Resin composition and resin molded article

文档序号：1412173 发布日期：2020-03-10 浏览：23次中文

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 2019-03-04 设计创作，主要内容包括：本申请涉及一种树脂组合物和包含该树脂组合物的树脂成型品。所述树脂组合物包含具有生物质来源的碳原子的树脂,所述树脂组合物满足条件(1A)和(2)：(1A)使用由所述树脂组合物制备的各自具有200g的重量和80mm×200mm的接触面积的试件,在移动速度为100mm/分钟的条件下,根据ISO 8295:1995测量,静态摩擦系数为0.2至0.4；和(2)使用由所述树脂组合物制备的厚度为4mm且宽度为10mm的试件,根据ISO 527-1:2012测量,拉伸弹性模量为1,400MPa至2,500MPa。(The present application relates to a resin composition and a resin molded article including the same. The resin composition includes a resin having a biomass-derived carbon atom, and satisfies the conditions (1A) and (2): (1A) using test pieces each having a weight of 200g and a contact area of 80mm × 200mm prepared from the resin composition, the static friction coefficient is 0.2 to 0.4 as measured according to ISO8295:1995 under the condition that the moving speed is 100 mm/min; and (2) a tensile modulus of elasticity of 1,400MPa to 2,500MPa, measured according to ISO527-1:2012, using a test piece prepared from the resin composition and having a thickness of 4mm and a width of 10 mm.)

1. A resin composition comprising a resin having biomass-derived carbon atoms,

the resin composition satisfies conditions (1A) and (2):

(1A) using test pieces each having a weight of 200g and a contact area of 80mm × 200mm prepared from the resin composition, the static friction coefficient measured according to ISO8295:1995 is 0.2 to 0.4; and

(2) the tensile modulus of elasticity measured according to ISO527-1:2012 of a test piece prepared from the resin composition and having a thickness of 4mm and a width of 10mm is 1,400MPa to 2,500 MPa.

2. A resin composition comprising a resin having biomass-derived carbon atoms,

the resin composition satisfies conditions (1B) and (2):

(1B) using test pieces each having a weight of 200g and a contact area of 80mm × 200mm prepared from the resin composition, the dynamic friction coefficient measured according to ISO8295:1995 under the condition that the moving speed is 100 mm/min is 0.1 to 0.3; and

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

4. The resin composition according to claim 1 or 3, which satisfies the condition (3): (3) the ratio of the static coefficient of friction (SFC) to the tensile modulus of Elasticity (EM) is 0.00009 < (SFC)/(EM) < 0.0003.

5. The resin composition according to claim 2, which satisfies the condition (4): (4) the ratio of the coefficient of Dynamic Friction (DFC) to the tensile modulus of Elasticity (EM) is 0.00004 < (DFC)/(EM) < 0.00018.

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

7. The resin composition according to claim 6, wherein the cellulose acylate (A) is at least one of Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB).

8. The resin composition according to claim 6 or 7, wherein the content of the cellulose acylate (A) is 50% by mass or more with respect to the resin composition.

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

Wherein the content of the first and second substances,

on-lineIn the formula (1), R¹¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, R¹²Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms;

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

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

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

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

10. The resin composition according to claim 9, wherein the resin having a biomass-derived carbon atom contains the cellulose acylate (a), and a mass ratio (B/a) of the ester compound (B) to the cellulose acylate (a) is from 0.0025 to 0.1.

11. The resin composition according to claim 9 or 10, wherein the ester compound (B) and the resin (a) having a biomass-derived carbon atom^Bio) Mass ratio (B/A) of^Bio) Is 0.002 to 0.08.

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

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

wherein, in the general formula (6),

R⁶¹represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms; and

R⁶²represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

14. The resin composition according to claim 12 or 13, wherein the plasticizer (C) comprises a cardanol compound.

15. The resin composition according to any one of claims 12 to 14, wherein the plasticizer (C) and the resin having a biomass-derived carbon atom (a) are mixed^Bio) Mass ratio (C/A) of^Bio) Is 0.04 to 0.18.

16. The resin composition according to any one of claims 1 to 15, wherein the resin composition comprises a thermoplastic elastomer (D).

17. The resin composition according to claim 16, wherein the thermoplastic elastomer (D) comprises at least one selected from the group consisting of:

a core-shell structure polymer (d1) having a core layer and a shell layer comprising an alkyl (meth) acrylate polymer on the surface of the core layer; and

an olefin polymer (d2) which is a polymer of α -olefin and alkyl (meth) acrylate and comprises 60 mass% or more of a structural unit derived from the α -olefin.

18. A resin molded article comprising the resin composition as defined in any one of claims 1 to 17.

19. The resin molded article according to claim 18, 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

Generally, various resin compositions have been provided and used for various purposes. In particular, the resin composition is used for various parts and housings of household appliances and automobiles. 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 of biological origin other than fossil resources) are used, and an example of one of generally known resins having carbon atoms of biomass origin includes cellulose acylate.

As ｃA conventional resin composition, JP-A-10-095862 discloses "ｃA cellulose acetate film which is ｃA cellulose acetate film having an average degree of acetylation of 58.0% to 62.5% (wherein the haze of the film converted to ｃA thickness of 80 μm is 0.6% or less, and the coefficient of dynamic friction of the film surface is 0.40 or less)".

Further, JP-A-2003-305787 discloses an "integrated film comprising ｃA transparent polymer support having surfaces for receiving polymer beads, wherein the swelling ratio, size and deposition of the beads are selected so that the static friction coefficient of one surface is 0.68 or less and the internal haze value is 0.1 or less".

Disclosure of Invention

An object of the present invention is to provide a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with a resin composition which contains a resin having a biomass-derived carbon atom and does not satisfy the condition (1A) or (2), or a resin composition which contains a resin having a biomass-derived carbon atom and does not satisfy the condition (1B) or (2).

Specific means for solving the problems include the following aspects.

[1] According to an aspect of the present disclosure, there is provided a resin composition comprising a resin having a biomass-derived carbon atom, the resin composition satisfying the conditions (1A) and (2):

[2] A resin composition comprising a resin having a biomass-derived carbon atom, the resin composition satisfying the conditions (1B) and (2):

[3] The resin composition according to any one of [1] and [2], wherein the content of biomass-derived carbon atoms in the resin composition determined in ASTM D6866: 2012 is 30% or more based on the total amount of carbon atoms in the resin composition.

[4] The resin composition according to [1] or [3], which satisfies the condition (3): (3) the ratio of the static coefficient of friction (SFC) to the tensile modulus of Elasticity (EM) is 0.00009 < (SFC)/(EM) < 0.0003.

[5] The resin composition according to [2], which satisfies the condition (4): (4) the ratio of the coefficient of Dynamic Friction (DFC) to the tensile modulus of Elasticity (EM) is 0.00004 < (DFC)/(EM) < 0.00018.

[6] The resin composition according to any one of [1] to [5], wherein the resin having a biomass-derived carbon atom comprises a cellulose acylate (A).

[7] The resin composition according to [6], wherein the cellulose acylate (A) is at least one of Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB).

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

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

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

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

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

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

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

[10] The resin composition according to [9], wherein the resin having a biomass-derived carbon atom contains the cellulose acylate (A), and a mass ratio (B/A) of the ester compound (B) to the cellulose acylate (A) is from 0.0025 to 0.1.

[11]According to [9]]Or [10]]The resin composition of (1), wherein the ester compound (B) and the resin having a biomass-derived carbon atom (A) are mixed^Bio) Mass ratio (B/A) of^Bio) Is 0.002 to 0.08.

[12] The resin composition according to any one of [1] to [11], further comprising a plasticizer (C).

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

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

[14] The resin composition according to [12] or [13], wherein the plasticizer (C) comprises a cardanol compound.

[15]According to [12]]To [14]]The resin composition of any one of, wherein the plasticizer (C) and the tree having a biomass-derived carbon atomFat (A)^Bio) Mass ratio (C/A) of^Bio) Is 0.04 to 0.18.

[16] The resin composition according to any one of [1] to [15], wherein the resin composition comprises a thermoplastic elastomer (D).

[17] The resin composition according to [16], wherein the thermoplastic elastomer (D) comprises at least one selected from the group consisting of a core-shell structure polymer (D1) having a core layer and a shell layer comprising an alkyl (meth) acrylate polymer on the surface of the core layer, and an olefin polymer (D2) which is a polymer of α -olefin and an alkyl (meth) acrylate and comprises 60 mass% or more of a structural unit derived from the α -olefin.

[18] A resin molded article comprising the resin composition according to any one of [1] to [17 ].

[19] The resin molded article according to [18], wherein the resin molded article is an injection molded article.

According to the embodiment of [1], there is provided a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with a resin composition containing a resin having a biomass-derived carbon atom and not satisfying the condition (1A) or (2).

According to the embodiment of [2], there is provided a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with a resin composition containing a resin having a biomass-derived carbon atom and not satisfying the condition (1B) or (2).

According to the embodiment of [3], there is provided a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with a resin composition in which the content of biomass-derived carbon atoms in the resin composition determined in ASTM D6866: 2012 is less than 30 mass% based on the total amount of carbon atoms in the resin composition.

According to the embodiment of [4], there is provided a resin composition from which a resin molded article having a high puncture strength can be obtained as compared with a resin composition which does not satisfy the condition (3).

According to the embodiment of [5], there is provided a resin composition from which a resin molded article having a high puncture strength can be obtained as compared with a resin composition which does not satisfy the condition (4).

According to the embodiment of [6], there is provided a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with a resin composition containing only polylactic acid as a resin having a biomass-derived carbon atom.

According to the embodiment of [7], there is provided a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with a resin composition in which the cellulose acylate (A) is cellulose acetate.

According to the embodiment of [8], there is provided a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with a resin composition in which the content of the cellulose acylate (a) in the resin composition is less than 50% by mass.

According to [9]]The resin composition of (1), and a resin composition comprising only a resin having a biomass-derived carbon atom, and R¹¹、R²¹、R²²、R³¹、R³²、R⁴¹、R⁴²、R⁴³、R⁵¹、R⁵²、R⁵³And R⁵⁴A resin composition having at least one of the above compounds (A) and (B) wherein R is an ester compound (B) having no aliphatic hydrocarbon group¹²The number of carbon atoms of less than 9 or more than 28), a resin molded article having a high puncture strength can be obtained from the resin composition of the present invention.

According to the embodiment of [10], there is provided a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with a resin composition in which the mass 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 [11]In one embodiment, there is provided a resin composition, and a resin (A) in which an ester compound (B) and a resin having a biomass-derived carbon atom are mixed^Bio) Mass ratio (B/A) of^Bio) A resin molded article having a high puncture strength can be obtained from the resin composition of the present invention, compared with a resin composition of less than 0.002 or more than 0.08.

According to the embodiment of [12], [13], or [16], there is provided a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with a resin composition containing only a resin having a biomass-derived carbon atom and satisfying the conditions (1) and (2).

According to [ 14)]The plasticizer (C) contains only a compound selected from the group consisting of a cardanol compound, a dicarboxylic acid diester, a citric acid ester, a polyether compound having at least one unsaturated bond in the molecule, a polyether ester compound, a diol benzoate, and a compound represented by the following general formula (1) (wherein R is¹²Has a carbon number of 8 or less) and at least one member selected from the group consisting of epoxidized fatty acid esters, a resin molded article having a high puncture strength can be obtained from the resin composition of the present invention.

According to [15]]In one embodiment, there is provided a resin composition, and a resin (A) in which a plasticizer (C) and a resin having a biomass-derived carbon atom are used^Bio) Mass ratio (C/A) of^Bio) A resin molded article having a high puncture strength can be obtained from the resin composition of the present invention, compared with a resin composition of less than 0.04 or more than 0.18.

According to the embodiment of [17], there is provided a resin composition from which a resin molded article having high puncture strength can be obtained, as compared with the case where the thermoplastic elastomer (D) is a core-shell structure polymer (D3), a styrene-ethylene-butadiene-styrene copolymer (D4), a polyurethane (D5) or a polyester (D6) which will be described later.

According to the embodiment of [18], a resin molded article having high puncture strength is provided as compared with a resin composition containing a resin having a biomass-derived carbon atom and not satisfying the conditions (1A) or (2) or with a resin composition containing a resin having a biomass-derived carbon atom and not satisfying the conditions (1B) or (2).

According to the embodiment of [19], there is provided an injection-molded body having high puncture strength as compared with a resin composition which contains a resin having a biomass-derived carbon atom and does not satisfy the condition (1A) or (2) or a resin composition which contains a resin having a biomass-derived carbon atom and does not satisfy the condition (1B) or (2).

Detailed Description

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

In the numerical ranges described in stages in the exemplary embodiment, 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 of the numerical range of another numerical range. In addition, in the numerical ranges described in the exemplary embodiments, the upper limit value or the lower limit value in the numerical range may be replaced with the numerical value shown in the examples.

In exemplary embodiments, each component may comprise a plurality of corresponding substances. In the present disclosure, when referring to the amount of each component in a composition, unless otherwise specified, it refers to the total amount of the plurality of materials present in the composition when the plurality of materials corresponding to each component in the composition is present.

In an exemplary embodiment, "(meth) propionyl group" refers to at least one of propionyl group and methylpropionyl group, and "(meth) acrylate" refers to at least one of acrylate and methacrylate.

In an exemplary embodiment, the cellulose acylate (a), the cardanol compound (B), the compound (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 the first embodiment is a resin composition that contains a resin having a biomass-derived carbon atom and satisfies the conditions (1A) and (2).

(1A) Using test pieces each having a weight of 200g and a contact area of 80 mm. times.200 mm prepared from the resin composition, the static friction coefficient measured according to ISO8295:1995 was 0.2 to 0.4 under the condition that the moving speed was 100 mm/min.

(2) The tensile modulus of elasticity measured according to ISO527-1:2012 was 1,400MPa to 2,500MPa using test pieces prepared from the resin composition having a thickness of 4mm and a width of 10 mm.

The resin composition according to the first embodiment may contain other components such as an ester compound (B), a plasticizer (C), or a thermoplastic elastomer (D), which will be described later.

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

On the other hand, the resin composition according to the first embodiment has the above configuration, and therefore a resin molded article having high puncture strength can be obtained. The reason for this is presumed as follows.

In the resin composition having a static friction coefficient of 0.4 or less shown in condition (1A), the rotational force (torque) at the start of rotation of the rotary body (screw) tends to be suppressed in the course of kneading each raw material at the time of forming the resin molded article. Therefore, during kneading, local heat generation tends to be suppressed, and decomposition of a resin having a carbon atom derived from a biomass sensitive to heat (e.g., a plant-derived component) is also suppressed. Therefore, it is estimated that the puncture strength can be improved.

The resin molded article obtained from the resin composition satisfying the condition (2) has a moderately high tensile elastic modulus of 1,400MPa to 2,500 MPa. The resin molded article tends to suppress excessive density of the molded body due to flow of the resin composition in the kneading step, the molding step (e.g., injection molding step), and the like. Further, when the resin composition is molded, the molding load is difficult to apply, the molding is easy, and the dispersibility of the resin composition is not lowered. Therefore, since the resin molded article has an appropriate density and high dispersibility, it is presumed that a resin molded article having high puncture strength can be obtained.

As described above, it is estimated that the resin molded article obtained from the resin composition satisfying the conditions (1A) and (2) has high puncture strength.

In addition, the resin composition according to the second embodiment contains a resin having a biomass-derived carbon atom and satisfies the conditions (1B) and (2).

(1B) Using test pieces each having a weight of 200g and a contact area of 80 mm. times.200 mm prepared from the resin composition, the dynamic friction coefficient measured according to ISO8295:1995 was 0.1 to 0.3 under the condition that the moving speed was 100 mm/min.

The resin composition according to the second embodiment may contain other components such as an ester compound (B), a plasticizer (C), or a thermoplastic elastomer (D), which will be described later.

As described above, it is difficult in some cases to impart desired properties to a resin composition containing a conventional biomass-derived component, and the puncture impact strength of a resin molded article may be insufficient.

On the other hand, the resin composition according to the second embodiment has the above configuration, and therefore a resin molded article having high puncture strength can be obtained. The reason is presumed as follows.

For example, when the resin composition in which the dynamic friction coefficient shown in the condition (1B) is from 0.1 to 0.3 is in a stable state at the kneading step, the mixing property of the kneaded resin composition tends to be easily stabilized. Therefore, a resin molded article in which the resin composition has high dispersibility is easily formed. Therefore, it is estimated that the puncture strength is improved.

The resin molded article obtained from the resin composition satisfying the condition (2) has a moderately high tensile elastic modulus of 1,400Mpa to 2,500 Mpa. As described above, the resin molded article is a resin molded article having an appropriate density and high dispersibility, and therefore it is estimated that a resin molded article having high puncture strength can be obtained.

As described above, it is estimated that the resin molded article obtained from the resin composition satisfying the conditions (1B) and (2) has high puncture strength.

The constitution of the resin composition according to the first and second embodiments (hereinafter referred to as "exemplary embodiments" for convenience) will be described in detail below. Reference numerals may be omitted.

(Properties of resin composition)

The resin composition according to the first embodiment satisfies the conditions (1A) and (2). The resin composition according to the first embodiment may also satisfy the condition (1B).

The resin composition according to the second embodiment satisfies the conditions (1B) and (2). The resin composition according to the second embodiment may also satisfy the condition (1A).

From the viewpoint of obtaining a resin molded article having a higher puncture strength, it is preferable that the resin composition according to the exemplary embodiment also satisfies the conditions (3) and (4).

Condition (1A) -

In the resin composition according to the first embodiment, using test pieces each having a weight of 200g and a contact area of 80mm × 200mm prepared from the resin composition, the static friction coefficient measured according to ISO8295:1995 at a moving speed of 100 mm/min is 0.2 to 0.4.

From the viewpoint of obtaining a resin molded article having a high puncture strength, the static friction coefficient is preferably 0.2 to 0.35, more preferably 0.2 to 0.3, and further preferably 0.2 to 0.28.

The static friction coefficient is adjusted by, for example, the type and content of the resin contained in the resin composition, the type and content of the ester compound (B) described later, and the type and content of the plasticizer (C) described later.

Condition (1B)

In the resin composition according to the second embodiment, from the viewpoint of obtaining a resin molded article having a higher puncture strength, the dynamic friction coefficient measured according to ISO8295:1995 at a moving speed of 100 mm/min was 0.1 to 0.3 using test pieces each having a weight of 200g and a contact area of 80mm × 200mm prepared from the resin composition.

From the viewpoint of obtaining a resin molded article having a high puncture strength, the dynamic friction coefficient is preferably 0.1 to 0.28, more preferably 0.1 to 0.25, and further preferably 0.1 to 0.24.

The dynamic friction coefficient is adjusted by, for example, the type and content of the resin contained in the resin composition, the type and content of the ester compound (B) described later, and the type and content of the plasticizer (C) described later.

Condition (2)

In the resin composition according to the exemplary embodiment, a test piece having a thickness of 4mm and a width of 10mm prepared from the resin composition is used, and a tensile elastic modulus measured according to ISO527-1:2012 is 1,400MPa to 2,500 MPa.

The tensile modulus of elasticity is preferably 1,450MPa to 2,400MPa, more preferably 1,550MPa to 2,200MPa, and still more preferably 1,600MPa to 2,000MPa, from the viewpoint of obtaining a resin molded article having a higher puncture strength.

The tensile elastic modulus is adjusted by, for example, the type and content of the resin contained in the resin composition, the type and content of the ester compound (B) described later, and the type and content of the plasticizer (C) described later.

Condition (3)

In the resin composition according to the exemplary embodiment, the ratio of the Static Friction Coefficient (SFC) to the tensile Elastic Modulus (EM) preferably satisfies 0.00009 < (SFC)/(EM) < 0.0003, more preferably satisfies 0.0001 < (SFC)/(EM) < 0.0003, and further preferably satisfies 0.00015 < (SFC)/(EM) < 0.00025.

The value of (SFC)/(EM) represents the ratio of the initial frictional resistance to the surface hardness. When the value of (SFC)/(EM) is large, self-deformation by friction tends to be reduced, and surface wear is more likely to occur. On the other hand, when the value of (SFC)/(EM) is small, surface abrasion hardly occurs, and thus self-deformation easily occurs.

As a method for obtaining a resin composition satisfying the condition (3), examples include: a method of adjusting the type and content of the resin contained in the resin composition, the type and content of the ester compound (B) described later, and the plasticizer (C) described later and the like; a method of controlling the high-order phase structure of each component by the preparation of kneading conditions; and a method of individually adjusting the surface and internal structure of the molded body by combining the above methods.

Condition (4)

In the resin composition according to the exemplary embodiment, the relationship between the Dynamic Friction Coefficient (DFC) and the tensile Elastic Modulus (EM) preferably satisfies 0.00004 < (DFC)/(EM) < 0.00018, more preferably satisfies 0.00008 < (DFC)/(EM) < 0.00016, and further preferably satisfies 0.0001 < (DFC)/(EM) < 0.00015.

The value of (DFC)/(EM) represents the ratio of hardness to stable friction, not initial friction, when the resin composition is rubbed. When the value of (DFC)/(EM) is large, the stability of friction tends to be high. On the other hand, when the value of (DFC)/(EM) is small, the occurrence of abnormal noise tends to be suppressed when the resin composition is rubbed.

As a method for obtaining a resin composition satisfying the condition (4), examples include: a method of adjusting the type and content of the resin contained in the resin composition, the type and content of the ester compound (B) described later, and the plasticizer (C) described later and the like; a method of controlling the high-order phase structure of each component by the preparation of kneading conditions; and a method of individually adjusting the surface and internal structure of the molded body by combining the above methods.

The components of the resin composition according to the exemplary embodiment will be described in detail below.

(resin having Biomass-derived carbon atoms)

The resin composition according to an exemplary embodiment includes a resin having biomass-derived carbon atoms.

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

Further, as the resin having a biomass-derived carbon atom, all of the resins may not necessarily be derived from biomass, and at least a part thereof may have a structure derived from biomass. Specifically, for example, as cellulose acylate to be described later, the cellulose structure may be derived from biomass, and the acylate structure may be derived from petroleum.

In an exemplary embodiment, the "resin having a biomass-derived carbon atom" is a resin having at least a carbon atom derived from an organic resource of biological origin other than fossil resources, and is prepared by ASTM D6866: 2012-based, which will be described later¹⁴C abundance indicates the presence of biomass-derived carbon atoms.

From the viewpoint of obtaining a resin molded article having better separability, the content of the 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, further preferably 35% or more, and particularly preferably 40% to 100%, relative to the total amount of carbon atoms in the resin composition.

In an exemplary embodiment, the method of measuring the content of biomass-derived carbon atoms in a resin composition is one in which all carbon atoms in the resin composition are measured according to ASTM D6866: 2012¹⁴C abundance and calculating the content of biomass-derived carbon atoms.

Examples of the resin having a biomass-derived carbon atom include cellulose acylate, polylactic acid, a biomass-derived polyolefin, a biomass-derived polyethylene terephthalate, a biomass-derived polyamide, poly (3-hydroxybutyric acid), polytrimethylene terephthalate (PTT), polybutylene succinate (PBS), Phosphatidylglycerol (PG), an isosorbide polymer, an acrylic-modified rosin, or the like.

Among them, as the resin having a biomass-derived carbon atom, from the viewpoint of obtaining a resin molded article having a higher puncture strength, the resin preferably includes cellulose acylate (a), and more preferably cellulose acylate (a).

[ cellulose acylate (A): component (A) ]

The cellulose acylate (a) is a cellulose derivative: wherein at least a part of the hydroxyl groups in the cellulose are substituted (acylated) with acyl groups. The acyl group is a group having the structure-CO-RAC (RAC represents a hydrogen atom or a hydrocarbon group).

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

In the general formula (CA), A¹、A²And A³Each independently represents a hydrogen atom or an acyl group, and n represents an integer of 2 or more. However, n A¹、n A²And n A³At least a part of (a) represents an acyl group. All n A in the molecule¹May be identical to, partially identical to, or different from each other. Similarly, all n A in the molecule²And n A³May be identical to, partially identical to, or different from each other.

From A¹、A²And A³The hydrocarbon group in the acyl group represented may be linear, branched or cyclic, preferably linear or branched, more preferably linear.

From A¹、A²And A³The hydrocarbon group in the acyl group represented may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and is more preferably a saturated hydrocarbon group.

From A¹、A²And A³The acyl group represented is preferably an acyl group having 1 to 6 carbon atoms. That is, the cellulose acylate (a) preferably has an acyl group having 1 to 6 carbon atoms. A resin molded article having higher puncture strength may be more easily obtained from a cellulose acylate having an acyl group having 1 to 6 carbon atoms than from a cellulose acylate having an acyl group having 7 or more carbon atoms (a).

From A¹、A²And A³The acyl group represented may be such that: wherein the hydrogen atom in the acyl group is substituted with a halogen atom (e.g., fluorine atom, bromine atom, and iodine atom), oxygen atom, or nitrogen atom, etc., and is preferably unsubstituted.

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

Examples of the cellulose acylate (a) include cellulose acetate (mono-acetate, cellulose Diacetate (DAC), cellulose triacetate), Cellulose Acetate Propionate (CAP), Cellulose Acetate Butyrate (CAB).

As the cellulose acylate (a), Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB) are preferable, and Cellulose Acetate Propionate (CAP) is more preferable, from the viewpoint of obtaining a resin molded product having a high puncture strength.

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

The weight-average polymerization degree of the cellulose acylate (a) is preferably 200 to 1000, more preferably 500 to 1000, and further more preferably 600 to 1000, from the viewpoint of moldability of the resin composition and a resin molded article having a higher puncture strength.

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

First, the weight average molecular weight (Mw) of the cellulose acylate (A) was determined from polystyrene by a gel permeation chromatography apparatus (GPC apparatus: HLC-8320 GPC, manufactured by Tosoh Corporation, column: TSK gel α -M) using tetrahydrofuran.

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

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

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

In the Cellulose Acetate Propionate (CAP), the ratio of the substitution degree of an acetyl group to the substitution degree of a propionyl group (acetyl group/propionyl group) is preferably 0.01 to 1, more preferably 0.05 to 0.1, from the viewpoint of moldability of the resin composition and obtaining a resin molded product having higher puncture strength.

The CAP preferably satisfies at least one of the following (1), (2), (3), and (4), preferably satisfies the following (1), (3), and (4), and more preferably satisfies the following (2), (3), and (4).

(1) The weight average molecular weight (Mw) according to polystyrene is 160,000 to 250,000, and the ratio Mn/Mz of the number average molecular weight (Mn) according to polystyrene to the Z average molecular weight (Mz) according to polystyrene is 0.14 to 0.21, when measured by a GPC method using tetrahydrofuran as a solvent.

(2) When measured by a GPC method using tetrahydrofuran as a solvent, the weight average molecular weight (Mw) according to polystyrene is 160,000 to 250,000, the ratio Mn/Mz of the number average molecular weight (Mn) according to polystyrene to the Z average molecular weight (Mz) according to polystyrene is 0.14 to 0.21, and the ratio Mw/Mz of the weight average molecular weight (Mw) according to polystyrene to the Z average molecular weight (Mz) according to polystyrene is 0.3 to 0.7.

(3) The ratio η 1/η 2 of the viscosity η 1(Pa · s) at a shear rate of 1216(/ sec) to the viscosity η 2(Pa · s) at a shear rate of 121.6(/ sec) is 0.1 to 0.3 when measured by Capirograph at 230 ℃ according to ISO 11443: 1995.

4) When a small square plate test piece (D11 test piece, designated by JIS K7139:2009, 60mm × 60mm, thickness of 1mm) obtained by injection molding of CAP was left standing for 48 hours in an atmosphere of a temperature of 65 ℃ and a relative humidity of 85%, the expansion coefficient in the MD direction and the expansion coefficient in the TD direction were 0.4% and 0.6%. Here, the MD direction refers to a longitudinal direction of a mold cavity for injection molding, and the TD direction refers to a direction orthogonal to the MD direction.

In Cellulose Acetate Butyrate (CAB), the ratio of the degree of substitution of acetyl groups to the degree of substitution of butyryl groups (acetyl group/butyryl group) is preferably 0.05 to 3.5, more preferably 0.5 to 3.0, from the viewpoint of moldability of the resin composition and a resin molded article having higher puncture strength.

The degree of substitution of the cellulose acylate (a) is an index indicating the degree of substitution of the hydroxyl group of the cellulose with the acyl group. That is, the substitution degree is an index indicating the degree of acylation of the cellulose acylate (a). Specifically, the substitution degree means an average number of substitutions within a molecule in which three hydroxyl groups in the D-glucopyranose unit of the cellulose acylate (a) are substituted with acyl groups.

The degree of substitution is by¹H-NMR (JMN-ECA, manufactured by JEOL RESONANCE co., ltd.) was determined from the ratio of the peak integral of cellulose-derived hydrogen to the peak integral of acyl group-derived hydrogen.

The resins having biomass-derived carbon atoms may be used alone or in combination of two or more.

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

From the viewpoint of obtaining a resin molded article having a higher puncture strength, the resin composition according to the exemplary embodiment preferably further includes: an ester compound (B) which is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4) and a compound represented by the following general formula (5).

Among them, in the resin composition according to the exemplary embodiment, the ester compound (B) is preferably at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3), from the viewpoint of obtaining a resin molded article having a higher puncture strength; more preferably at least one selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2); particularly preferred is a compound comprising a compound represented by the following general formula (1).

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

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

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

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

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

R¹¹Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms. From the viewpoint that the group easily functions as a lubricant for the molecular chain of the resin, R¹¹The 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 the viewpoint of easy introduction of groups into the molecular chain of the resin (particularly cellulose acylate (A), the same applies hereinafter), by R¹¹The group represented is preferably an aliphatic hydrocarbon group having 24 or less carbon atoms, more preferably 20 or moreAliphatic hydrocarbon groups having a small number of carbon atoms, and aliphatic hydrocarbon groups having 18 or less carbon atoms are more preferable. From R¹¹The radicals represented are particularly preferably aliphatic hydrocarbon radicals having 17 carbon atoms.

From R¹¹The group represented may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. From the viewpoint that the groups are easily taken into between molecular chains of the resin, from R¹¹The radicals represented are preferably saturated aliphatic hydrocarbon radicals.

From R¹¹The group represented may be a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing an alicyclic ring. From the viewpoint that the groups are easily taken into between molecular chains of the resin, from R¹¹The group represented is preferably an aliphatic hydrocarbon group containing no alicyclic ring (i.e., a chain aliphatic hydrocarbon group), and more preferably a linear aliphatic hydrocarbon group.

When represented by R¹¹When the group represented is an unsaturated aliphatic hydrocarbon group, the number of unsaturated bonds in the group is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1, from the viewpoint that the group is easily taken into between molecular chains of the resin.

When represented by R¹¹When the group represented is a saturated aliphatic hydrocarbon group, the group preferably contains, from the viewpoint that the group easily enters between molecular chains of the resin and easily functions as a lubricant for the molecular chains of the resin: a linear saturated hydrocarbon chain having 5 to 24 carbon atoms, more preferably a linear saturated hydrocarbon chain having 7 to 22 carbon atoms, still more preferably a linear saturated hydrocarbon chain having 7 to 22 carbon atoms, yet more preferably a linear saturated hydrocarbon chain having 9 to 20 carbon atoms, and particularly preferably a linear saturated hydrocarbon chain having 15 to 18 carbon atoms.

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

When represented by R¹¹When the group represented is a branched aliphatic hydrocarbon group, the group is easily introduced between molecular chains of the resin and easily introduced into the molecular chains of the resinFrom the viewpoint of the effect of the lubricant, the main chain of the group preferably has 5 to 24 carbon atoms, more preferably 7 to 22 carbon atoms, still more preferably 9 to 20 carbon atoms, and particularly preferably 15 to 18 carbon atoms.

When represented by R¹¹When the group represented is an aliphatic hydrocarbon group containing an alicyclic ring, the number of alicyclic rings in the group is preferably 1 or 2, more preferably 1, from the viewpoint that the group is easily taken into the molecular chains of the resin.

When represented by R¹¹When the group represented is an aliphatic hydrocarbon group containing an alicyclic ring, the alicyclic ring in the group is preferably an alicyclic ring having 3 or 4 carbon atoms, more preferably an alicyclic ring having 3 carbon atoms, from the viewpoint that the group is easily taken into the molecular chain of the resin.

From the viewpoint of obtaining a resin molded article having a high puncture strength, R is¹¹The group represented is preferably a straight-chain saturated aliphatic hydrocarbon group, a straight-chain unsaturated aliphatic hydrocarbon group, a branched-chain saturated aliphatic hydrocarbon group or a branched-chain unsaturated aliphatic hydrocarbon group, and particularly preferably a straight-chain saturated aliphatic hydrocarbon group. The preferred number of carbon atoms in these aliphatic hydrocarbon groups is as described above.

From R¹¹The group represented may be such that: wherein the hydrogen atom in the aliphatic hydrocarbon group is substituted with a halogen atom (fluorine atom, bromine atom and iodine atom), an oxygen atom, a nitrogen atom or the like, and is preferably unsubstituted.

R¹²Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms. From R¹²Examples of the radicals represented include¹¹The same forms as those described. However, from R¹²The number of carbon atoms of the group represented is preferably within the above range.

From the viewpoint that the group easily functions as a lubricant for the molecular chain of the resin, R¹²The 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 the angle at which the groups easily enter between the molecular chains of the cellulose acylate (A)Consider the expression of R¹²The group represented is preferably an aliphatic hydrocarbon group having 24 or less carbon atoms, more preferably an aliphatic hydrocarbon group having 20 or less carbon atoms, and still more preferably an aliphatic hydrocarbon group having 18 or less carbon atoms. From R¹²The radicals represented are particularly preferably aliphatic hydrocarbon radicals having 18 carbon atoms.

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

Shown below by R¹¹、R²¹、R²²、R³¹、R³²、R⁴¹、R⁴²、R⁴³、R⁵¹、R⁵²、R⁵³And R⁵⁴Specific examples of the aliphatic hydrocarbon group having 7 to 28 carbon atoms represented and the compound represented by R¹²Specific examples of the aliphatic hydrocarbon group having 9 to 28 carbon atoms are shown, but the exemplary embodiments are not limited thereto.

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

[ plasticizer (C): component (C) ]

From the viewpoint of obtaining a resin molded article having higher puncture strength, it is preferable that the resin composition according to the exemplary embodiment further contains a plasticizer (C).

Examples of the plasticizer (C) include a cardanol compound, an ester compound other than the ester compound (B), camphor, a metal soap, a polyol, a polyoxyalkylene, or the like. The plasticizer (C) is preferably a cardanol compound from the viewpoint of obtaining a resin molded article having a high puncture strength.

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

The plasticizer (C) is preferably a cardanol compound or an ester compound other than the ester compound (B) from the viewpoint of easily obtaining an effect of improving puncture strength by adding the ester compound (B). Cardanol compounds and ester compounds suitable for use as the plasticizer (C) will be specifically described below.

< Cardanol Compound >

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

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

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

The resin composition according to an exemplary embodiment may include a derivative derived from a mixture derived from cashew nuts as a cardanol compound. Examples of derivatives derived from mixtures derived from cashew nuts include the following mixtures or pure substances.

Mixtures prepared by adjusting the composition ratio of the components in the cashew nut-derived mixtures

Pure substance obtained by separating only specific component from mixture obtained from cashew nut

Mixtures containing modified products (obtained by modifying components in cashew nut-derived mixtures)

Mixtures containing polymers (obtained by polymerizing components in cashew nut-derived mixtures)

Mixtures containing modified polymers (obtained by modifying and polymerizing components in cashew nut-derived mixtures)

Mixtures comprising modified products (obtained by further varying the components of the mixture whose composition ratios have been adjusted)

Mixtures comprising polymers (obtained by further polymerizing the components of the mixture whose composition ratios have been adjusted)

Mixtures comprising modified polymers (obtained by further modifying and polymerizing the components of the mixture whose composition ratios have been adjusted)

Modified products obtained by further modification of the isolated pure substances

Polymers obtained by further polymerization of the isolated pure substances

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

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

From the viewpoint of obtaining a resin molded article having a higher puncture strength, the cardanol compound is preferably at least one compound selected from the group consisting of a compound represented by general formula (CDN1) and a polymer obtained by polymerizing a compound represented by general formula (CDN 1).

In the general formula (CDN1), R¹Represents an alkyl group optionally having a substituent, or an unsaturated aliphatic group optionally having a double bond and a substituent. R²Represents a hydroxyl group, a carboxyl group, an alkyl group optionally having a substituent, or an unsaturated aliphatic group optionally having a double bond and a substituent. P2 represents an integer of 0 to 4. When P2 is 2 or more, plural R' s²May be the same group or different groups.

In the general formula (CDN1), R is represented by¹The alkyl group optionally having a substituent represented by (a) is preferably an alkyl group having 3 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms, and still more preferably an alkyl group having 8 to 20 carbon atoms.

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

Examples of the alkyl group which may be substituted include pentadecan-1-yl, heptane-1-yl, octane-1-yl, nonane-1-yl, decan-1-yl, undecane-1-yl, dodecane-1-yl, tetradecan-1-yl and the like.

In the general formula (CDN1), R is represented by¹The unsaturated aliphatic group optionally having a double bond and 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 those enumerated as the substituent of the alkyl group.

Examples of the unsaturated aliphatic group which may optionally have a double bond and a substituent include pentadecan-8-en-1-yl, pentadecan-8, 11-dien-1-yl, pentadecan-8, 11, 14-trien-1-yl, pentadecan-7-en-1-yl, pentadecan-7, 10-dien-1-yl, or pentadecan-7, 10, 14-trien-1-yl, and the like.

In the general formula (CDN1), R¹Preferred are pentadecan-8-en-1-yl, pentadecan-8, 11-dien-1-yl, pentadecan-8, 11, 14-trien-1-yl, pentadecan-7-en-1-yl, pentadecan-7, 10-dien-1-yl and pentadecan-7, 10, 14-trien-1-yl.

In the general formula (CDN1), R is represented by²Preferred examples of the optionally substituted alkyl group and the optionally substituted unsaturated aliphatic group represented by (A) are included as represented by R¹Those exemplified for the optionally substituted alkyl group and the optionally double-bonded and substituted unsaturated aliphatic group are exemplified.

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

In the group (EP) and the general formula (CDN1-e), LEP represents a single bond or a divalent linking group. In the general formula (CDN1-e), R¹、R²And P2 each independently has the same general formula (CDN1) as R¹、R²The same meaning as P2.

In the group (EP) and the general formula (CDN1-e), from L_EPExamples of the divalent linking group represented include an alkylene group optionally having a substituent (preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 carbon atom), or-CH₂CH₂OCH₂CH₂-and the like.

Examples of substituents include those for R as general formula (CDN1)¹Those listed as substituents of (A) are mentioned.

L_EPMethylene groups are preferred.

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

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

In the general formula (CDN2), R¹¹、R¹²And R¹³Each independently represents an alkyl group optionally having a substituent, or an unsaturated aliphatic group optionally having a double bond and a substituent. R²¹、R²²And R²³Each independently represents a hydroxyl group, a carboxyl group, an alkyl group optionally having a substituent, or an unsaturated aliphatic group optionally having a double bond and a substituent. P21 and P23 each independently represent an integer of 0 to 3, and P22 represents an integer of 0 to 2. L is¹And L²Each independently represents a divalent linking group. n represents an integer of 0 to 10. Plural R when P21 is 2 or more²¹R when P22 is 2 or more²²And a plurality of R when P23 is 2 or more²³May be the same group or different groups, respectively. Plural R when n is 2 or more¹²、R²²And L¹May be the same group or different groups, respectively, and the plurality of P22 s when n is 2 or more may be the same group or different groups.

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

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

Examples of substituents include those for R as general formula (CDN1)¹Those listed as substituents of (A) are mentioned.

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

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

In the general formula (CDN2-e), R¹¹、R¹²、R¹³、R²¹、R²²、R²³、P21、P22、P23、L¹And L²Each having the same general formula as R in (CDN2)¹¹、R¹²、R¹³、R²¹、R²²、R²³、P21、P22、P23、L¹、L²And n have the same meaning.

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

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

The polymer obtained by polymerizing the compound represented by the general formula (CDN1) may be, for example, a polymer obtained by three-dimensional crosslinking and polymerizing at least three compounds represented by the general formula (CDN1) in the presence or absence of a linking group. Examples of the polymer obtained by three-dimensionally crosslinking and polymerizing the compound represented by the general formula (CDN1) include compounds represented by the following structural formulae.

In the above formula, R¹⁰、R²⁰And P20 each independently has the same general formula (CDN1) as R¹、R²The same meaning as P2. L is¹⁰Represents a single bond or a divalent linking group. Plural R¹⁰、R²⁰And L¹⁰May be the same group or different groups. The plurality of P20 may be the same number or different numbers.

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

Examples of substituents include R as general formula (CDN1)¹Those listed as substituents of (A).

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

In the above formula, R¹⁰、R²⁰And P20 each independently has the same general formula (CDN1-e) as R¹、R²The same meaning as P2. L is¹⁰Represents a single bond or a divalent linkageAnd (3) a linking group. Plural R¹⁰、R²⁰And L¹⁰May be the same group or different groups, respectively. The plurality of P20 may be the same number or different numbers.

Examples of substituents include R as general formula (CDN1)¹Those listed as substituents of (A).

From the viewpoint of obtaining a resin molded product having higher puncture strength, the cardanol compound preferably contains a cardanol compound having an epoxy group, more preferably a cardanol compound having an epoxy group.

Commercially available products can be used as cardanol compounds. 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 (all manufactured by Cardolite Corporation); LB-7000, LB-7250 and CD-5L (all manufactured by Tohoku Chemical Industry Co., Ltd.); and the like. Examples of commercially available products of cardanol compounds with epoxy groups include NC-513, NC-514S, NC-547, LITE 513E and Ultra LTE 513 manufactured by Cardolite Corporation.

From the viewpoint of obtaining a resin molded article having a higher puncture strength, the hydroxyl value of the cardanol compound is preferably 100mgKOH/g or more, more preferably 120mgKOH/g or more, and still more preferably 150mgKOH/g or more. The hydroxyl number of the cardanol compound is measured according to ISO14900, method a.

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

< ester Compound >

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

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

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

From R⁶¹Specific forms and preferred forms of the group represented include those represented by R in the general formula (1)¹¹The groups represented are in the same form.

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

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

The ester compound included as the plasticizer (C) in the resin composition according to the exemplary embodiment has a molecular weight (or weight average molecular weight) of 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 not particularly limited, and is a value measured according to the method for measuring the weight average molecular weight of the cellulose acylate (a).

The plasticizer (C) is preferably an adipate. The adipate ester has a high affinity with the cellulose acylate (a) and is dispersed to the cellulose acylate (a) in a nearly uniform state, thereby further improving the heat fluidity as compared with other plasticizers.

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

In the general formula (AE), R^AE1And R^AE2Each independently represents an alkyl group or a polyoxyalkyl 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 the general formula (APE), 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. ) And R is^AE3Represents an alkylene group. m1 represents an integer of 1 to 10, and m2 represents an integer of 1 to 20.

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

R in the general formula (AE) and the general formula (APE)^AE1And R^AE2A polyoxyalkylene group of the formula [ - (C)_xH_2X-O)_y-R^A1]In the formula (II) is represented by R^A1The alkyl group represented is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. From R^A1The alkyl groups represented may be linear, branched or cyclic, and are preferably linear or branched.

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

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

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

The adipate ester has a molecular weight (weight average molecular weight) of preferably 250 to 2,000, more preferably 280 to 1,500, and still more preferably 300 to 1,000. The weight average molecular weight of adipate is a value measured according to the method of measuring the weight average molecular weight of cellulose acylate (a).

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

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

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

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

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

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

The polyetherester compound may be a polyester unit or a polyether unit, each of which is aromatic or aliphatic (including alicyclic rings). The mass ratio of the polyester unit to the polyether unit is, for example, 20:80 to 80: 20. The polyether compound has a molecular weight (weight average molecular weight) of preferably 250 to 2000, more preferably 280 to 1500, and still more preferably 300 to 1000. Examples of commercially available products of polyetherester compounds include ADK Cizer RS-1000 (ADEKA).

Examples of the polyether compound having at least one unsaturated bond in the molecule include polyether compounds having an allyl group at the terminal, and polyalkylene glycol allyl ethers are preferable. The polyether compound having at least one unsaturated bond in the molecule has a molecular weight (weight average molecular weight) of 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(NOF CORPORATION).

(thermoelastic elastomer (D): component (D))

From the viewpoint of obtaining a resin molded article having a higher puncture strength, it is preferable that the resin composition according to the exemplary embodiment further contains the thermoplastic elastomer (D).

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

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

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

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

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

polyurethane (d 5); and

polyester (d 6).

The thermoplastic elastomer (D) is, for example, a thermoplastic elastomer having elasticity at ordinary temperature (25 ℃) and softening at high temperature (as with a thermoplastic resin).

From the viewpoint of obtaining a resin molded article having a higher puncture strength, the thermoplastic elastomer (D) preferably contains at least one thermoplastic elastomer selected from the group consisting of the following polymers: a core-shell structure polymer (d1) having a core layer (comprising a butadiene polymer), the core layer comprising a butadiene polymer, and a shell layer comprising a polymer selected from the group consisting of a styrene polymer and an acrylonitrile-styrene polymer on the surface of the core layer; a core-shell structure polymer (d2) having a shell layer comprising an alkyl (meth) acrylate polymer on the surface of the core layer; styrene-ethylene-butadiene-styrene copolymer (d 4); polyurethane (d5) and polyester (d6), more preferably a core-shell structure polymer (d2) having a shell layer comprising an alkyl (meth) acrylate polymer on the surface of the core layer.

The thermoplastic elastomer (D) is preferably a particulate thermoplastic elastomer from the viewpoint of obtaining a resin molded article having a high puncture strength. That is, the resin composition according to the exemplary embodiment preferably contains thermoplastic elastomer particles as the thermoplastic elastomer (D) from the viewpoint of obtaining a resin molded article having a higher puncture strength.

Core-shell structure polymer (d 1): component (d1)

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

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

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

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

Examples of the (meth) acrylic rubber include polymer rubbers obtained by polymerizing (meth) acrylic components (for example, alkyl esters of (meth) acrylic acid having 2 to 8 carbon atoms).

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

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

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

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

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

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

Among them, from the viewpoint of obtaining a resin molded article having a higher puncture strength by adding component (B), the alkyl (meth) acrylate polymer is preferably an alkyl (meth) acrylate polymer having an alkyl chain containing 1 to 8 carbon atoms, more preferably an alkyl (meth) acrylate polymer having an alkyl chain containing 1 to 2 carbon atoms, and still more preferably an alkyl (meth) acrylate polymer having an alkyl chain containing 1 carbon atom.

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

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

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

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

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

The average primary particle diameter of the core-shell structured polymer is not particularly limited, and is preferably from 50nm to 500nm, more preferably from 50nm to 400nm, further preferably from 100nm to 300nm, and particularly preferably from 150nm to 250nm, from the viewpoint of obtaining a resin molded article having a higher puncture strength by adding component (B).

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

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

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

Examples of commercially available products of the core-shell structured polymer (d1) include "METABLEN" (registered trademark) manufactured by Mitsubishi Chemical Corporation, "Kane Ace" (registered trademark) manufactured by Kaneka Corporation, "PARALOID" (registered trademark) manufactured by Dow Chemical Japan, "STAPHYLOID" (registered trademark) manufactured by Aica Kogyo Company, "Paraface" (registered trademark) manufactured by KURAY CO., LTD.

-core-shell structured polymer (d 2): component (d2)

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

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

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

The core layer containing a butadiene polymer is not particularly limited as long as it contains a polymer obtained by polymerizing a butadiene-containing component, and may be a core layer containing a butadiene homopolymer, or a core layer containing a copolymer of butadiene and another monomer, examples of the other monomer include a vinyl aromatic monomer, among the vinyl aromatic monomers, 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)) are preferable, styrene components may be used alone, or two or more kinds may be used in combination.

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

The butadiene polymer contained in the core layer contains 60 to 100 mass% (preferably 70 to 100 mass%) of a structural unit derived from butadiene and 0 to 40 mass% (preferably 0 to 30 mass%) of a structural unit derived from another monomer (preferably a styrene component). For example, the percentage of the structural unit derived from each monomer constituting the butadiene polymer is preferably 60 to 100 mass% for butadiene and 0 to 40 mass% for styrene. The percentage of divinylbenzene is preferably 0 to 5 mass% based on the total amount of styrene and divinylbenzene.

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

Among them, the styrene polymer contained in the shell layer is preferably a copolymer of styrene and an alkyl (meth) acrylate from the viewpoint of obtaining a resin molded article having a higher puncture strength by adding component (B). In the same view, a copolymer of styrene and an alkyl (meth) acrylate having an alkyl chain of 1 to 8 carbon atoms is preferable, and an alkyl (meth) acrylate polymer having an alkyl chain of 1 to 4 carbon atoms is more preferable.

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

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

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

Among the components (d2), examples of commercially available products of the core-shell structure polymer (d3) including a core layer (containing a butadiene polymer) and a shell layer (containing a styrene polymer) on the surface of the core layer include "metabelen" (registered trademark) manufactured by mitsubishi Chemical Corporation, "KaneAce" (registered trademark) manufactured by Kaneka Corporation, "cleartrength" (registered trademark) manufactured by Arkema, and "PARALOID" (registered trademark) manufactured by Dow Chemical Japan.

As for the component (d2), examples of commercially available products of the core-shell structured polymer (d3) including a core layer (containing a butadiene polymer) and a shell layer (containing an acrylonitrile-styrene polymer) on the surface of the core layer include "Blendex" (registered trademark) manufactured by GalataChemicals, "ELIX" manufactured by ELIX POLYMERS, and the like.

The average primary particle diameters of the core-shell structure polymer (d1) and the core-shell structure polymer (d2) are not particularly limited, but are preferably 50nm to 500nm, more preferably 50nm to 400nm, further preferably 100nm to 300nm, and particularly preferably 150nm to 250nm, from the viewpoint of the resin molded article or the resin molded article having a high puncture strength.

Olefin polymer (d 3): component (d3)

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

Examples of the α -olefin in the olefin polymer include ethylene, propylene, 2-methylpropylene and the like from the viewpoint of obtaining a resin molded article having a higher puncture strength by adding the component (B), α -olefin having 2 to 8 carbon atoms is preferable, α -olefin having 2 to 3 carbon atoms is more preferable, of which ethylene is 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, octadecyl (meth) acrylate, and the like from the viewpoint of obtaining a resin molded article having higher puncture strength by adding component (B), alkyl (meth) acrylates having an alkyl chain containing 1 to 8 carbon atoms are preferable, alkyl (meth) acrylates having an alkyl chain containing 1 to 4 carbon atoms are more preferable, and alkyl (meth) acrylates having an alkyl chain containing 1 to 2 carbon atoms are even more preferable.

The olefin polymer is preferably a polymer of ethylene and methyl acrylate from the viewpoint of obtaining a resin molded article having higher puncture strength by adding component (B).

From the viewpoint of obtaining a resin molded article having higher puncture strength by adding component (B), the olefin polymer preferably contains from 60 to 97 mass%, more preferably from 70 to 85 mass% of structural units derived from α -olefin.

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

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

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

The copolymer (d4) is preferably a hydrogenated product of a styrene-ethylene-butadiene-styrene copolymer, from the viewpoint of obtaining a resin molded article having a higher puncture strength. From the same viewpoint, the copolymer (d4) is preferably a block copolymer, for example, a copolymer (styrene-ethylene/butylene-styrene triblock copolymer) preferably having a block of a styrene moiety at both ends and a block comprising a central portion of ethylene/butylene by hydrogenating at least a part of the double bond 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 known methods. When the copolymer (d4) is a hydrogenated product of a styrene-ethylene-butadiene-styrene copolymer, for example, the copolymer can be obtained by hydrogenating the butadiene portion (wherein the conjugated diene portion contains 1,4 bonds) of a styrene-butadiene-styrene block copolymer.

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

-polyurethane (d 5): component (d5)

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

From the viewpoint of obtaining a resin molded article having a high puncture strength, the polyurethane (d5) is preferably an aliphatic polyurethane. The aliphatic polyurethane is preferably obtained, for example, by reacting a polyol component containing a polycarbonate polyol with an isocyanate component containing an aliphatic diisocyanate.

The polyurethane (d5) can have been obtained by reacting a polyol component with an organic isocyanate component in the following manner: the NCO/OH ratio in the starting materials in the synthesis of the polyurethanes is from 0.90 to 1.5. The polyurethane (d5) is obtained by a known method such as a one-shot method, a prepolymerization method, etc.

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

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

The polyester (d6) is not particularly limited as long as it is a thermoplastic elastomer, and examples thereof include known polyesters. The polyester (d6) is preferably an aromatic polyester from the viewpoint of obtaining a resin molded article having a high puncture strength. In an exemplary embodiment, the aromatic polyester means a polyester having an aromatic ring in its structure.

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

The polyester copolymer as the polyester (d6) can be obtained by a known method. The polyester copolymer is preferably a linear polyester copolymer. The polyester copolymer is obtained, for example, by esterifying or de-esterifying a dicarboxylic acid component having 4 to 20 carbon atoms, a diol component having 2 to 20 carbon atoms and a polyalkylene glycol component having a number average molecular weight of 300 to 20000 (alkylene oxide adduct containing polyalkylene glycol), and then polycondensing the oligomer (polycondensation method). In addition, examples of the esterification or deesterification method include a method using a dicarboxylic acid component having 4 to 20 carbon atoms, a diol component having 2 to 20 carbon atoms, and an aliphatic polyester component having a number average molecular weight of 300 to 20,000. The dicarboxylic acid component is an aromatic or aliphatic dicarboxylic acid or an esterified derivative thereof, the diol component is an aromatic or aliphatic diol, and the polyalkylene glycol component is an aromatic or aliphatic polyalkylene glycol.

Among them, from the viewpoint of obtaining a resin molded article having a higher puncture strength, it is preferable to use a dicarboxylic acid component having an aromatic ring as the dicarboxylic acid component of the polyester copolymer. It is preferable to use an aliphatic diol component and an aliphatic polyalkylene glycol component as the diol component and the polyalkylene glycol component.

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

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

[ content or content ratio of respective Components ]

The resin composition according to the exemplary embodiment contains a resin having a biomass-derived carbon atom (component (a), etc.), and optionally contains component (B), component (C), component (D). From the viewpoint of easy obtainment of a resin molded article having a higher puncture strength, it is preferable that the content or content ratio (all on a mass basis) of each component in the resin composition according to the exemplary embodiment is within the following range.

Abbreviations for the respective components are as follows.

Component (A) ═ cellulose acylate (A)

Component (B) ═ ester compound (B)

Component (C) is plasticizer (C)

Component (D) ═ thermoplastic elastomer (D)

The content of the resin having a biomass-derived carbon atom in the resin composition according to the exemplary embodiment is preferably 50 mass% or more, more preferably 60 mass% or more, and still more preferably 70 mass% or more, based on the total amount of the resin composition.

The content of the component (a) in the resin composition according to the exemplary embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more based on the total amount of the resin composition.

The content of component (a) in the resin composition according to the exemplary embodiment is preferably 50 parts by mass or more, more preferably 80% by mass or more, and still more preferably 95% by mass to 100 parts by mass based on 100 parts by mass of the content of the resin having a biomass-derived carbon atom.

The content of the component (B) in the resin composition according to the exemplary embodiment is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%, and still more preferably 1 to 5 mass%, based on 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 mass%, more preferably 3 to 20 mass%, and still more preferably 5 to 15 mass%, based on 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 mass%, more preferably 3 to 15 mass%, and still more preferably 5 to 10 mass%, based on the total mass of the resin composition.

Component (B) and resin (A) having biomass-derived carbon atoms^Bio) Content ratio (B/A)^Bio) Preferably 0.002. ltoreq. (B/A)^Bio) 0.08 or less, more preferably 0.005 or less (B/A)^Bio) 0.05 or less, and more preferably 0.01 or less (B/A)^Bio)≤0.03。

The content ratio (B/A) of the component (B) to the component (A) is preferably 0.0025. ltoreq. B/A.ltoreq.0.1, more preferably 0.003. ltoreq. B/A.ltoreq.0.095, further preferably 0.05. ltoreq. B/A.ltoreq.0.05.

Component (C) and resin (A) having biomass-derived carbon atoms^Bio) Content ratio of (C/A)^Bio) Preferably 0.04. ltoreq. (C/A)^Bio)≤0.18, more preferably 0.05. ltoreq. C/A^Bio) 0.15 or less, and more preferably 0.07 or less (C/A)^Bio)≤0.10。

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, still more preferably 0.07. ltoreq. C/A.ltoreq.0.2.

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 more preferably 0.07 or less (D/A)^Bio))≤0.1。

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, 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) as a whole is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total amount of the resin composition.

Examples of the other component (E) include: flame retardants, compatibilizers, oxidation inhibitors, stabilizers, antiblocking agents, light-resistant agents, corrosion inhibitors, colorants, pigments, modifiers, drip inhibitors, antistatic agents, hydrolysis inhibitors, fillers, reinforcing agents (such as 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 (oxides such as magnesium oxide and alumina, metal hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and hydrotalcite; calcium carbonate; talc; etc.), reaction traps (such as epoxy compounds, anhydride compounds, and carbodiimides), and the like.

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

The resin composition according to the exemplary embodiment may contain other resins as the other component (E) in addition to the resin having a biomass-derived carbon atom (component (a) and the like), component (B), component (C), and component (D). However, in the case where other resin is contained, the content of the other resin is preferably 5% by mass or less, more preferably less than 1% by mass, based on the total amount of the resin composition. It is particularly preferable that no other resin is contained (i.e., 0 mass%).

Examples of the other resins include thermoplastic resins known in the related art, specifically including: a polycarbonate resin; a polypropylene resin; a polyester resin; a polyolefin resin; a polyester carbonate resin; a polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; polyether sulfone resin; a polyarylene resin; a polyetherimide resin; an acetal 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 poly (terephthalic acid) resin; a vinyl polymer or a copolymer obtained by polymerizing or copolymerizing a vinyl monomer selected from one or more of 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; an arylalkenyl compound-diene-vinyl cyanide-N-phenyl maleimide copolymer; vinyl cyanide- (ethylene-diene-propylene (EPDM)) -aromatic alkenyl compound copolymers; vinyl chloride resin; chlorinated vinyl chloride resin; and so on. The above resins may be used alone, or two or more kinds may be used in combination.

The polyester as the other component (E) may contain an aliphatic polyester (E2). Examples of the aliphatic polyester (e1) include polymers of hydroxyalkanoates (hydroxyalkanoic acids), polycondensates of polycarboxylic acids and polyols, ring-opening polycondensates of lactams, and polymers in which lactic acid is polymerized through an ester bond.

Further, it is also preferable that the resin composition according to the exemplary embodiment 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.

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

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

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

[ method for producing resin composition ]

Examples of the method of manufacturing the resin composition according to the exemplary embodiment include, for example: a method of mixing and melt-kneading a resin having biomass-derived carbon atoms (such as component (a)) and, if necessary, component (B), component (C), component (D), and other component (E); dissolving a resin having a biomass-derived carbon atom (e.g., component (A)) and, if necessary, component (B), component (C), component (D), and other component (E) in a solvent; and so on. The melt-kneading apparatus is not particularly limited, and examples thereof include a twin-screw extruder, a henschel mixer, a banbury mixer, a single-screw extruder, a multi-screw extruder, a co-kneader and the like.

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 resin composition according to the exemplary embodiment.

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

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

Injection molding of a resin molded article according to an exemplary embodiment may be performed, for example, by using commercial apparatuses such as NISSEIPLASTIC INDUSTRIAL co., NEX 500, NISSEI PLASTIC input standard co., manufactured by Ltd, NEX 150, NISSEI PLASTIC input standard co, manufactured by Ltd, NEX 7000, NISSEI plasticintestal co., manufactured by Ltd, PNX 40 and Sumitomo Heavy Industries, SE50D, manufactured by Ltd.

The molding method for obtaining the resin molded article according to the exemplary embodiment is not limited to the above injection molding, but injection molding, extrusion molding, blow molding, hot press molding, calendar molding, coat molding, cast molding, dip molding, vacuum molding, transfer molding, and the like are also applicable.

The resin molded article according to the exemplary embodiment is suitable for various applications such as electronic and electrical equipment, office equipment, home appliances, automotive interior materials, toys, containers, and the like. Specific applications of the resin molded article according to the exemplary embodiment include: a housing of an electronic/electric appliance device or a home appliance; parts of electronic/electric devices or household appliances; interior parts of automobiles; building blocks are assembled into a toy; a plastic mold box; CD-ROM or DVD storage cases; tableware; beverage bottles; a food pan; a packaging material; a film; a sheet material; and so on.

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