JP2011132468A - Thermoplastic resin composition, molding, and method for producing the same, and housing for electrical and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having good impact resistance, high rigidity, good wear resistance, and high flowability suitable for molding process. <P>SOLUTION: The thermoplastic resin composition contains a cellulose derivative including: at least one group obtained by substituting a hydrogen atom of a hydroxy group included in cellulose by (A) a hydrocarbon group, -R<SB>A</SB>; and at least one group obtained by substituting the same by (B) an acyl group, -CO-R<SB>B</SB>(wherein R<SB>B</SB>is a hydrocarbon group), and a polyester elastomer. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a thermoplastic resin composition, a molded body, a method for producing the same, and a casing for electric and electronic equipment.

Various materials are used for members constituting electric and electronic devices such as copiers and printers in consideration of characteristics and functions required for the members. For example, PC (Polycarbonate), ABS (Acrylonitrile-butadiene-styrene) resin, PC / ABS, etc. are generally used as a member (housing) that stores a drive machine for electrical and electronic equipment and protects the drive machine. In large amounts (Patent Document 1). These resins are produced by reacting compounds obtained from petroleum as a raw material.
By the way, fossil resources such as oil, coal, and natural gas are mainly composed of carbon that has been fixed in the ground for many years. When such fossil resources or products made from fossil resources are burned and carbon dioxide is released into the atmosphere, carbon that was originally not deep in the atmosphere but fixed deep in the ground Is rapidly released as carbon dioxide, and carbon dioxide in the atmosphere greatly increases, which causes global warming. Therefore, polymers such as ABS and PC made from petroleum, which is a fossil resource, have excellent characteristics as materials for electrical and electronic equipment, but are made from petroleum, which is a fossil resource. Therefore, it is desirable to reduce the amount used from the viewpoint of preventing global warming.
On the other hand, a plant-derived resin is originally produced by a photosynthesis reaction using carbon dioxide and water in the atmosphere as raw materials. Therefore, even if plant-derived resin is incinerated to generate carbon dioxide, the carbon dioxide is equivalent to carbon dioxide originally in the atmosphere, so the balance of carbon dioxide in the atmosphere is plus or minus zero After all, there is an idea that the total amount of CO _{2 in} the atmosphere is not increased. Based on this idea, plant-derived resins are referred to as so-called “carbon neutral” materials. The use of carbon-neutral materials in place of petroleum-derived resins is an urgent need to prevent global warming in recent years.
For this reason, in PC polymer, the method of reducing petroleum origin resources is proposed by using plant origin resources, such as starch, as some raw materials derived from petroleum (patent documents 2).
However, further improvements are required from the perspective of aiming for a more complete carbon neutral material.

As known cellulose derivatives, hydroxypropylmethylacetylcellulose is described in Patent Document 3 and Patent Document 4. Patent Document 3 and Patent Document 4 describe that this hydroxypropylmethylacetylcellulose is useful as an additive for reducing the vapor pressure of an organic solvent that easily volatilizes. In addition, the substitution degree of each substituent in hydroxypropylmethylacetylcellulose described in Patent Document 3 and Patent Document 4 is, for example, a molar substitution degree (MS) of hydroxypropyl group in a range of about 2 to 8, a substitution degree of methyl group Is in the range of about 0.1 to 1 and the degree of substitution of the acetyl group is in the range of about 0.8 to 2.5.
Further, hydroxypropylmethylpropylcellulose, hydroxypropylmethylbutylcellulose and the like (Patent Document 5), hydroxypropylmethylserose phthalate and the like (Patent Document 6) are disclosed as uses such as drug coating.

  Patent Documents 7 and 8 describe resin compositions containing a cellulose ester and a polyester elastomer.

JP-A-56-55425 JP 2008-24919 A US Pat. No. 3,979,179 U.S. Pat. No. 3,940,384 International Publication No. 09/010837 Japanese Patent No. 3017412 JP 2006-111858 A JP 2006-241664 A

The present inventors paid attention for the first time to use cellulose as a carbon neutral resin. However, since cellulose generally does not have thermoplasticity, it is difficult to mold by heating or the like, and thus is not suitable for molding. Further, even if thermoplasticity can be imparted, there is a problem that strength such as impact resistance is greatly reduced.
For example, the cellulose derivatives described in Patent Documents 3, 4, and 6 are water-soluble or swellable and lack strength, which is not preferable as a molding material. Moreover, although it is described that the cellulose derivative described in Patent Document 5 is poorly water-soluble, only the description is included in the text, and its synthesis method and usage form are specifically disclosed in Examples and the like. Absent.
Moreover, since the resin composition containing a cellulose ester and a polyester elastomer as described in Patent Documents 7 and 8 is inferior in DuPont impact strength, abrasion resistance, and moldability (fluidity), improvement is necessary. is there.

  The object of the present invention is to have good impact resistance (particularly Charpy impact strength and high resistance in the DuPont impact test that does not affect the resin orientation), high rigidity (flexural modulus), good wear resistance, and molding processing. It is to provide a thermoplastic resin composition having high fluidity (melt flow rate) suitable for the above. Another object of the present invention is to provide a molded body obtained by molding the thermoplastic resin composition, a method for producing the molded body, and a casing composed of the molded body.

The present inventors paid attention to the molecular structure of cellulose, and made cellulose a cellulose derivative having a specific structure having an ether structure and an ester structure, and a thermoplastic resin composition containing the cellulose derivative having the specific structure and a polyester elastomer, The inventors have found that excellent performance is exhibited from all the viewpoints of melt flow rate, Charpy impact strength, DuPont impact strength, flexural modulus, and wear resistance, and have completed the present invention.
That is, the said subject can be achieved by the following means.

[1]
The hydrogen atom of the hydroxyl group contained in cellulose
A cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below;
A thermoplastic resin composition containing a polyester elastomer.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)
[2]
The thermoplastic resin composition according to [1], wherein the cellulose derivative further includes at least one group in which a hydrogen atom of a hydroxyl group contained in cellulose is substituted by the following C).
C) a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms. )
[3]
The thermoplastic resin composition according to [1] or [2], wherein the group C) containing an alkyleneoxy group and an acyl group is a group containing a structure represented by the following general formula (3).

(Wherein R _C1 represents a hydrocarbon group, R _C2 represents an alkylene group having 2 or 3 carbon atoms, and n represents an integer of 1 or more.)
[4]
The thermoplastic resin composition according to any one of [1] to [3], wherein R _A is an alkyl group having 1 to 4 carbon atoms.
[5]
The thermoplastic resin composition according to any one of [1] to [4], wherein R _A is a methyl group or an ethyl group.
[6]
The thermoplastic resin composition according to any one of [1] to [5], wherein R _B and R _C1 are each independently an alkyl group or an aryl group.
[7]
The thermoplastic resin composition according to any one of [1] to [6], wherein R _B and R _C1 are each independently a methyl group, an ethyl group, or a propyl group.
[8]
The thermoplastic resin composition according to any one of [1] to [6], wherein R _B is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms.
[9]
The thermoplastic resin composition according to any one of [2] to [8], wherein the alkyleneoxy group is a group represented by the following formula (1) or (2).

[10]
The thermoplastic resin composition according to any one of [1] to [9], wherein the cellulose derivative substantially does not have a carboxyl group, a sulfonic acid group, or a salt thereof.
[11]
The thermoplastic resin composition according to any one of [1] to [10], wherein the cellulose derivative is insoluble in water.
[12]
The thermoplastic resin composition according to any one of [1] to [11], wherein the polyester elastomer is a polyether polyester elastomer of polytetramethylene glycol and polytetramethylene terephthalate.
[13]
The thermoplastic resin composition according to any one of [1] to [11], wherein the polyester elastomer is a polyester block copolymer of polycaprolactone and polytetramethylene terephthalate.
[14]
The thermoplastic resin composition according to any one of [1] to [13], wherein the polyester elastomer is a polyester elastomer having a flexural modulus of 1.5 GPa (measured value according to JIS K-7203) or less.
[15]
The molded object obtained by shape | molding the thermoplastic resin composition in any one of [1]-[14].
[16]
The manufacturing method of a molded object including the process of heating and molding the thermoplastic resin composition in any one of [1]-[14].
[17]
[15] A casing for an electric and electronic device comprising the molded article according to [15].

  Since the thermoplastic resin composition of the present invention has excellent thermoplasticity, it can be formed into a molded body. In addition, the molded body formed by the thermoplastic resin composition of the present invention has good impact resistance (particularly Charpy impact strength and high resistance in a DuPont impact test that hardly affects the resin orientation), and high rigidity (flexural modulus). ), Good wear resistance, and high fluidity (melt flow rate) suitable for molding, such as components for automobiles, home appliances, electrical and electronic equipment, mechanical parts, housing and building materials Etc. can be suitably used. Moreover, since it is a plant-derived resin, it can be replaced with a conventional petroleum-derived resin as a material that can contribute to the prevention of global warming.

In the present invention, the hydrogen atom of the hydroxyl group contained in cellulose is
A cellulose derivative (hereinafter also referred to as “cellulose derivative”) comprising at least one group substituted with A) below and at least one group substituted with B) below;
The present invention relates to a thermoplastic resin composition containing a polyester elastomer.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)
Hereinafter, the present invention will be described in detail.

1. Cellulose derivative The cellulose derivative contained in the molding material of the present invention has a hydrogen atom of a hydroxyl group contained in cellulose.
A cellulose derivative comprising at least one group substituted with A) below and at least one group substituted with B) below.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)
That is, the cellulose derivative in the present invention is a cellulose ether ester, and at least a part of the hydrogen atoms of the hydroxyl group contained in cellulose {(C ₆ H ₁₀ O ₅ ) _n } is A) a hydrocarbon group: —R _A , B) Acyl group: substituted with —CO—R _B (R _B represents a hydrocarbon group).
More specifically, the cellulose derivative in the present invention has a repeating unit represented by the following general formula (A).

In the above general formula (A), R ² , R ³ and R ⁶ are each independently a hydrogen atom, A) a hydrocarbon group: —R _A , B) an acyl group: —CO—R _B (R _B is carbonized) Represents a hydrogen group) or other substituents. However, at least a part of R ² , R ³ , and R ⁶ represents A) a hydrocarbon group, and at least a part of R ² , R ³ , and R ⁶ represents B) an acyl group.

As described above, the cellulose derivative in the present invention has thermoplasticity due to etherification and esterification of at least part of the hydroxyl group of the β-glucose ring by A) a hydrocarbon group and B) an acyl group. It can be expressed and is suitable for molding.
Furthermore, since cellulose is a complete plant-derived component, it is carbon neutral and can greatly reduce the burden on the environment.

  The “cellulose” referred to in the present invention is a polymer compound in which a large number of glucoses are bonded by β-1,4-glycosidic bonds, and the carbon atoms at the 2nd, 3rd and 6th positions in the glucose ring of cellulose. Means that the hydroxyl group bonded to is unsubstituted. Further, “hydroxyl group contained in cellulose” refers to a hydroxyl group bonded to carbon atoms at the 2nd, 3rd and 6th positions in the glucose ring of cellulose.

The cellulose derivative only needs to contain the A) hydrocarbon group and B) acyl group in any part of the whole, and may be composed of the same repeating unit, or a plurality of types. It may consist of repeating units. The cellulose derivative does not need to contain all of the A) hydrocarbon group and B) acyl group in one repeating unit.
More specific embodiments include the following embodiments, for example.
(1) At least one of R ² , R ³ and R ⁶ is A) a repeating unit substituted with a hydrocarbon group, and at least one of R ² , R ³ and R ⁶ is substituted with B) an acyl group A cellulose derivative composed of repeating units.
(2) Any one of R ² , R ³ and R ⁶ of one repeating unit is substituted with A) a hydrocarbon group, and B) an acyl group (that is, the above A) and B in one repeating unit A cellulose derivative composed of the same type of repeating unit.
(3) A cellulose derivative in which repeating units having different substitution positions and different types of substituents are bonded at random.
The cellulose derivative may contain an unsubstituted repeating unit (that is, a repeating unit in which R ² , R ³ and R ⁶ are all hydrogen atoms in the general formula (A)).
Moreover, the cellulose derivative may have other substituents other than a hydrogen atom, A) a hydrocarbon group, and B) an acyl group.

A) Hydrocarbon group: -R _A may be either an aliphatic group or an aromatic group.
When R _A is an aliphatic group, it may be linear, branched, or cyclic, and may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
When R _A is an aromatic group, it may be either a single ring or a condensed ring. When R _A is an aromatic group, the preferable carbon number is 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. Examples of the aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
A) The hydrocarbon group is preferably an aliphatic group because the resulting resin composition has excellent impact resistance, and more preferably an alkyl group because molding processability such as melt flow rate is excellent. And more preferably an alkyl group having 1 to 4 carbon atoms (lower alkyl group). Specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, tert-butyl group, isoheptyl group, and the like. A group or an ethyl group is particularly preferred.

B) an acyl group: In _{-CO-R B, R B} represents a hydrocarbon group. R _B is an aliphatic group, and may be any aromatic group.
If R _B is an aliphatic group, straight chain, branched, and may be any of circular, it may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
If R _B is an aromatic group may be either monocyclic and condensed. Examples of the aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
R _B is preferably an alkyl group or an aryl group. R _B is more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group, still more preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. An alkyl group having 1 or 2 carbon atoms (that is, a methyl group or an ethyl group) is preferable.
Also, R _B, it is also preferably a hydrocarbon group having a branched structure having 3 to 10 carbon atoms, more preferably an alkyl group having a branched structure having 3 to 10 carbon atoms, having a carbon number of 7 to 9 More preferably, it is an alkyl group having a branched structure.
The R _B, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, tert- butyl group, and isoheptyl Etc. Preferably, R _B is a methyl group, an ethyl group, a propyl group, or a 2-ethylhexyl group, more preferably a methyl group, an ethyl group, or a 2-ethylhexyl group.

The cellulose derivative in the thermoplastic resin composition of the present invention contains at least one group in which the hydrogen atom of the hydroxyl group contained in cellulose is substituted with A) and at least one group substituted with B). Although it is a cellulose derivative, it is further preferable from a viewpoint of a bending elastic modulus and abrasion resistance to contain at least 1 group by which the hydrogen atom of the hydroxyl group contained in a cellulose was substituted by following C).
C) a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms. )

In the acyl group (—CO—R _C1 ) contained in C), R _C1 represents a hydrocarbon group. As the hydrocarbon group represented by R _{C1, the same} groups as those described above for R _B can be applied. The preferred range of R _C1 is the same as R _B.

In the alkyleneoxy group (—R _C2 —O—) contained in C), R _C2 represents an alkylene group having 2 or 3 carbon atoms. R _C2 may be linear, branched or cyclic, but is preferably linear or branched, and more preferably branched.
Specific examples of the alkyleneoxy group (—R _C2 —O—) include the following structures.

Among them, a group represented by the following formula (1) or (2) in which —RC ₂ —O— is branched is preferable because the resulting resin composition has excellent bending elastic modulus.

  The group C) may contain a plurality of alkyleneoxy groups or may contain only one. Preferably, the group of C) can be represented by the following general formula (3).

In the general formula (3), R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms. The preferred ranges of R _C1 and R _C2 are the same as those described above. n is an integer of 1 or more. The upper limit of n is not particularly limited, and varies depending on the amount of alkyleneoxy group introduced, but is about 10, for example. n is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1. When a plurality of R _C2 are present, they may be the same or different, but are preferably the same.
In addition, the cellulose derivative in the present invention is a group of C) containing only one alkyleneoxy group (a group in which n is 1 in the general formula (3)) and C) containing two or more alkyleneoxy groups. And a group (a group in which n is 2 or more in the above general formula (3)).

Further, the bonding direction of the alkyleneoxy group to the cellulose derivative in the group C) is not particularly limited, but it is preferable that the alkylene group part (R _C2 ) of the alkyleneoxy group is bonded to the cellulose derivative molecule side.

R _A in A), R B in _B ), R _C1 and R _C2 in C) may have a further substituent or may be unsubstituted, but are preferably unsubstituted.

_{R A} in the A), _{R B} in the B), in the case where the _{where R C1} and _{R C2} in the C) has a further substituent, examples of the further substituent include a halogen atom (e.g. fluorine atom, chlorine atom, bromine Atoms, iodine atoms), hydroxy groups, alkoxy groups (the alkyl group portion preferably has 1 to 5 carbon atoms), alkenyl groups, and the like. However, even when a substituent is included, R _C2 has 2 or 3 carbon atoms. In _the case R A, _{R B,} and _{R C1} is other than alkyl group, an alkyl group (preferably having from 1 to 5 carbon atoms) may have as a substituent.

In particular, when R _B and R _C1 have a further substituent, it is preferable that they substantially have no carboxyl group, sulfonic acid group, and salts thereof. By making the cellulose derivative substantially free of carboxyl groups, sulfonic acid groups, and salts thereof, the thermoplastic resin composition of the present invention can be made water-insoluble, and the moldability can be further improved. . In addition, when the cellulose derivative has a carboxyl group, a sulfonic acid group, and a salt thereof, it is known that the compound stability is deteriorated, and in particular, thermal decomposition may be promoted. It is preferable.
Note that “substantially free of carboxyl groups, sulfonic acid groups, and salts thereof” means only when the cellulose derivative in the present invention has no carboxyl groups, sulfonic acid groups, and salts thereof. In addition, the case where the cellulose derivative in the present invention has a trace amount of carboxyl groups, sulfonic acid groups, and salts thereof in a range insoluble in water is included. For example, a cellulose which is a raw material may contain a carboxyl group, and a cellulose derivative in which the substituents A) to C) are introduced using this may contain a carboxyl group. , A sulfonic acid group, and a cellulose derivative substantially free of salts thereof.
In this case, the preferred content of the carboxyl group, sulfonic acid group, and salts thereof is 1% by mass or less, more preferably 0.5% by mass or less, based on the cellulose derivative.

  Moreover, it is preferable that the cellulose derivative in this invention is insoluble in water. Here, “being insoluble in water” means that the solubility in 100 parts by mass of water at 25 ° C. is 5 parts by mass or less.

  Specific examples of the cellulose derivative in the present invention include acetyl methyl cellulose, acetyl ethyl cellulose, acetyl propyl cellulose, acetyl butyl cellulose, acetyl pentyl cellulose, acetyl hexyl cellulose, acetyl cyclohexyl cellulose, acetyl phenyl cellulose, acetyl naphthyl cellulose, propionyl methyl cellulose, propionyl ethyl cellulose. , Propionylpropylcellulose, propionylbutylcellulose, propionylpentylcellulose, propionylhexylcellulose, propionylcyclohexylcellulose, propionylphenylcellulose, propionylnaphthylcellulose, butyrylmethylcellulose, butyrylethylcellulose, butyrylpropylcellulose Butyrylbutylcellulose, butyrylpentylcellulose, butyrylhexylcellulose, butyrylcyclohexylcellulose, butyrylphenylcellulose, butyrylnaphthylcellulose, methylcellulose-2-ethylhexanoate, ethylcellulose-2-ethylhexanoate, propylcellulose 2-ethylhexanoate, butylcellulose-2-ethylhexanoate, pentylcellulose-2-ethylhexanoate, hexylcellulose-2-ethylhexanoate, cyclohexylcellulose-2-ethylhexanoate, phenylcellulose 2-ethylhexanoate, naphthylcellulose-2-ethylhexanoate, acetoxyethylmethylacetylcellulose, acetoxyethylethylacetylcellulose Acetoxyethylpropylacetylcellulose, acetoxyethylbutylacetylcellulose, acetoxyethylpentylacetylcellulose, acetoxyethylhexylacetylcellulose, acetoxyethylcyclohexylacetylcellulose, acetoxyethylphenylacetylcellulose, acetoxyethylnaphthylacetylcellulose, acetoxyethylmethylpropionylcellulose, acetoxy Ethylethylpropionylcellulose, acetoxyethylpropylpropionylcellulose, acetoxyethylbutylpropionylcellulose, acetoxyethylpentylpropionylcellulose, acetoxyethylhexylpropionylcellulose, acetoxyethylcyclohexylpropionylcellulose, acetoxyethyl Ruphenylpropionylcellulose, acetoxyethylnaphthylpropionylcellulose, acetoxyethylmethylcellulose-2-ethylhexanoate, acetoxyethylethylcellulose-2-ethylhexanoate, acetoxyethylpropylcellulose-2-ethylhexanoate, acetoxyethylbutylcellulose 2-ethylhexanoate, acetoxyethylpentylcellulose-2-ethylhexanoate, acetoxyethylhexylcellulose-2-ethylhexanoate, acetoxyethylcyclohexylcellulose-2-ethylhexanoate, acetoxyethylphenylcellulose-2-ethyl Hexanoate, acetoxyethyl naphthylcellulose-2-ethylhexanoate, propionyloxyethylmeth Ruacetylcellulose, propionyloxyethylethylacetylcellulose, propionyloxyethylpropylacetylcellulose, propionyloxyethylbutylacetylcellulose, propionyloxyethylpentylacetylcellulose, propionyloxyethylhexylacetylcellulose, propionyloxyethylcyclohexylacetylcellulose, propionyloxyethylphenylacetyl Cellulose, propionyloxyethyl naphthylacetyl cellulose, propionyloxyethylmethylpropionylcellulose, propionyloxyethylethylpropionylcellulose, propionyloxyethylpropylpropionylcellulose, propionyloxyethylbutylpropionylcellulose, propionyl Nyloxyethylpentylpropionylcellulose, propionyloxyethylhexylpropionylcellulose, propionyloxyethylcyclohexylpropionylcellulose, propionyloxyethylphenylpropionylcellulose, propionyloxyethylnaphthylpropionylcellulose, propionyloxyethylmethylcellulose-2-ethylhexanoate, propionyloxyethylethylcellulose 2-ethylhexanoate, propionyloxyethylpropylcellulose-2-ethylhexanoate, propionyloxyethylbutylcellulose-2-ethylhexanoate, propionyloxyethylpentylcellulose-2-ethylhexanoate, propionyloxyethylhexyl Cellulose 2-ethylhexanoate, propionyloxyethylcyclohexylcellulose-2-ethylhexanoate, propionyloxyethylphenylcellulose-2-ethylhexanoate, propionyloxyethylnaphthylcellulose-2-ethylhexanoate, acetoxypropylmethylacetyl Cellulose, acetoxypropylethylacetylcellulose, acetoxypropylpropylacetylcellulose, acetoxypropylbutylacetylcellulose, acetoxypropylpentylacetylcellulose, acetoxypropylhexylacetylcellulose, acetoxypropylcyclohexylacetylcellulose, acetoxypropylphenylacetylcellulose, acetoxypropylnaphthylacetylcellulose, Propioni Oxypropylmethylacetylcellulose, propionyloxypropylethylacetylcellulose, propionyloxypropylpropylacetylcellulose, propionyloxypropylbutylacetylcellulose, propionyloxypropylpentylacetylcellulose, propionyloxypropylhexylacetylcellulose, propionyloxypropylcyclohexylacetylcellulose, propionyloxy Examples thereof include propylphenylacetylcellulose, propionyloxypropylnaphthylacetylcellulose, and the like.

A) Hydrocarbon group: —R _A , B) Acyl group: —CO—R _B , and C) Alkyleneoxy group: —R _C2 —O— and acyl group: —CO—R _C1 in the cellulose derivative of the present invention And the number of substitution groups per β-glucose ring unit (substitution degree) are not particularly limited.

For example, A) Hydrocarbon group: Degree of substitution DS _{A of} -R _A (number of R _A with respect to hydroxyl groups at the 2nd, 3rd and 6th positions of the β-glucose ring in the repeating unit) is 1.0 <DS _A It is preferable that 1.0 <DS _A <2.5. Further, DS _A is preferably 1.1 or more.
B) Degree of substitution DS _{B of} acyl group (—CO—R _B ) (number of —CO—R _B with respect to hydroxyl groups at the 2nd, 3rd and 6th positions of the cellulose structure of the β-glucose ring in the repeating unit) 0.1 <DS _B is preferable, and 0.1 <DS _B <2.0 is more preferable.
C) Degree of substitution DS _C of a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (in the repeating unit, the 2nd, 3rd and 6th positions of the cellulose structure of the β-glucose ring) position of C to the hydroxyl group) alkyleneoxy _{group: -R} C2 -O- acyl group: the number of groups containing a _{-CO-R C1)} is preferably _{0 <DS C, 0 <DS} C <1 0.0 is more preferable. 0 <By a DS _C, it is possible to lower the melting initiation temperature of the cellulose derivative can be performed thermoforming easier.
By setting the degree of substitution within the above range, mechanical strength, moldability, and the like can be improved.

Further, the number of unsubstituted hydroxyl groups present in the cellulose derivative is not particularly limited. The degree of substitution DS _{H of} hydrogen atoms (ratio in which the hydroxyl groups at the 2nd, 3rd and 6th positions in the repeating unit are unsubstituted) can be in the range of 0 to 1.5, preferably 0 to 0.6. And it is sufficient. By the DS _H and 0.6 or less, or to improve the fluidity of the thermoplastic resin composition, foaming or the like due to water absorption of the thermoplastic resin composition at the time of acceleration and molding of the pyrolysis can or is suppressed.

In addition, the cellulose derivative in the present invention may have a substituent other than A) a hydrocarbon group, B) an acyl group, and C) a group containing an alkyleneoxy group and an acyl group. Examples of the substituent that may be included include a hydroxyethyl group, a hydroxypropyl group, a hydroxyethoxyethyl group, a hydroxypropoxypropyl group, a hydroxyethoxyethoxyethyl group, and a hydroxypropoxypropoxypropyl group. Therefore, the sum of the degree of substitution of all the substituents of the cellulose derivative is 3, but (DS _A + DS _B + DS _C + DS _H ) is 3 or less.

  The amount of alkyleneoxy group introduced in the group C) is expressed in terms of molar substitution (MS: number of moles of substituent introduced per glucose residue) (edited by Cellulose Society, Cellulose Dictionary P142). The molar substitution degree MS of the alkyleneoxy group is preferably 0 <MS, more preferably 0 <MS ≦ 1.5, and further preferably 0 <MS <1.0. When MS is 1.5 or less (MS ≦ 1.5), heat resistance, moldability and the like can be improved, and a cellulose derivative suitable for a thermoplastic resin composition can be obtained.

As for the molecular weight of the cellulose derivative in the present invention, the number average molecular weight (Mn) is preferably in the range of 5 × 10 ^{3 to} 1000 × 10 ³ , more preferably in the range of 10 × 10 ^{3 to} 500 × 10 ³ , and 10 × 10 ³ to. A range of 200 × 10 ³ is most preferred. The mass average molecular weight (Mw) is preferably in the range of 7 × 10 ^{3 to} 10000 × 10 ³ , more preferably in the range of 15 × 10 ^{3 to} 5000 × 10 ³ , and in the range of 100 × 10 ^{3 to} 3000 × 10 ³ . Is most preferred. By setting the average molecular weight within this range, it is possible to improve the moldability and mechanical strength of the molded body.
The molecular weight distribution (MWD) is preferably in the range of 1.1 to 10.0, more preferably in the range of 1.5 to 8.0. By setting the molecular weight distribution within this range, moldability and the like can be improved.
In the present invention, the number average molecular weight (Mn), mass average molecular weight (Mw) and molecular weight distribution (MWD) can be measured using gel permeation chromatography (GPC). Specifically, N-methylpyrrolidone is used as a solvent, polystyrene gel is used, and the molecular weight can be obtained using a conversion molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene.

2. Method for Producing Cellulose Derivative The method for producing a cellulose derivative in the present invention is not particularly limited, and the cellulose derivative in the present invention can be produced by using cellulose as a raw material and etherifying and esterifying cellulose. The raw material for cellulose is not limited, and examples thereof include cotton, linter, and pulp.

A preferred embodiment of the method for producing a cellulose derivative having the above-mentioned A) hydrocarbon group: -R _A and B) acyl group: -CO-R _B (R _B represents a hydrocarbon group) includes cellulose ether, It includes a step of esterification by reacting acid chloride or acid anhydride in the presence.
As the cellulose ether, for example, one in which at least a part of the hydrogen atoms of the hydroxyl groups at the 2nd, 3rd and 6th positions of the β-glucose ring contained in cellulose is substituted with a hydrocarbon group can be used. Specific examples include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, allyl cellulose, and benzyl cellulose.

A) hydrocarbon group: —R _A , B) acyl group: —CO—R _B (R _B represents a hydrocarbon group), and C) alkyleneoxy group: —R _C2 —O— and an acyl group: A preferred embodiment of a method for producing a cellulose derivative having a group containing —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms) is a hydrocarbon group. And a hydroxyethyl cellulose ether having a hydroxyethyl group or a hydroxypropyl cellulose ether having a hydroxypropyl group are reacted with an acid chloride or an acid anhydride to cause esterification (acylation). .
Further, as another embodiment, for example, after etherification with cellulose ether such as methyl cellulose or ethyl cellulose with propylene oxide or the like, alkyl chloride such as methyl chloride or ethyl chloride / alkylene oxide having 3 carbon atoms or the like is allowed to act on cellulose. Furthermore, a method including a step of esterification by reacting an acid chloride or an acid anhydride is also included.
As a method for reacting acid chloride, for example, the method described in Cellulose 10; 283-296, 2003 can be used.
Specific examples of the cellulose ether having a hydrocarbon group and a hydroxyethyl group include hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl propyl cellulose, hydroxyethyl allyl cellulose, and hydroxyethyl benzyl cellulose. Preferred are hydroxyethyl methyl cellulose and hydroxyethyl ethyl cellulose.
Specific examples of the cellulose ether having a hydrocarbon group and a hydroxypropyl group include hydroxypropylmethylcellulose, hydroxypropylethylcellulose, hydroxypropylpropylcellulose, hydroxypropylallylcellulose, hydroxypropylbenzylcellulose, and the like. Preferred are hydroxypropylmethylcellulose and hydroxypropylethylcellulose.

  As the acid chloride, B) acyl group and carboxylic acid chloride corresponding to the acyl group contained in C) can be used. Examples of the carboxylic acid chloride include acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, pentanoyl chloride, 2-methylbutanoyl chloride, 3-methylbutanoyl chloride, pivaloyl chloride, hexanoyl chloride, 2-methylpentanoyl chloride, 3-methylpentanoyl chloride, 4-methylpentanoyl chloride, 2,2-dimethylbutanoyl chloride, 2,3-dimethylbutanoyl chloride, 3,3-dimethylbutanoyl chloride, 2- Ethylbutanoyl chloride, heptanoyl chloride, 2-methylhexanoyl chloride, 3-methylhexanoyl chloride, 4-methylhexanoyl chloride, 5-methylhexanoyl chloride, 2,2-dimethylpentanoyl chloride, , 3-dimethylpentanoyl chloride, 3,3-dimethylpentanoyl chloride, 2-ethylpentanoyl chloride, cyclohexanoyl chloride, octanoyl chloride, 2-methylheptanoyl chloride, 3-methylheptanoyl chloride, 4-methyl Heptanoyl chloride, 5-methylheptanoyl chloride, 6-methylheptanoyl chloride, 2,2-dimethylhexanoyl chloride, 2,3-dimethylhexanoyl chloride, 3,3-dimethylhexanoyl chloride, 2-ethylhexanoyl Chloride, 2-propylpentanoyl chloride, nonanoyl chloride, 2-methyloctanoyl chloride, 3-methyloctanoyl chloride, 4-methyloctanoyl chloride, 5-methyloctanoyl chloride, 6-methyloctanoy Chloride, 2,2-dimethylheptanoyl chloride, 2,3-dimethylheptanoyl chloride, 3,3-dimethylheptanoyl chloride, 2-ethylheptanoyl chloride, 2-propylhexanoyl chloride, 2-butylpentanoyl chloride, Decanoyl chloride, 2-methylnonanoyl chloride, 3-methylnonanoyl chloride, 4-methylnonanoyl chloride, 5-methylnonanoyl chloride, 6-methylnonanoyl chloride, 7-methylnonanoyl chloride, 2,2- Examples include dimethyloctanoyl chloride, 2,3-dimethyloctanoyl chloride, 3,3-dimethyloctanoyl chloride, 2-ethyloctanoyl chloride, 2-propylheptanoyl chloride, 2-butylhexanoyl chloride and the like.

As the acid anhydride, for example, carboxylic acid anhydrides corresponding to the acyl group contained in the above B) acyl group and C) can be used. Examples of such carboxylic anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, 2-ethylhexanoic acid. An anhydride, nonanoic acid anhydride, etc. are mentioned.
As described above, since the cellulose derivative in the present invention preferably has no carboxylic acid as a substituent, for example, a dicarboxylic acid such as phthalic anhydride, maleic anhydride, or the like, and a compound that generates a carboxyl group by reacting with cellulose. It is preferable not to use.

  Other specific production conditions and the like can follow conventional methods. For example, a method described in “Encyclopedia of Cellulose” pages 131 to 164 (Asakura Shoten, 2000) can be referred to.

3. Polyester elastomer The thermoplastic resin composition of the present invention contains a polyester elastomer. Since the polyester elastomer has high affinity with the cellulose derivative due to its high polarity, it has a soft segment. Therefore, the polyester elastomer is mixed with the specific cellulose derivative in the present invention to form a thermoplastic resin composition. Impact resistance, moldability, and abrasion resistance can be improved as compared with the case where a cellulose derivative is used alone. Since the specific cellulose derivative in the present invention includes an ether structure and an ester structure, it has an ether bond with a higher degree of freedom around the main chain than a conventional cellulose ester and the like. Excellent affinity. Therefore, the polyester elastomer is excellent in dispersibility with respect to the specific cellulose derivative in the present invention, and both are well mixed, and thus it is considered that such an effect is exhibited.

The polyester elastomer in the present invention preferably has a mass average molecular weight of 10,000 or more and an A hardness measured by JIS K6301 of 100 or less. The mass average molecular weight can be determined using gel permeation chromatography (GPC). Specifically, chloroform / hexafluoroisopropanol = 9/1 (volume ratio) is used as a solvent, polystyrene gel is used, and it is obtained using a conversion molecular weight calibration curve obtained in advance from a standard monodisperse polystyrene composition curve. it can.
The polyester elastomer is not particularly limited, but is preferably a polyether ester block copolymer or a polyester / ester block copolymer having a hard segment made of an aromatic polyester and a soft segment made of poly (alkylene oxide) glycol and / or an aliphatic polyester. Polymer, polyetherester / ester block copolymer.
The aromatic polyester constituting the hard segment is preferably a polymer obtained by condensation polymerization of a dicarboxylic acid component and a diol component in which 60 mol% or more is a terephthalic acid component. Here, as dicarboxylic acid components other than terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4, Aromatic dicarboxylic acids such as 4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid Aliphatic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and derivatives thereof are preferably used. The diol component is preferably an aliphatic glycol having 2 to 20 carbon atoms, specifically, for example, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, Examples include 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, and derivatives thereof.

  Specific examples of the aromatic polyester include polyethylene terephthalate, polytetramethylene terephthalate, polybutylene terephthalate, polyethylene (terephthalate / isophthalate), polybutylene (terephthalate / isophthalate), and the like.

  Specific examples of poly (alkylene oxide) glycol and aliphatic polyester constituting the soft segment include polyethylene glycol, polytetramethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol, and poly (tetramethylene oxide). ) Glycols, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and tetrahydrofuran, polyethylene adipate, polybutylene adipate, poly-ε-caprolactone, polyethylene sebacate, polybutylene sebacate and the like.

  The ratio of the soft segment and the hard segment in the polyester elastomer in the present invention is excellent in the balance between the impact resistance and the wear resistance of the resulting resin composition, so that the soft segment / hard segment has a mass ratio of 95 / 5-10 / 90 is preferable and 90 / 10-30 / 70 is more preferable.

Specific examples of the polyester elastomer in the present invention include polyethylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / poly ( Tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / decane dicarboxylate / poly (tetramethylene oxide) glycol block copolymer, Polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / Isophthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene tephthalate / decane dicarboxylate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene tetophthalate / poly (ethylene oxide) Glycol block copolymer, polybutylene terephthalate / polyethylene adipate block copolymer, polybutylene terephthalate / polybutylene adipate block copolymer, polybutylene terephthalate / polybutylene sebacate block copolymer, polybutylene terephthalate / poly-ε -A caprolactone block copolymer etc. are mentioned preferably.
Among these polyester elastomers, in particular, polybutylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / poly (propylene) Oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / polybutylene adipate block copolymer, polybutylene terephthalate / poly-ε- A caprolactone block copolymer is preferably used.
As the polyester elastomer in the present invention, a polyether polyester elastomer of polytetramethylene glycol and polytetramethylene terephthalate, and a polyester block copolymer of polycaprolactone and polytetramethylene terephthalate are particularly preferable.

The polyester elastomer in the present invention preferably has a relative viscosity ηrel of 1.4 to 4.0, particularly 1.6 to 3.0. Here, the relative viscosity ηrel of the polyester elastomer used in the present invention is a value when measured using a phenol / tetrachloroethane mixed solvent having a mass ratio of 60/40 at a concentration of 1.0 g / dl at 20 ° C.
In addition, the polyester elastomer should be a polyester elastomer having a flexural modulus of 1.5 GPa or less (measured value according to JIS K-7203), so that both the impact resistance and the wear resistance of the resulting resin composition can be achieved. It is preferable that More preferably, it is 5 MPa-1 GPa, More preferably, it is 10 MPa-500 MPa.
The method for controlling the polyester elastomer used in the present invention to such a preferable elastic modulus is not particularly limited, but can be achieved by changing the above-described soft segment and hard segment within the above range.
These polyester elastomers can be used in combination of two or more.

As a method for obtaining the polyester elastomer in the present invention, any known method such as JP-A-47-25295 and JP-A-59-13530 can be employed. For example, any of a melt polymerization method, a solution polymerization method, a solid phase polymerization method and the like can be used as appropriate. In the case of a melt polymerization method, a transesterification method or a direct polymerization method may be used. In order to improve the viscosity of the resin, it is of course desirable to perform solid phase polymerization after melt polymerization.
As the catalyst used for the reaction, an antimony catalyst, a germanium catalyst, and a titanium catalyst are preferable. In particular, the titanium catalyst is preferably a tetraalkyl titanate such as tetrabutyl titanate or tetramethyl titanate, or an oxalic acid metal salt such as titanium potassium oxalate. The other catalyst is not particularly limited as long as it is a known catalyst, and examples thereof include tin compounds such as dibutyltin oxide and dibutyltin dilaurate, and lead compounds such as lead acetate.
Commercially available polyester elastomers can also be used in the present invention. For example, perprene P30B (copolymer of polytetramethylene glycol and polytetramethylene terephthalate), perprene P40H (copolymer of polytetramethylene glycol and polytetramethylene terephthalate), perprene P90B (polytetramethylene glycol and polytetramethylene) Copolymer with terephthalate), perprene S1001 (copolymer of polycaprolactone and polytetramethylene terephthalate), perprene S6001 (copolymer of polycaprolactone and polytetramethylene terephthalate) (all manufactured by Toyobo Co., Ltd.) Etc.

4). Thermoplastic resin composition and molded article The thermoplastic resin composition of the present invention contains the cellulose derivative and the polyester elastomer described above, and may contain other additives as necessary.
The content rate of the component contained in the molding material of this invention is not specifically limited.
The content ratio of the cellulose derivative contained in the molding material of the present invention is not particularly limited. Preferably, the cellulose derivative is contained in an amount of 35% by mass or more, more preferably 45% by mass or more and 99% by mass, and still more preferably 60% by mass or more and 95% by mass with respect to the total solid content.
The content ratio of the polyester elastomer contained in the molding material of the present invention is not particularly limited. Preferably, the polyester elastomer is contained in an amount of 1 to 70% by mass, more preferably 5 to 50% by mass, based on the total solid content.
In addition, from the standpoint of impact resistance, molding processability, and wear resistance, the mass composition ratio of the cellulose derivative and the polyester elastomer (cellulose derivative / polyester elastomer) is 20/80 to 95/5. It is preferably 40/60 to 90/10, more preferably 60/40 to 90/10.

  The thermoplastic resin composition of the present invention may contain various additives such as an antioxidant, a filler (reinforcing material), and a flame retardant as required, in addition to the cellulose derivative and the polyester elastomer.

  It is preferable that the thermoplastic resin composition of the present invention further contains an antioxidant. Examples of the antioxidant include phenolic antioxidants, amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like, and phenolic antioxidants are preferable. As the phenolic antioxidant, Irganox 1010, Irganox 1076, Irganox 3114 manufactured by Ciba Specialty Chemicals Co., Ltd. can be suitably used.

  When the thermoplastic resin composition of the present invention is an antioxidant, its content is not particularly limited, but is usually 5% by mass or less, preferably 0.005 to 5% by mass, based on the thermoplastic resin composition, More preferably, it is 0.01-1 mass%.

The thermoplastic resin composition of the present invention may contain a filler (reinforcing material). By containing the filler, the mechanical properties of the molded body formed by the thermoplastic resin composition can be enhanced.
A well-known thing can be used as a filler. The shape of the filler may be any of fibrous, plate-like, granular, powdery and the like. Further, it may be inorganic or organic.
Specifically, as the inorganic filler, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, and other inorganic fillers; glass flakes, non-swellable mica, carbon black, graphite, metal foil , Ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silica, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide Um, aluminum oxide, titanium oxide, magnesium oxide, aluminum silicate, silicon oxide, aluminum hydroxide, magnesium hydroxide, gypsum, novaculite, dawsonite, and a plate-like or granular inorganic fillers of clay or the like.

  Organic fillers include synthetic fibers such as polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, and acetate fiber, and natural fibers such as kenaf, ramie, cotton, jute, hemp, sisal, Manila hemp, flax, linen, silk, and wool. Examples thereof include fibrous organic fillers obtained from microcrystalline cellulose, sugar cane, wood pulp, paper waste, waste paper and the like, and granular organic fillers such as organic pigments.

  When the thermoplastic resin composition contains a filler, the content is not limited, but is usually 30 parts by mass or less, preferably 5 to 10 parts by mass with respect to 100 parts by mass of the cellulose derivative.

The thermoplastic resin composition of the present invention may contain a flame retardant. Thereby, the flame retarding effect such as reduction or suppression of the burning rate can be improved.
The flame retardant is not particularly limited, and a conventional flame retardant can be used. For example, brominated flame retardants, chlorine-based flame retardants, phosphorus-containing flame retardants, silicon-containing flame retardants, nitrogen compound-based flame retardants, inorganic flame retardants and the like can be mentioned. Among these, hydrogen halides are not generated by thermal decomposition during resin compounding or molding, and do not corrode processing machines or molds or deteriorate the working environment. Phosphorus-containing flame retardants and silicon-containing flame retardants are preferred because they are less likely to adversely affect the environment through the generation of harmful substances such as dioxins when they are diffused or decomposed.

  The phosphorus-containing flame retardant is not particularly limited, and a commonly used one can be used. Examples thereof include organic phosphorus compounds such as phosphate esters, phosphate condensation esters, and polyphosphates.

  Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) Phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl Acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl Examples include 2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate be able to.

  Examples of phosphoric acid condensed esters include resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof. Aromatic phosphoric acid condensed ester and the like.

  Moreover, the polyphosphate which consists of a salt of phosphoric acid, polyphosphoric acid, a periodic table group 1-14 group metal, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts and triazines.

In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate), and structures in which a phosphorus atom and a nitrogen atom are connected by a double bond Phosphazene compounds having phosphoric acid and phosphoric ester amides.
These phosphorus-containing flame retardants may be used singly or in combination of two or more.

  Examples of the silicon-containing flame retardant include an organosilicon compound having a two-dimensional or three-dimensional structure, polydimethylsiloxane, or a methyl group at a side chain or a terminal of polydimethylsiloxane, a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, Examples thereof include those substituted or modified with an aromatic hydrocarbon group, so-called silicone oils, or modified silicone oils.

Examples of the substituted or unsubstituted aliphatic hydrocarbon group and aromatic hydrocarbon group include an alkyl group, a cycloalkyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, a polyether group, a carboxyl group, a mercapto group, Examples include a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group.
These silicon-containing flame retardants may be used alone or in combination of two or more.

  Examples of the flame retardant other than the phosphorus-containing flame retardant or the silicon-containing flame retardant include, for example, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, Metastannic acid, tin oxide, tin oxide salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, tungsten Inorganic flame retardants such as acid metal salts, complex oxides of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, and swellable graphite can be used. . These other flame retardants may be used alone or in combination of two or more.

  When the thermoplastic resin composition of the present invention contains a flame retardant, the content is not limited, but is usually 30 parts by mass or less, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the cellulose derivative. Good. By setting it as this range, impact resistance, brittleness, etc. can be improved, or generation | occurrence | production of pellet blocking can be suppressed.

In addition to those described above, the thermoplastic resin composition of the present invention contains other components for the purpose of further improving various properties such as moldability and flame retardancy, as long as the object of the present invention is not impaired. May be.
Examples of other components include polymers other than the cellulose derivatives and the polyester elastomers, plasticizers, stabilizers (antioxidants, ultraviolet absorbers, etc.), mold release agents (fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters). , Aliphatic partially saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone), antistatic agent, difficult Examples include a combustion aid, a processing aid, an anti-drip agent, an antibacterial agent, and an antifungal agent. Furthermore, a coloring agent containing a dye or a pigment can be added.

As the polymer other than the cellulose derivative and the polyester elastomer, either a thermoplastic polymer or a thermosetting polymer can be used, but a thermoplastic polymer is preferable from the viewpoint of moldability. Specific examples of polymers other than cellulose derivatives include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene- 1 copolymer, polypropylene homopolymer, polypropylene copolymer (such as ethylene-propylene block copolymer), polyolefins such as polybutene-1 and poly-4-methylpentene-1, polybutylene terephthalate, polyethylene terephthalate and other aromatic polyesters, etc. Polyamide such as polyester, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 12, etc., polystyrene, high impact polystyrene, poly Settals (including homopolymers and copolymers), polyurethanes, aromatic and aliphatic polyketones, polyphenylene sulfide, polyetheretherketone, thermoplastic starch resins, polymethyl methacrylate and methacrylate-acrylate copolymers Acrylic resin, AS resin (acrylonitrile-styrene copolymer), ABS resin, AES resin (ethylene rubber reinforced AS resin), ACS resin (chlorinated polyethylene reinforced AS resin), ASA resin (acrylic rubber reinforced AS resin) , Polyvinyl chloride, polyvinylidene chloride, vinyl ester resin, maleic anhydride-styrene copolymer, MS resin (methyl methacrylate-styrene copolymer), polycarbonate, polyarylate, polysulfone, polyethersulfone, pheno Thermoplastic polyimide such as silicone resin, polyphenylene ether, modified polyphenylene ether, polyetherimide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-perfluoro Fluoropolymers such as alkyl vinyl ether copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, cellulose acetate, polyvinyl alcohol, unsaturated polyester, melamine resin, A phenol resin, a urea resin, a polyimide, etc. can be mentioned.
In addition, various acrylic rubbers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers), ethylene-acrylic acid alkyl ester copolymers (for example, ethylene-ethyl acrylate copolymer) Copolymer, ethylene-butyl acrylate copolymer), diene rubber (for example, 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (for example, Styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer Polymer, polybutadiene Styrene-grafted styrene, butadiene-acrylonitrile copolymer), polyisobutylene, copolymer of isobutylene and butadiene or isoprene, butyl rubber, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, nitrile rubber, Examples include polyether rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, and other thermoplastic elastomers such as polyurethane, polyester, and polyamide.

Furthermore, those having various degrees of crosslinking, those having various microstructures such as cis structure and trans structure, those having vinyl groups, those having various average particle diameters, core layers and the like A multi-layer structure polymer called a so-called core shell rubber, which is composed of one or more shell layers to be covered and whose adjacent layers are composed of different types of polymers, can also be used, and further a core shell rubber containing a silicone compound Can also be used.
These polymers may be used alone or in combination of two or more.

  When the thermoplastic resin composition of the present invention contains a polymer other than the cellulose derivative and the polyester elastomer, the content is preferably 30 parts by mass or less, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the cellulose derivative. preferable.

  The thermoplastic resin composition of the present invention may contain a plasticizer. Thereby, a flame retardance and a moldability can be improved further. As the plasticizer, those commonly used for polymer molding can be used. Examples thereof include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

  Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4 -Polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid. Trimellitic acid esters such as tributyl, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipic acid Adipic acid esters such as benzylbutyl diglycol, citrates such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacin Dibutyl, and di-2-ethylhexyl sebacate, and the like.

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, bisphenols And polyalkylene glycols such as propylene oxide addition polymers and bisphenol tetrahydrofuran addition polymers, or terminal epoxy-modified compounds thereof, terminal ester-modified compounds, and terminal ether-modified compounds.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

  Specific examples of other plasticizers include benzoate esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxy acid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, and various sorbitols.

  When the thermoplastic resin composition of the present invention contains a plasticizer, its content is usually 30 parts by mass or less, and 0.005 to 20 parts by mass with respect to 100 parts by mass in total of the cellulose derivative and the polyester elastomer. Preferably, it is 0.01-10 mass parts.

The molded article of the present invention can be obtained by molding a thermoplastic resin composition containing the cellulose derivative and the polyester elastomer. More specifically, it is obtained by a production method including a step of heating the cellulose derivative or the thermoplastic derivative composition containing the cellulose derivative and various additives as necessary, and molding by various molding methods. .
The manufacturing method of the molded object of this invention includes the process of heating and molding the said thermoplastic resin composition.
Examples of the molding method include injection molding, extrusion molding, blow molding and the like.
The heating temperature is usually 160 to 300 ° C, preferably 180 to 260 ° C.

  The use of the molded product of the present invention is not particularly limited. For example, interior or exterior parts of electric and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.), automobiles, mechanical parts, etc. And materials for housing and construction. Among these, from the viewpoint of having excellent heat resistance and impact resistance and low environmental load, for example, exterior parts for electric and electronic devices such as copiers, printers, personal computers, televisions (especially casings) ) Can be suitably used.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the scope of the present invention is not limited to the examples shown below.

<Synthesis Example 1: Synthesis of acetoxypropylmethylacetylcellulose (C-1)>
Weigh 60 g of hydroxypropylmethylcellulose (trade name Metrolose 90SH-100; manufactured by Shin-Etsu Chemical Co., Ltd.) and 2100 mL of N, N-dimethylacetamide in a 5 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser and dropping funnel, and stir at room temperature. did. After confirming that the reaction system became transparent and completely dissolved, 101 mL of acetyl chloride was slowly added dropwise to raise the temperature of the system to 80 ° C to 90 ° C. After stirring for 3 hours, the temperature of the reaction system was cooled to room temperature. When the reaction solution was added to 10 L of water with vigorous stirring, a white solid was precipitated. The white solid was filtered off by suction filtration and washed with a large amount of water three times. The obtained white solid was vacuum-dried at 100 ° C. for 6 hours to obtain the objective cellulose derivative (C-1) (acetoxypropylmethylacetylcellulose) as a white powder.

<Synthesis Examples 2, 3, and 4: Synthesis of acetoxyethyl methyl acetyl cellulose (C-2), methyl acetyl cellulose (C-3), and ethyl acetyl cellulose (C-4)>
Hydroxypropyl methylcellulose (trade name Metrolose 90SH-100; manufactured by Shin-Etsu Chemical Co., Ltd.) in Synthesis Example 1 was replaced with hydroxyethyl methylcellulose (trade name Marporose ME-250T; manufactured by Matsumoto Yushi), methylcellulose (trade name Marporose M-4000: Matsumoto Yushi Co., Ltd.) Acetoxyethyl methyl acetyl cellulose (C-2), methyl acetyl cellulose (C-3), ethyl acetyl cellulose (C-3), and ethyl cellulose (trade name Etcel 300CP: manufactured by Dow Chemical). C-4) was obtained.

<Synthesis Example 5: Synthesis of methylcellulose-2-ethylhexanoate (C-5)>
In a 3 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 80 g of methyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1.8) and 1500 mL of pyridine were weighed and stirred at room temperature. 173 mL of 2-ethylhexanoyl chloride was dripped slowly under water cooling here, and also it stirred at 60 degreeC for 6 hours. After the reaction, the reaction solution was returned to room temperature and quenched by adding 200 mL of methanol under ice cooling. When the reaction solution was added to 12 L of water with vigorous stirring, a white solid was precipitated. The white solid was filtered off by suction filtration and washed 3 times with a large amount of methanol solvent. The obtained white solid was vacuum-dried at 100 ° C. for 6 hours to obtain methylcellulose-2-ethylhexanoate (C-5).

<Synthesis Example 6: Synthesis of valeroxypropylmethyl valeroyl cellulose (C-6)>
Instead of methyl cellulose in Synthesis Example 5 (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1.8), valeroyl was changed to hydroxypropyl methylcellulose (trade name Metroze 90SH-100; manufactured by Shin-Etsu Chemical Co., Ltd.) and 2-ethylhexanoyl chloride. Valeroxypropyl bvaleroylcellulose (C-6) was obtained in the same manner as in Synthesis Example 5 except that chloride was used.

<Synthesis Example 7: Synthesis of valeroxybutyl methyl valeroyl cellulose (C-7)>
Valeroxybutyl methyl valeroyl cellulose in the same manner as in Synthesis Example 6 except that hydroxybutyl methyl cellulose (Metroze SM4000: manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the hydroxypropyl methyl cellulose (commercial name Metroze 90SH-100; manufactured by Shin-Etsu Chemical Co., Ltd.) in Synthesis Example 6. (C-7) was obtained.

  In addition, the kind and substitution degree of the hydrocarbon group, the kind and molar substitution degree of the alkyleneoxy group, the kind of acyl group, and the acylation degree of the cellulose derivative obtained above are as described in Cellulose Communication 6, 73-79 (1999). Were observed and determined by 1H-NMR. The degree of substitution of the hydrocarbon group is the number of moles of the hydrocarbon group substituted on the glucose ring unit, and takes a value of 0 or more and less than 3. The molar substitution degree of the alkyleneoxy group is the number of moles of the alkyleneoxy group substituted on the glucose ring unit, and takes a value of 0 or more. The degree of acylation indicates the degree of substitution with an acyl group by esterifying a hydroxyl group present in the glucose ring or ether substituent of cellulose, and is represented by 0 or more and 100 or less.

<Measurement of molecular weight of cellulose derivative>
About the obtained cellulose derivative, the number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured. These measuring methods are as follows.
[Molecular weight and molecular weight distribution]
For the measurement of the number average molecular weight (Mn) and the mass average molecular weight (Mw), gel permeation chromatography (GPC) was used. Specifically, N-methylpyrrolidone was used as a solvent, a polystyrene gel was used, and the molecular weight was determined using a conversion molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) was used.

  The number average molecular weight (Mn), the mass average molecular weight (Mw) and the degree of substitution are shown together in Table 1.

<Polyester elastomer>
(P-1); Perprene P30B manufactured by Toyobo Co., Ltd. (copolymer of polytetramethylene glycol and polytetramethylene terephthalate, A hardness 71, flexural modulus 15 MPa)
(P-2): Perprene P40H manufactured by Toyobo Co., Ltd. (polytetramethylene glycol and polytetramethylene terephthalate copolymer, A hardness 89, flexural modulus 51 MPa)
(P-3); Perprene P90B manufactured by Toyobo Co., Ltd. (copolymer of polytetramethylene glycol and polytetramethylene terephthalate, A hardness 96, flexural modulus 160 MPa)
(P-4); Toyobo Co., Ltd. perprene S1001 (polycaprolactone and polytetramethylene terephthalate copolymer, A hardness 96, flexural modulus 125 MPa)
(P-5); Perprene S6001 manufactured by Toyobo Co., Ltd. (copolymer of polycaprolactone and polytetramethylene terephthalate, A hardness 99, flexural modulus 570 MPa)

<Example 1: Preparation of thermoplastic resin composition and production of molded article>
85 parts by weight of cellulose derivative (C-1), 15 parts by weight of polyester elastomer (P-1) and 1.0 part by weight of antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals) are mixed for 3 minutes with a Henschel mixer and heated. A plastic resin composition was prepared. This was pelletized with a Ikekai biaxial kneader PCM-30 (L / D = 25) at a barrel temperature of 210 ° C. and a screw rotation speed of 300 rpm.
Next, the pellets were supplied to an injection molding machine (Semi-automatic injection molding machine manufactured by Imoto Seisakusho Co., Ltd.) and 80 mm × 10 mm × at a cylinder temperature of 200 ° C., a mold temperature of 30 ° C., and an injection pressure of 1.5 kgf / cm ² . A 4 mm multipurpose specimen was molded. The mold temperature was 30 ° C.

<Examples 2-14, Comparative Examples 1-3>
In the same manner as in Example 1, as shown in Table 2 below, using the cellulose derivatives (C-2) to (C-7) and the polyester elastomers (P-2) to (P-5), thermoplastic resins A composition was prepared and pelletized to produce a test piece. In Table 2, the content of the cellulose derivative and the polyester elastomer was expressed in “parts by mass”.

<Measurement of physical properties of molded article>
The molded product was measured for Charpy impact strength, DuPont impact strength, melt flow rate, flexural modulus, and abrasion resistance according to the following method. The results are shown in Table 2.

[Charpy impact strength]
In accordance with ISO 179, a notch having an incident angle of 45 ± 0.5 ° and a tip of 0.25 ± 0.05 mm is formed on the multi-purpose test piece molded by injection molding, 23 ° C. ± 2 ° C., 50% ± 5 After standing at% RH for 48 hours or more, the impact strength was measured edgewise with a Charpy impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

[DuPont impact]
Using each of the thermoplastic resin compositions, a 100 mm × 100 mm × 3 mmt molding plate was produced by injection molding, and the 50% fracture energy was measured according to JIS K5400.

[Melt flow rate]
The pellet-shaped thermoplastic resin composition was measured at a cylinder temperature of 220 ° C. and a load of 10 kgf in accordance with JIS K7210.

[Bending elastic modulus]
Based on JIS K7203, it measured at the atmospheric temperature of 23 degreeC using the said multipurpose test piece.

[Abrasion resistance]
In accordance with JIS K7218 A method, a hollow cylindrical test piece having an outer diameter of 25.6 mm, an inner diameter of 20 mm, a height of 15 mm, and a contact area of 2 cm ² is used, and an atmospheric temperature is measured using a thrust wear tester (manufactured by Toyo Seiki Seisakusho). The self-material was selected as a wear partner material at 23 ° C. without lubrication, and the sliding linear velocity was 6 cm / sec, the surface pressure was 2 kg / cm ² , the total travel distance was 50 km, and the wear amount per unit distance was determined.

In Table 2, “NB” means “not destroyed”.
The thermoplastic resin compositions of Examples 1 to 14 all had high Charpy impact strength, DuPont impact strength, melt flow rate, and flexural modulus, and were excellent in wear resistance.
Here, C) a molded product obtained from a thermoplastic resin composition containing a cellulose derivative having a group containing an alkyleneoxy group and an acyl group is C) a cellulose derivative having no group containing an alkyleneoxy group and an acyl group There was a tendency that the bending elastic modulus was higher and the wear resistance was further improved with respect to a molded product obtained from the thermoplastic resin composition containing.
The thermoplastic resin composition using the cellulose ester having no ether structure of Comparative Example 3 had a low DuPont impact strength and a low melt flow rate.

Claims (17)

The hydrogen atom of the hydroxyl group contained in cellulose
A cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below;
A thermoplastic resin composition containing a polyester elastomer.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.) The thermoplastic resin composition according to claim 1, wherein the cellulose derivative further comprises at least one group in which a hydrogen atom of a hydroxyl group contained in cellulose is substituted by the following C).
C) a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms. ) The thermoplastic resin composition according to claim 1 or 2, wherein the C) group containing an alkyleneoxy group and an acyl group is a group containing a structure represented by the following general formula (3).

(Wherein R _C1 represents a hydrocarbon group, R _C2 represents an alkylene group having 2 or 3 carbon atoms, and n represents an integer of 1 or more.) The thermoplastic resin composition according to any one of claims 1 to 3, wherein R _A is an alkyl group having 1 to 4 carbon atoms. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the _RA is a methyl group or an ethyl group. The thermoplastic resin composition according to claim 1, wherein R _B and R _C1 are each independently an alkyl group or an aryl group. The thermoplastic resin composition according to any one of claims 1 to 6, wherein R _B and R _C1 are each independently a methyl group, an ethyl group, or a propyl group. The thermoplastic resin composition according to any one of claims 1 to 6, wherein R _B is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms. The thermoplastic resin composition according to any one of claims 2 to 8, wherein the alkyleneoxy group is a group represented by the following formula (1) or (2).

  The thermoplastic resin composition according to any one of claims 1 to 9, wherein the cellulose derivative is substantially free of carboxyl groups, sulfonic acid groups, and salts thereof.   The thermoplastic resin composition according to any one of claims 1 to 10, wherein the cellulose derivative is insoluble in water.   The thermoplastic resin composition according to any one of claims 1 to 11, wherein the polyester elastomer is a polyether polyester elastomer of polytetramethylene glycol and polytetramethylene terephthalate.   The thermoplastic resin composition according to any one of claims 1 to 11, wherein the polyester elastomer is a polyester block copolymer of polycaprolactone and polytetramethylene terephthalate.   The thermoplastic resin composition according to any one of claims 1 to 13, wherein the polyester elastomer is a polyester elastomer having a flexural modulus of 1.5 GPa (measured value according to JIS K-7203) or less.   The molded object obtained by shape | molding the thermoplastic resin composition in any one of Claims 1-14.   The manufacturing method of a molded object including the process of heating and shape | molding the thermoplastic resin composition in any one of Claims 1-14.   A housing for electrical and electronic equipment comprising the molded body according to claim 15.