl group or a branched alkyl group.

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

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

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

Examples of commercially available products of epoxidized fatty acid esters include ADEKA SIZER D-32, D-55, O-130P and O-180A (manufactured by ADEKA CORPORATION), 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 polyester unit of the polyetherester compound may be aromatic or aliphatic (including alicyclic), and the polyether unit of the polyetherester compound may be aromatic or aliphatic (including alicyclic). The weight ratio of the polyester unit to the polyether unit is, for example, 20:80 to 80: 20. The molecular weight (or weight average molecular weight) of the polyetherester compound is preferably 250 to 2000, more preferably 280 to 1500, and still more preferably 300 to 1000. Examples of commercially available products of polyether ester compounds include ADEKA SIZERRS-1000 (manufactured by ADEKA CORPORATION).

As the polyether compound having at least one unsaturated bond in the molecule, a polyether compound having an allyl group at the terminal thereof is exemplified, and a polyalkylene glycol allyl ether is preferable. The molecular weight (or 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 still more 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 according to the exemplary embodiment preferably further includes a thermoplastic elastomer (D) which is at least one thermoplastic elastomer selected from the group consisting of a polymer (D1) having a core-shell structure having 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 a surface of the core layer, a polymer (D2) having a core layer and a shell layer containing a polymer of an alkyl (meth) acrylate on a surface of the core layer, an olefin polymer (D3) which is a polymer of α -olefin and an alkyl (meth) acrylate and contains 60% by weight or more of a structural unit derived from the α -olefin, a styrene-ethylene-butadiene-styrene copolymer (D4), a polyurethane (D5), and a polyester (D6).

Component (D) is, for example, a thermoplastic elastomer having elasticity at ordinary temperature (25 ℃) and having softening properties similar to those of a thermoplastic resin at high temperature.

From the viewpoint of puncture impact strength of the obtained resin molded article, the thermoplastic elastomer (D) is preferably at least one thermoplastic elastomer selected from the group consisting of: a core layer containing a butadiene polymer, a polymer (d1) having a core-shell structure, which 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 a surface of the core layer; a polymer (d2) having a core-shell structure, which has a core layer and a shell layer of a polymer containing an alkyl (meth) acrylate on the surface of the core layer; styrene-ethylene-butadiene-styrene copolymer (d 4); polyurethane (d 5); and polyester (d 6); more preferably, the thermoplastic elastomer (D) comprises at least one thermoplastic elastomer selected from the group consisting of: a core layer containing a butadiene polymer, a polymer (d1) having a core-shell structure, which 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 a surface of the core layer; a polymer (d2) having a core-shell structure, which has a core layer and a shell layer of a polymer containing an alkyl (meth) acrylate on the surface of the core layer; and still more preferably the thermoplastic elastomer (D) comprises a polymer (D2) having a core-shell structure, which has a core layer and a shell layer comprising a polymer of an alkyl (meth) acrylate on the surface of the core layer.

In addition, the thermoplastic elastomer (D) is preferably a particulate thermoplastic elastomer from the viewpoint of puncture impact strength of the resulting resin molded article. That is, the resin composition according to the exemplary embodiment preferably includes thermoplastic elastomer particles as the thermoplastic elastomer (D) from the viewpoint of puncture impact strength of the obtained resin molded article.

(Polymer having core-Shell Structure (d 1): component (d1))

The polymer having a core-shell structure (d1) is a polymer having a core-shell structure having a core layer and a shell layer on a surface of the core layer. The polymer having a core-shell structure (d1) is a polymer having a core layer as an innermost layer and a shell layer as an outermost layer (specifically, a polymer in which the shell layer is obtained by graft polymerizing a polymer of alkyl (meth) acrylate to a polymer which becomes the core layer). One or more other layers (e.g., 1 to 6 other layers) may be provided between the core layer and the shell layer. In the case where other layers are provided between the core layer and the shell layer, the polymer having a core-shell structure (d1) is a polymer obtained by graft polymerizing a plurality of polymers to a polymer which becomes the core layer to form a multilayered 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.

As examples of the (meth) acrylic rubber, there may be cited polymer rubbers obtained by polymerizing (meth) acrylic components (alkyl esters of (meth) acrylic acid having 2 to 8 carbon atoms, and the like), examples of the silicone rubber include rubbers made of siloxane components (polydimethylsiloxane, polyphenylsiloxane, and the like), examples of the styrene rubber include polymer rubbers obtained by polymerizing styrene components (styrene, α -methylstyrene, and the like), examples of the conjugated diene rubber include polymer rubbers obtained by polymerizing conjugated diene components (butadiene, isoprene, and the like), examples of the α -olefin rubber include polymer rubbers obtained by polymerizing α -olefin components (ethylene, propylene, and 2-methacrylic), examples of the copolymer rubbers include copolymer rubbers obtained by polymerizing two or more (meth) acrylic components, copolymer rubbers obtained by polymerizing (meth) acrylic components and siloxane components, and copolymer rubbers obtained by polymerizing (meth) acrylic components, conjugated diene, and styrene components.

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, and octadecyl (meth) acrylate. 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 and halogeno.

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

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, and 4-glycidylstyrene.

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

In the case where other layers are provided between the core layer and the shell layer, examples of the other layers include the polymer layers described for the shell layer.

The weight ratio of the shell layer is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, and still more preferably 5 to 15% by weight, relative to the entire core-shell structure.

The average primary particle diameter of the polymer having a core-shell structure is not particularly limited, and is preferably from 50nm to 500nm, more preferably from 50nm to 400nm, still more preferably from 100nm to 300nm, and particularly preferably from 150nm to 250nm, from the viewpoint that the effect of improving toughness is easily obtained by adding component (B). The average primary particle diameter refers to a value measured by the following method. The average primary particle diameter is a number-uniform primary particle diameter which is an average of primary particle diameters of more than 100 particles. Each primary particle size is the maximum diameter in each primary particle, and is measured by observing the particles with a scanning electron microscope. Specifically, the average primary particle diameter is obtained by observing the dispersion form of the polymer having a core-shell structure in the resin composition with a scanning electron microscope.

The polymer having a core-shell structure (d1) can be prepared by a known method. As a known method, an emulsion polymerization method can be mentioned. Specifically, the following method will be exemplified as the preparation method. First, the core particle (core layer) is prepared by emulsion polymerization of a monomer mixture, and then the other monomer mixture is emulsion polymerized in the presence of the core particle (core layer) to form a polymer having a core-shell structure in which a shell layer is formed around the core particle (core layer). In the case where other layers are formed between the core layer and the shell layer, emulsion polymerization of other monomer mixtures is repeated to obtain a polymer having a core-shell structure composed of the target core layer, other layers, and shell layer.

Examples of commercially available products of the polymer having a core-shell structure (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 Limited, "STAPHYLOID" (registered trademark) manufactured by Aica Kogyo company, Limited, and "PARAFACE" (registered trademark) manufactured by KURAY Co., Ltd.

(Polymer having core-Shell Structure (d 2): component (d2))

The polymer having a core-shell structure (d2) is a polymer having a core-shell structure having a core layer and a shell layer on a surface of the core layer. The polymer having a core-shell structure (d2) is a polymer having a core layer as an innermost layer and a shell layer as an outermost layer (specifically, a polymer obtained by graft polymerizing a styrene polymer or an acrylonitrile-styrene polymer to a core layer containing a butadiene polymer to form a shell layer). One or more other layers (e.g., 1 to 6 other layers) may be provided between the core layer and the shell layer. In the case where other layers are provided between the core layer and the shell layer, the polymer having a core-shell structure (d3) is a polymer obtained by graft polymerizing a plurality of polymers to a polymer which becomes the core layer to form a multilayered polymer.

In the case where the core layer is a copolymer of butadiene and other monomers, examples of the other monomers include vinyl aromatic compounds, 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) may be used alone or two or more thereof may be used in combination.

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

In the butadiene polymer contained in the core layer, the proportion of the structural unit derived from butadiene is preferably 60% by weight to 100% by weight (preferably 70% by weight to 100% by weight), and the proportion of the structural unit derived from the other monomer (preferably styrene component) is preferably 0% by weight to 40% by weight (preferably 0% by weight to 30% by weight). For example, as the proportion of the structural unit derived from each monomer constituting the butadiene polymer, butadiene is 60 to 100% by weight, styrene is 0 to 40% by weight, and divinylbenzene may be contained in an amount of 0 to 5% by weight with respect to the total amount of styrene and divinylbenzene.

The shell layer containing a styrene polymer is not particularly limited as long as the shell layer contains a polymer obtained by polymerizing a styrene component, and may be a shell layer of a homopolymer of styrene or a copolymer of styrene and other monomers. Examples of the styrene component include the same components as the styrene component 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.

The alkyl (meth) acrylate may be used alone, or two or more thereof may be used in combination. 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 may be a copolymer in which the styrene component is 85 to 100% by weight and the other monomer component (preferably, alkyl (meth) acrylate) is 0 to 15% by weight.

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 effect of improving toughness 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 a polymer of an alkyl (meth) acrylate 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 copolymers having an acrylonitrile component of 10 to 80% by weight and a styrene component of 20 to 90% by weight. Examples of the styrene component copolymerized with the acrylonitrile component include the same components as those 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.

In the case where other layers are provided between the core layer and the shell layer, examples of the other layers include the polymer layers described for the shell layer.

The weight ratio of the shell layer is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, and still more preferably 5 to 15% by weight, relative to the entire core-shell structure.

Among the components (d2), examples of commercially available products of the polymer having a core-shell structure (d2) having a core layer containing a butadiene polymer and a shell layer containing a styrene polymer on the core layer include "METABLEN" (registered trademark) manufactured by Mitsubishi Chemical Corporation, "KANE ACE" (registered trademark) manufactured by Kaneka Corporation, "Clearstrength" (registered trademark) manufactured by Arkema, and "PARALOID" (registered trademark) manufactured by Dow Chemical Japan Limited. Examples of commercially available products of the polymer of core-shell structure (d3) having a core layer containing a butadiene polymer and a shell layer containing an acrylonitrile-styrene polymer on the surface of the core layer among the component (d2) include "blendex" (registered trademark) produced by Galata Chemicals and "ELIX" produced by ELIX POLYMERS.

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

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

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

Examples of the alkyl (meth) acrylate 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, and octadecyl (meth) acrylate from the viewpoint that the effect of improving toughness is easily obtained by adding component (B), the alkyl (meth) acrylate having an alkyl chain of 1 to 8 carbon atoms is preferable, the alkyl (meth) acrylate having an alkyl chain of 1 to 4 carbon atoms is more preferable, and the alkyl (meth) acrylate having an alkyl chain of 1 carbon atom or 2 carbon atoms is still more preferable.

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

From the viewpoint of easily obtaining the effect of improving toughness by adding component (B), in the olefin polymer, the structural unit derived from α -olefin is preferably 60 to 97% by weight, and more preferably 70 to 85% by weight.

The olefin polymer may have other structural units than the structural unit derived from α -olefin and the structural unit derived from alkyl (meth) acrylate here, the other structural units may be 10% by weight or less with respect to the entire 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 known styrene-ethylene-butadiene-styrene copolymers. The copolymer (d4) may be a styrene-ethylene-butadiene-styrene copolymer and a hydrogenated product thereof.

The copolymer (d4) is preferably a hydrogenated product of a styrene-ethylene-butadiene-styrene copolymer from the viewpoint that the effect of improving toughness is easily obtained by adding the component (B). From the same viewpoint, the copolymer (d4) may be a block copolymer, for example, it is preferably a copolymer (triblock copolymer of styrene-ethylene/butylene-styrene) having a block having a styrene moiety at both ends and a partial block containing central ethylene/butylene by hydrogenating at least a part of the double bonds of a butadiene moiety. The ethylene/butylene block portion of the styrene-ethylene/butylene-styrene copolymer may be a random copolymer.

The copolymer (d4) is obtained by a known method. In the case where the copolymer (d4) is a hydrogenated product of a styrene-ethylene-butadiene-styrene copolymer, for example, the copolymer (d4) is obtained by hydrogenating the butadiene moiety of a styrene-butadiene-styrene block copolymer in which the conjugated diene moiety is composed of 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) can be obtained, for example, by reacting a polyol component (polyether polyol, polyester polyol, polycarbonate polyol, or the like), an organic isocyanate component (aromatic diisocyanate, aliphatic (including alicyclic) diisocyanate, or the like), and, if necessary, a chain extender (aliphatic or (including alicyclic) diol, or the like). The polyol component may be used alone, or two or more thereof may be used in combination, and the organic isocyanate component may be used alone, or two or more thereof may be used in combination.

From the viewpoint of easily obtaining the effect of improving toughness by adding component (B), polyurethane (d5) is preferably an aliphatic polyurethane. As the aliphatic polyurethane, for example, an aliphatic polyurethane obtained by reacting a polyol component containing a polycarbonate polyol with an isocyanate component containing an aliphatic diisocyanate is preferable.

The polyurethane (d5) can be obtained by reacting a polyol component with an organic isocyanate component such that the NCO/OH ratio in the raw materials at the time of synthesizing the polyurethane is in the range of, for example, 0.90 to 1.5. The polyurethane (d5) is obtained by known methods (e.g., one-shot method and pre-polymerization method).

Examples of commercially available products of polyurethane (d5) include "Estane" (registered trademark) manufactured by Lubrizol and "Elastollan" (registered trademark) manufactured by BASF. "Desmopan" (registered trademark) produced by Bayer is exemplified.

(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 effect of improving toughness 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 (polyether esters or polyester esters, etc.). Specific examples thereof include polyester copolymers having a hard segment composed of polyester units and a soft segment composed of polyester units; a polyester copolymer having a hard segment composed of polyester units and a soft segment composed of polyether units; and a polyester copolymer having a hard segment composed of polyester units and a soft segment composed of polyether units and polyester units. The weight ratio of the hard segment to the soft segment (hard segment/soft segment) of the polyester copolymer may be, 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) is obtained by using a known method. The polyester copolymer is preferably a linear polyester copolymer. The polyester copolymer is obtained by, for example, a method of esterifying or transesterifying a dicarboxylic acid component having 4 to 20 carbon atoms, a diol component having 2 to 20 carbon atoms and a polyalkylene glycol component (including alkylene oxide adducts of polyalkylene glycols) having a number average molecular weight of 300 to 20000, and a method of esterifying or transesterifying these components to prepare an oligomer and then polycondensing the oligomer. In addition, for example, a method of esterifying or transesterifying 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 can be exemplified. 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, the dicarboxylic acid component of the polyester copolymer preferably uses a dicarboxylic acid component having an aromatic ring from the viewpoint that the effect of improving toughness is easily obtained by adding the component (B). Each of the diol component and the polyalkylene glycol component preferably uses an aliphatic diol component and an aliphatic polyalkylene glycol component.

Examples of commercially available products of the polyester (d6) include "perprene" (registered trademark) manufactured by Toyobo co., ltd., and "HYTREL" (registered trademark) manufactured by Du Pont-Toray co., ltd.).

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

[ contents or content ratios of the above-mentioned respective Components ]

The resin composition according to the exemplary embodiment contains a resin having a carbon atom derived from biomass (component (a), etc.), and if necessary, contains component (B), component (C), and component (D), and other component (E) described below. The content or content ratio of each component of the resin composition according to the exemplary embodiment is preferably within the following range (all by mass) from the viewpoint of puncture impact strength of the resulting resin molded article.

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)

The content of the resin having a carbon atom derived from biomass in the resin composition according to the exemplary embodiment is preferably 50% by weight or more, more preferably 60% by weight or more, and still more preferably 70% by weight or more, with respect to the total mass of the resin composition.

The content of the component (a) in the resin composition according to the exemplary embodiment is preferably 50% by weight or more, more preferably 60% by weight or more, and still more preferably 70% by weight or more, with respect to the total mass of the resin composition. In addition, the content of the component (a) in the resin composition according to the exemplary embodiment is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and still more preferably 95 to 100 parts by mass with respect to 100 parts by mass of the content of the resin having a carbon atom derived from biomass.

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

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

The content of the component (D) in the resin composition according to the exemplary embodiment is preferably 1 to 20% by weight, more preferably 3 to 15% by weight, and still more preferably 5 to 10% by weight, 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, and still more preferably 0.07 or less (C/A)^Bio) Less than or equal to 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, and still more 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) Preferably 0.025. ltoreq. (D/A)^Bio) 0.3 or less, more preferably 0.05 or less (D/A)^Bio) 0.2 or less, and still more preferably 0.07 or less (D/A)^Bio) Less than or equal to 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, and still more preferably 0.07. ltoreq. D/A.ltoreq.0.1.

[ other component (E) ]

The resin composition according to an 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) is preferably 15% by weight or less, and more preferably 10% by weight or less, relative to the total content of the resin composition.

Examples of the other component (E) include flame retardants, compatibilizers, oxidation inhibitors, stabilizers, mold release agents, light stabilizers, weather-resistant agents, colorants, pigments, modifiers, drip inhibitors, antistatic agents, hydrolysis inhibitors, fillers, reinforcing agents (for example, 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 for preventing acetic acid release (for example, oxides such as magnesium oxide and alumina, metal hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide and hydrotalcite, calcium carbonate and talc), reactive trapping agents (for example, epoxy compounds, acid anhydride compounds and carbodiimides). The content of each of the other components (E) is preferably 0% by weight to 5% by weight with respect to the total amount of the resin composition. Here, "0% by weight" means that no other component (E) is contained.

The resin composition according to the exemplary embodiment may contain other resins as the other component (E) in addition to the resin having a carbon atom derived from biomass (component (a), etc.), the component (B), the component (C), and the component (D). However, in the case where other resin is contained, the content of the other resin is preferably 5% by weight or less, and more preferably less than 1% by weight, relative to the total amount of the resin composition. It is particularly preferred that no other resin (i.e., 0 wt%) is contained in the resin composition. Examples of the other resins include thermoplastic resins in the related art, and specific examples thereof include: a polycarbonate resin; a polypropylene resin; a polyester resin; a polyolefin resin; a polyester carbonate resin; polyphenylene ether resins; 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 polyoxamide resin; a vinyl polymer or copolymer obtained by polymerizing or copolymerizing one or more vinyl monomers selected from the group consisting of an aromatic alkenyl compound, a methacrylate, an acrylate, and a vinyl cyanide compound; a diene-aromatic alkenyl compound copolymer; vinyl cyanide-diene-aromatic alkenyl compound copolymers; aromatic alkenyl compound-diene-vinyl cyanide-N-phenyl maleimide copolymer; vinyl cyanide- (ethylene-diene-propylene (EPDM)) -aromatic alkenyl compound copolymers; vinyl chloride resin; and chlorinated vinyl chloride resins. These resins may be used alone, or two or more thereof may be used in combination.

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 polyol, a ring-opening polycondensate of a cyclic lactam, and a polymer obtained by polymerizing lactic acid through an ester bond.

Further, the resin composition according to the exemplary embodiment preferably includes an oxidation inhibitor or a stabilizer as the other component (E). The oxidation inhibitor or stabilizer preferably comprises at least one compound (e3) selected from the group consisting of hindered phenol compounds, tocopherol compounds, tocotrienol compounds, phosphite compounds and hydroxylamine compounds. The compound (e3) may be used alone or in combination of two or more, but it is preferably used in combination from the viewpoint of puncture impact strength of the obtained resin molded article. The form in which two or more thereof are used in combination may be any one of the forms in which two or more thereof are used in combination in the same group (for example, two or more hindered phenol compounds), and the form in which two or more thereof are used in combination with other groups (for example, hindered phenol compounds and tocopherol compounds). From the viewpoint of puncture impact strength of the resulting resin molded article, a form in which two or more thereof are used in combination is preferably a form in which at least one selected from the group consisting of a hindered phenol compound and a hydroxylamine compound and a phosphite compound is used in combination, and more preferably a form in which a hindered phenol compound and a phosphite compound are used in combination. The content of the compound (e3) in the resin composition according to the exemplary embodiment is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, and still more preferably 0.1 to 1% by weight, 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" prepared by BASF, "ADK STAB AO-80", "ADKSTAB AO-60", "ADK STAB AO-50", "ADK STAB AO-40", "ADK STAB AO-30", "ADK STAB AO-20" and "ADK STAB AO-330" prepared by ADEKA CORPORATION, and "Sumilizer GA-80", "Sumilizer GM" and "Sumilizer GS" prepared by Sumitomo Chemical Company, Limited; phosphite compounds, such as "Irgafos 38" (bis (2, 4-di-tert-butyl-6-methylphenyl) -ethyl-phosphite), "Irgafos 168", "Irgafos TNPP" and "Irgafos P-EPQ", prepared by BASF; and hydroxylamine compounds such as "Irgastab FS-042" by BASF.

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

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

[ method for preparing resin composition ]

Examples of the method of producing the resin composition according to the exemplary embodiment include a method of mixing and melt-kneading a resin having a carbon atom derived from a biomass (component (a) and the like) and, if necessary, component (B), component (C), component (D), and other component (E); and a method of dissolving the resin having a carbon atom derived from biomass (component (a) and the like) and, if necessary, component (B), component (C), component (D) and other component (E) in a solvent. The method for melt-kneading 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, and a co-mixer.

< resin molded article >

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

From the viewpoint of a high degree of freedom in shape, injection molding is preferable as a method of molding the resin molded article according to the exemplary embodiment. Therefore, the resin molded article according to the exemplary embodiment is preferably an injection molded article obtained by injection molding from the viewpoint of a high degree of freedom in shape.

The cylinder temperature at the time of injection molding the resin molded article according to the exemplary embodiment is preferably 160 ℃ to 280 ℃, and more preferably 180 ℃ to 240 ℃, for example. The mold temperature at the time of injection molding the resin molded article according to the exemplary embodiment is preferably, for example, 40 ℃ to 90 ℃, and more preferably 40 ℃ to 60 ℃. Injection molding of a resin molded article according to an exemplary embodiment may be performed by using commercially available equipment such as NEX500 manufactured by Nissei Plastic Industrial co., ltd., NEX150 manufactured by Nissei Plastic Industrial co., ltd., NEX7000 manufactured by Nissei Plastic Industrial co., ltd., PNX40 manufactured by Nissei Plastic Industrial co., ltd., pnd. and SE50D manufactured by Sumitomo health Industries, ltd.

The molding method for obtaining the resin molded article according to the exemplary embodiment is not limited to the above-described injection molding, and for example, extrusion molding, blow molding, hot press molding, calendar molding, coating molding, cast molding, dip molding, vacuum molding, transfer molding, and the like may be applied.

The resin-molded article according to the exemplary embodiment is suitable for applications such as electronic and electrical equipment, office equipment, home appliances, automotive interior materials, toys, and containers. Specific applications of the resin molded article according to the exemplary embodiment include housings of electronic and electric appliances or home appliances; various components of electronic and electrical equipment or household appliances; an automotive interior trim part; assembling the toy in sections; a plastic model kit; a storage case for CD-ROMs or DVDs; tableware; beverage bottles; a food tray; a packaging material; a film; and a sheet.