JP2011132435A - Molding material, molded article, manufacturing method therefor, and housing for electric/electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding material excellent in all viewpoints of charpy impact strength, flexural modulus and dispersibility and making sufficient injuring-resistance and weather-resistance compatible. <P>SOLUTION: The molding material includes a cellulose derivative containing at least one group (A) in which a hydrogen atom of a hydroxyl group contained in the cellulose is substituted by a 1-3C hydrocarbon group: -R<SB>A</SB>only comprising carbon and hydrogen and containing at least one group (B) in which the hydrogen atom of the hydroxyl group contained in the cellulose is substituted by an acyl group: -CO-R<SB>B</SB>(R<SB>B</SB>represents a hydrocarbon group only comprising carbon and hydrogen), and an aromatic polyamide. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a molding material, a molded body, a manufacturing method thereof, and an electrical and electronic device.

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 Document 7 describes that cellulose ester and thermoplastic resin polyamide can be used in combination.
Patent Document 8 describes that a cellulose ether ester obtained by esterifying hydroxypropyl cellulose phthalate with propylene oxide and a polyester amide are used in combination.
Patent Document 9 describes that acetylbutyl cellulose and urethane (including amide) are used in combination.

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 Japanese Patent Laid-Open No. 9-188879 JP 2008-94104 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, what combined the cellulose ester or cellulose ether ester and polyamide which were described in patent documents 7-9 is inferior to Charpy impact strength, scratch resistance, and a weather resistance, and needs improvement.
In addition, although aromatic polyamide is excellent in scratch resistance, it is known by Unexamined-Japanese-Patent No. 5-98111 etc. that it is inferior to calcium chloride aqueous solution property performed as an accelerated test of weather resistance evaluation.

  An object of the present invention is to provide a molding material having good impact resistance and having both good scratch resistance and weather resistance. Another object of the present invention is to provide a method for producing the molding material, a molding obtained by molding the molding material, a method for producing the molding, and a casing for electrical and electronic equipment comprising the molding. Is to provide.

The present inventors paid attention to the molecular structure of cellulose, made cellulose a cellulose derivative having a specific structure having an ether structure and an ester structure, and formed a Charpy impact using a molding material containing the cellulose derivative having the specific structure and an aromatic polyamide. The inventors have found that the viewpoints of strength and flexural modulus are all excellent, and that both good scratch resistance and weather resistance are exhibited, and the present invention has been completed.
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 molding material containing an aromatic polyamide.
A) A hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group consisting of only carbon and hydrogen.)

2. 2. The molding material according to 1 above, 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. )

3. The molding material according to 1 or 2 above, 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.)

4). 4. Molding material in any one of said 1-3 whose said _RA is a methyl group or an ethyl group.
5. 5. The molding material according to any one of 1 to 4, wherein R _B and R _C1 are each independently an alkyl group or an aryl group.
6). The molding material according to any one of 1 to 5, wherein R _B and R _C1 are each independently a methyl group, an ethyl group, or a propyl group.
7). Wherein R _B is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms, molding material according to any of the above 1-5.

8). 8. The molding material according to any one of 2 to 7, wherein the alkyleneoxy group is a group represented by the following formula (1) or (2).

9. The molding material according to any one of 1 to 8 above, wherein the cellulose derivative does not substantially contain a carboxyl group, a sulfonic acid group, and a salt thereof.
10. 10. The molding material according to any one of 1 to 9 above, wherein the cellulose derivative is insoluble in water.
11. The molding material according to any one of claims 1 to 10, wherein the aromatic polyamide is a condensation polymer of metaxylenediamine and adipic acid or adipic acid halide.
12 Furthermore, the molding material in any one of said 1-11 containing a compatibilizing agent.
13. 13. The molding material according to 12 above, wherein the compatibilizing agent is a modified polymer containing at least one functional group selected from an acid anhydride group, an epoxy group, and an organic acid metal base.
14 The modified polymer is an ethylene-α olefin copolymer, an ethylene-α, β-unsaturated carboxylic acid copolymer, an ethylene-α, β-unsaturated carboxylic acid and / or a metal salt copolymer, styrene-α. 14. The molding material according to 13, wherein the main skeleton is an α, β-unsaturated carboxylic acid ester copolymer or an α, β-unsaturated carboxylic acid ester copolymer.

15. The molded object obtained by heat-molding the molding material in any one of said 1-14.
16. The manufacturing method of a molded object including the process of heating and shape | molding the molding material in any one of said 1-14.
17. 16. A casing for an electric and electronic device comprising the molded article as described in 15 above.

  Since the molding material of the present invention has excellent thermoplasticity, it can be molded by heat molding or the like. Further, the molding material and the molded body of the present invention have both good scratch resistance and weather resistance while having good impact resistance, for example, components such as automobiles, home appliances, electrical and electronic equipment, It can be suitably used as a machine part, a house / building material, or the like. Moreover, since the molding material of this invention uses the cellulose derivative obtained from the cellulose which is plant-derived resin, it can substitute for the conventional petroleum-derived resin as a raw material which can contribute to global warming prevention.

In the present invention, the hydrogen atom of the hydroxyl group contained in cellulose is
A cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below;
The present invention relates to a molding material containing an aromatic polyamide.
A) A hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group consisting of only carbon and hydrogen.)

Hereinafter, the present invention will be described in detail.
1. Cellulose derivative The cellulose derivative contained in the molding material of the present invention comprises:
The hydrogen atom of the 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) A hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group consisting of only carbon and hydrogen.)
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 carbon number consisting of carbon and hydrogen alone. Is substituted by 1 to 3 hydrocarbon groups: —R _A , B) acyl group: —CO—R _B (R _B represents a hydrocarbon group consisting of only carbon and hydrogen).
More specifically, the cellulose derivative in the present invention has a repeating unit represented by the following general formula (A).

In the general formula (A), R ² , R ³ and R ⁶ are each independently a hydrogen atom, A) a hydrocarbon group having 1 to 3 carbon atoms consisting of carbon and hydrogen only: —R _A , B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group consisting only of carbon and hydrogen) or other substituents. Provided that at least a part of R ² , R ³ , and R ⁶ represents A) a hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen, and at least one of R ² , R ³ , and R ⁶ . The part represents B) an acyl group.

As described above, the cellulose derivative in the present invention is etherified by A) a hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen, and B) an acyl group. And by being esterified, thermoplasticity can be expressed and it becomes a thing suitable for a shaping | molding process.
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 A) a hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen, and B) an acyl group in any part of the cellulose derivative. It may be composed of a plurality of types of repeating units. Further, the cellulose derivative does not need to contain all of A) a hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen, and B) an acyl group in one repeating unit.
More specific embodiments include the following embodiments, for example.
(1) A repeating unit in which at least one of R ² , R ³ and R ⁶ is substituted with A) a hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen, and R ² , R ³ and R ^A cellulose derivative comprising at least one of ⁶ ) and B) a repeating unit substituted with an acyl group.
(2) One of R ² , R ³ and R ⁶ of one repeating unit is substituted with A) a hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen, and B) an acyl group ( That is, a cellulose derivative composed of the same type of repeating units having the substituents A) and B) in one repeating unit.
(3) A cellulose derivative in which repeating units having different substitution positions and different types of substituents are bonded at random.
In addition, 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 and B) an acyl group.

A) A hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen: -R _A is an aliphatic group.
The aliphatic group of _RA 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.
A) A hydrocarbon group having 1 to 3 carbon atoms composed of only carbon and hydrogen has impact resistance of the obtained molding material (hereinafter sometimes referred to as “cellulose resin composition” or “resin composition”), An alkyl group is preferred because of excellent molding processability such as melt flow rate. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like, and a methyl group or an ethyl group is particularly preferable.

B) an acyl group: In _{-CO-R B, R B} represents a hydrocarbon radical consisting of only carbon and hydrogen. 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 molding material of the present invention is a cellulose derivative in which the hydrogen atom of the hydroxyl group contained in cellulose contains at least one group substituted with A) and at least one group substituted with B). However, it is preferable from the viewpoint of impact resistance that it further contains at least one group in which the hydrogen atom of the 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. )

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 obtained molding material 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 β-glucose ring structure side.

R _C1 and R _C2 in C) may have further substituents or may be unsubstituted, but are preferably unsubstituted.

When R _C1 and R _C2 in C) have a further substituent, examples of the further substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxy group, and an alkoxy group (an alkyl group). The number of carbon atoms in the moiety is preferably 1 to 5), and alkenyl groups and the like can be mentioned. However, even when a substituent is included, R _C2 has 2 or 3 carbon atoms. In addition, when _RC1 is other than an alkyl group, it can also have an alkyl group (preferably C1-C5) as a substituent.

In particular, when R _C1 has a further substituent, it is preferable that the R _C1 has substantially no carboxyl group, sulfonic acid group, and salts thereof. When the cellulose derivative is substantially free of carboxyl groups, sulfonic acid groups, and salts thereof, the molding material 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.

As a specific example of the cellulose derivative in the present invention,
Acetyl methyl cellulose, acetyl ethyl cellulose, acetyl propyl cellulose,

Propionylmethylcellulose, propionylethylcellulose, propionylpropylcellulose,

Butyrylmethylcellulose, butyrylethylcellulose, butyrylpropylcellulose, methylcellulose-2-ethylhexanoate, ethylcellulose-2-ethylhexanoate, propylcellulose-2-ethylhexanoate,

Acetoxyethylmethylacetylcellulose, acetoxyethylethylacetylcellulose, acetoxyethylpropylacetylcellulose, acetoxyethylmethylpropionylcellulose, acetoxyethylethylpropionylcellulose, acetoxyethylpropylpropionylcellulose,

Acetoxyethylmethylcellulose-2-ethylhexanoate, acetoxyethylethylcellulose-2-ethylhexanoate, acetoxyethylpropylcellulose-2-ethylhexanoate, propionyloxyethylmethylacetylcellulose, propionyloxyethylethylacetylcellulose, propionyloxy Ethylpropylacetylcellulose,

Propionyloxyethyl methylpropionylcellulose, propionyloxyethylethylpropionylcellulose, propionyloxyethylpropylpropionylcellulose,

Propionyloxyethyl methylcellulose-2-ethylhexanoate, propionyloxyethylethylcellulose-2-ethylhexanoate, propionyloxyethylpropylcellulose-2-ethylhexanoate,

Acetoxypropylmethylacetylcellulose, acetoxypropylethylacetylcellulose, acetoxypropylpropylacetylcellulose,

Propionyloxypropylmethylacetylcellulose, propionyloxypropylethylacetylcellulose, propionyloxypropylpropylacetylcellulose,

Examples include valeroxypropylmethyl valeroyl cellulose and valeroxybutyl methyl valeroyl cellulose.

  The molding material of the present invention may contain only one kind of the specific cellulose derivative, or may contain two or more kinds.

In the cellulose derivative according to the present invention, A) a hydrocarbon group having only 1 to 3 carbon atoms consisting of carbon and hydrogen: —R _A , B) an acyl group: —CO—R _B , and C) an alkyleneoxy group: —R The substitution position of the group containing _C2- O- and acyl group: -CO-R _C1 and the number of each substituent (substitution degree) per β-glucose ring unit are not particularly limited.

For example, A) a hydrocarbon group having 1 to 3 carbon atoms consisting of carbon and hydrogen only: -R _A substitution degree DS _A (in the repeating unit, with respect to the hydroxyl groups at the 2nd, 3rd and 6th positions of the β-glucose ring) the number of R _a) is preferably from _{1.0 <DS a, 1.0 <DS} a <2.5 is more preferable. 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 molding material, the foaming and the like due to water absorption of the molding material during acceleration and molding of the pyrolysis can or is suppressed.

In addition, the cellulose derivative in the present invention is a substituent other than A) a hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen, B) an acyl group, and C) an alkyleneoxy group and an acyl group. You may have. 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 molding material 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) a hydrocarbon group having 1 to 3 carbon atoms consisting only of carbon and hydrogen: —R _A , and B) an acyl group: —CO—R _B (R _B represents a hydrocarbon group consisting only of carbon and hydrogen. A preferred embodiment of a method for producing a cellulose derivative having a.) Comprises a step of esterifying cellulose ether by reacting with acid chloride or acid anhydride in the presence of a base.
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, and allyl cellulose.

A) Hydrocarbon group having 1 to 3 carbon atoms composed of only carbon and hydrogen: —R _A , B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group composed of only carbon and hydrogen. ) And 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 is an alkylene group having 2 or 3 carbon atoms. A preferred embodiment of a method for producing a cellulose derivative having a hydrocarbon group and a hydroxypropyl cellulose ether having a hydroxyethyl group or a hydroxyethyl group is reacted with an acid chloride or an acid anhydride. This is performed by a method including a step of 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 does not have a carboxylic acid or the like as a substituent, a carboxyl group is generated by reacting with cellulose, for example, a dicarboxylic acid such as phthalic anhydride or maleic anhydride. It is preferable not to use a compound.

  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. Aromatic polyamide The molding material of the present invention contains an aromatic polyamide.
When the aromatic polyamide is mixed with the specific cellulose derivative in the present invention, the dispersibility is improved, and both good scratch resistance and weather resistance can be achieved.

As the aromatic polyamide, for example, an aromatic polyamide that is polymerized by dehydration condensation of a diamine and a dicarboxylic acid and that uses an aromatic diamine or dicarboxylic acid can be used.
As the diamine, aliphatic diamine, alicyclic diamine, aromatic diamine, and the like can be used. As the aliphatic diamine or alicyclic diamine, those represented by the following general formula (1) can be used. Incidentally, R ₁ in formula represents an aliphatic or alkyl alicyclic represented by _{C n H 2n (n = 6~12} ).
H ₂ N—R ₁ —NH ₂ (1)
As this diamine, it is particularly preferable to use a mixture of hexamethylene diamine and 2-methylpentamethylene diamine because they can exhibit excellent characteristics even at high temperatures.

  Moreover, xylylenediamine, metaxylylenediamine, etc. can be used as aromatic diamine.

As the dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid and the like can be used. The aliphatic dicarboxylic acid or alicyclic dicarboxylic acid is represented by the following general formula (2). Can be used. R ₂ in the following formula represents an aliphatic or alicyclic alkyl represented by C _n H _2n (n = 4 to 25).
_{HOOC-R 2 -COOH ··· (2} )

As the aliphatic dicarboxylic acid, adipic acid or the like can be used.
As the aromatic dicarboxylic acid, terephthalic acid, methyl terephthalic acid, naphthalenedicarboxylic acid, or the like can be used.
As the aromatic dicarboxylic acid, it is particularly preferable to use a mixture of terephthalic acid and isophthalic acid in that excellent characteristics can be exhibited even at high temperatures.

  In the aromatic polyamide, these diamines and dicarboxylic acids may be used alone or in combination with a plurality of kinds. Further, if necessary, components other than diamine and dicarboxylic acid may be contained.

  The aromatic polyamide used in the present invention is preferably a condensation polymer of metaxylenediamine and adipic acid or adipic acid halide.

The molecular weight of the aromatic polyamide in the present invention is not particularly limited, as the mass-average molecular weight, 5 × preferably ^{10 3 ~10000} × ¹⁰ 3, more preferably in the range of from in the range of ¹⁰ × 10 ³ ~5000 × 10 3 There, more preferably in the range of ^{30 × 10 3 ~1000 × 10 3} . 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.

  Commercially available aromatic polyamides can also be used in the present invention. Examples include MX nylon S6001 (nylon MXD6) manufactured by Mitsubishi Gas Chemical Co., Ltd., Clara Co., Ltd., Genesta N1000A (nylon 9T), and the like.

  These aromatic polyamides can be used alone or in combination of two or more.

4). Molding material and molded body The molding material of the present invention contains the above-described cellulose derivative and aromatic polyamide, 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. Preferably, the cellulose derivative is contained in an amount of 30% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, and particularly preferably 45 to 80% by mass.
The content ratio of the aromatic polyamide contained in the molding material of the present invention is preferably 10 to 70% by mass, more preferably 20 to 70% by mass.
In the molding material of the present invention, the content ratio of the cellulose derivative and the aromatic polyamide is preferably a cellulose derivative / aromatic polyamide mass ratio of 90/10 to 30/70, more preferably 80 / 20-40 / 60.

  The molding material of the present invention may contain various additives such as a compatibilizing agent, a filler (reinforcing material), and a flame retardant as required, in addition to the cellulose derivative and the aromatic polyamide.

  The molding material of the present invention preferably contains a compatibilizing agent. The compatibilizing agent is used for compatibilizing the cellulose derivative and the aromatic polyamide in the present invention. When a compatibilizing agent is added to the molding material of the present invention, the dispersibility of the aromatic polyamide with respect to the cellulose derivative in the present invention is further improved, and the fluidity (molding processability), impact resistance, scratch resistance, and weather resistance of the molding material. Performance such as gender is improved.

  In the present invention, the compatibilizer is preferably a modified polymer containing at least one functional group selected from an acid anhydride group, an epoxy group, and an organic acid metal base. Such modified polymers include ethylene-α olefin copolymers, ethylene-α, β-unsaturated carboxylic acid copolymers, ethylene-α, β-unsaturated carboxylic acids and / or metal salt copolymers. A styrene-α, β-unsaturated carboxylic acid ester copolymer and an α, β-unsaturated carboxylic acid ester copolymer as the main skeleton are preferred.

  As such a modified polymer, commercially available products include, for example, Tafmer MP-0610 (maleic anhydride modified-ethylene propylene copolymer), Tafmer MH-7020 (maleic anhydride modified) manufactured by Mitsui Chemicals, Inc. -Ethylenebutene copolymer), Asahi Kasei Corporation Tuftec M1913 (maleic anhydride modified-hydrogenated styrene-butadiene-styrene block polymer), Sumitomo Chemical Co., Ltd. Bond Fast E (ethylene-glycidyl acrylate copolymer) Bondfast 2B (ethylene-methyl glycidyl acrylate-vinyl acetate copolymer), Bond Fast 7M (ethylene-methyl glycidyl acrylate-methyl acrylate copolymer), Mitsui DuPont Polychemical Co., Ltd. HPR AR201 (Maleic anhydride modified ethylene Ethyl acrylate copolymer), Himiran 1557 (ethylene-zinc acrylate copolymer), Himiran 1555 (ethylene-sodium acrylate copolymer), Toa Gosei Co., Ltd. ARUFON UG-4070 (styrene-glycidyl acrylic acid) Methyl-styrene-glycidyl acrylate copolymer), Reseda GP-301 (epoxy group-containing methyl methacrylate copolymer), styrene-maleic anhydride copolymer (product code 17925-1A) manufactured by Kanto Chemical Co., Inc. Etc.

  The content of the compatibilizing agent in the molding material of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 with respect to 100 parts by mass of the total amount of the cellulose derivative and aromatic polyamide in the present invention. Part by mass. By setting it within this range, a sufficient compatibility improvement effect can be obtained, and problems such as an increase in the viscosity of the molding material are unlikely to occur.

  The molding material of the present invention preferably contains an antioxidant. Thereby, even if the addition amount to the cellulose derivative is small, a sufficient effect can be exhibited. Therefore, the impact resistance, moldability, rigidity, bending strength, heat resistance and the like of a specific cellulose derivative can be suppressed, and scratch resistance and antifouling properties can be imparted.

The antioxidant in the present invention may be a low molecular compound or a high molecular compound, for example, a hindered phenol antioxidant, a phosphorus antioxidant, an amine antioxidant, a sulfur oxidation. An inhibitor can be used.
Specific examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], 1.6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadodecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide, 3,5 -Di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester and 1,3,5-trimethyl-2,4,6-tri (3,5-di -t- butyl-4-hydroxybenzyl) benzene, and the like.
Phosphorus antioxidants include calcium hypophosphite, 2,6-di-t-butyl-4-methylphenol, tetrakis (methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ) Phenol compounds such as methane, tris (3,5-di-t-butyl-4-hydroxybenzidine) isocyanurate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropio Examples thereof include sulfur compounds such as nates, phosphorus compounds such as trisnonylphenyl phosphite and distearyl pentaerythritol diphosphite, among which calcium hypophosphite is preferable.
Specific examples of the sulfur-based antioxidant include sulfur-containing compounds such as thioethers, dithioacid salts such as nickel dithiocarbamate, mercaptobenzimidazole, thiocarbanilide, and thiodipropion ester. Among these, the use of a thiodipropion ester-based compound is particularly preferable.
Examples of the antioxidant in the present invention include phosphorus antioxidants, hindered phenol antioxidants (for example, “Irganox 1010”, “Irganox 1076”, “Irganox 3114” manufactured by Ciba Specialty Chemicals, It is preferable to use “Sumerator GP” manufactured by Sumitomo Chemical Co., Ltd.).
The blending amount of the antioxidant is usually 30% by mass or less, preferably 0.1 to 10% by mass in the molding material. By setting it within this range, the resin can obtain a sufficient stability improving effect against heating in the kneading or molding process, which is preferable.

The molding material of the present invention may contain a filler (reinforcing material). By containing the filler, the mechanical properties of the molded body formed of the molding material 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 molding material of the present invention contains a filler, the content is not limited, but is usually 30% by mass or less, preferably 5 to 10% by mass in the molding material.

The molding material 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 molding material of the present invention contains a flame retardant, the content is not limited, but is usually 30% by mass or less, preferably 2 to 10% by mass in the molding material. By setting it as this range, impact resistance, brittleness, etc. can be improved, or generation | occurrence | production of pellet blocking can be suppressed.

The molding material of the present invention may contain other components other than those described above for the purpose of further improving various properties such as moldability and flame retardancy within the range not impairing the object of the present invention. .
Examples of other components include polymers other than the cellulose derivative and the aromatic polyamide, stabilizers (ultraviolet absorbers, etc.), mold release agents (fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, and aliphatic partially saponified esters. , 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, flame retardant aid, processing aid Agents, antidrip agents, antibacterial agents, antifungal agents and the like. Furthermore, a coloring agent containing a dye or a pigment can be added.

As the polymer other than the cellulose derivative and the aromatic polyamide, any of a thermoplastic polymer and 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 thereof include polyether rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, and other thermoplastic elastomers such as polyurethane and polyester.

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 molding material of this invention contains polymers other than a cellulose derivative and the said aromatic polyamide, 30 mass% or less is preferable in a molding material, and 2-10 mass% is more preferable.

  The molding material 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 molding material of the present invention contains a plasticizer, the content is usually 30 parts by mass or less, preferably 0.005 to 20 parts by mass with respect to 100 parts by mass of the total amount of the cellulose derivative and the aromatic polyamide. More preferably, it is 0.01-10 mass parts.

The molded body of the present invention can be obtained by molding a molding material containing the cellulose derivative and the aromatic polyamide. More specifically, the cellulose derivative or the cellulose derivative and, if necessary, a molding material containing various additives and the like are heated and obtained by a production method including a step of molding by various molding methods.
The method for producing a molded body of the present invention includes a step of heating and molding the molding material.
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, impact resistance and scratch resistance, and having a low environmental impact, for example, exterior parts for electrical and electronic equipment such as copiers, printers, personal computers, televisions, etc. It can be suitably used as (especially a housing).

  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.

<Synthesis Example 8: Synthesis of acetylbutyl cellulose (H-2)>
50 g of cellulose (manufactured by Nippon Paper Industries Co., Ltd .: KC Flock W400) and 1800 mL of dimethylacetamide were weighed in a 3 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel and stirred at 120 ° C. for 2 hours. Next, 150 g of lithium chloride was added, and the mixture was further stirred for 1 hour. After returning the reaction solution to room temperature, 84 g of butyl chloride was added dropwise at room temperature, and the mixture was further stirred at 90 ° C. for 2 hours. When the reaction solution was added to 10 L of water / methanol (1/1 = v / v) with vigorous stirring, a white solid was precipitated. The white solid was filtered off by suction filtration and washed with a large amount of methanol three times. The obtained white solid was vacuum-dried at 100 ° C. for 6 hours to obtain the desired butyl cellulose (butyl substitution degree 1.80) as a white powder (77.3 g).
Next, 60 g of butyl cellulose and 2100 mL of N, N-dimethylacetamide prepared in a 5 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel were weighed and stirred at room temperature. 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 (H-2) (acetylbutyl cellulose) as a white powder.

  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.

<Examples 1-14, Comparative Examples 1-6>
[Production of molded body]
Cellulose derivatives (C-1 to C-7, H-1 to 2, hydroxypropyl cellulose phthalate 1 to 2), aromatic polyamide, compatibilizer, and antioxidant are mixed in the blending ratio shown in Table 2, and cellulose A resin composition (molding material) was produced. This resin composition was supplied to a twin-screw kneading extruder (manufactured by Technobel, Ultranano) to produce pellets, and the resulting pellets were then injected into an injection molding machine (FANUC ROBOSHOT S-2000i, automatic injection molding). Machine), 4 × 10 × 80 mm multi-purpose test pieces were molded.
Moreover, the pellet of cellulose resin composition was shape | molded the film test piece (scratch resistance) of 0.2x10x10mm on 230 degreeC conditions using the heating type press molding machine.

In Table 2, aromatic polyamides, compatibilizers and antioxidants are shown below.
[Aromatic polyamide]
MX Nylon S6001: Nylon MXD6, manufactured by Mitsubishi Gas Chemical Co., Ltd. [Compatibilizer]
TAFMER MP-0610: Maleic anhydride modified ethylene propylene copolymer, manufactured by Mitsui Chemicals, Inc. HPR AR201: Maleic anhydride modified ethylene ethyl acrylate copolymer, manufactured by Mitsui DuPont Polychemical Co., Ltd. High Milan 1557: Ethylene -Zinc acrylate copolymer, ARUFON UG-4070 manufactured by Mitsui DuPont Polychemical Co., Ltd .: styrene-methyl glycidyl acrylate-styrene-methyl glycidyl acrylate copolymer, Reseda GP-301 manufactured by Toagosei Co., Ltd .: Epoxy group-containing methyl methacrylate copolymer, manufactured by Toa Gosei Co., Ltd.

  Antioxidant: Phenolic antioxidant, Irganox 1010, Ciba Specialty Chemicals Co., Ltd.

[Evaluation]
The following items were evaluated using the obtained multipurpose test piece or film test piece. The evaluation results are shown in Table 2.

(Flexural modulus)
In accordance with ISO178, after adjusting the test piece molded by injection molding for 48 hours or more at 23 ° C ± 2 ° C, 50% ± 5% RH, the distance between fulcrums by Instron (Toyo Seiki, Strograph V50) The flexural modulus was measured at 64 mm and a test speed of 2 mm / min. The measurement is an average of three measurements.

(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 a test piece molded by injection molding, 23 ° C. ± 2 ° C., 50% ± 5% RH Then, the impact strength was measured edgewise with a Charpy impact tester (manufactured by Toyo Seiki Seisakusho). The measurement is an average of three measurements.

(Dispersibility evaluation)
As an index of dispersibility, evaluation was performed using a scanning electron microscope (ULTRA55 manufactured by SII Nanotechnology Co., Ltd.). Observation was made after the surface was smoothed using a microtome, and the number average dispersion diameter of the dispersed phase was determined and ranked as follows.
○: Number average dispersed diameter of dispersed phase is less than 2 μm Δ: Number average dispersed diameter of dispersed phase is 2 μm or more and less than 5 μm ×: Number average dispersed diameter of dispersed phase is 5 μm or more

(Scratch resistance)
The film which consists of a cellulose resin composition of an Example and a comparative example is used for a stainless steel plate, a cutter blade is applied to the film, and a load is applied. In this state, the film surface is moved so as to be cut by a cutter.
Even when a 120 g load is applied, ◎,
When the film is cut within a load range of less than 120 g and 70 g or more,
When the film is cut within a load range of less than 70 g and 50 g or more, Δ,
When the film is cut with a load of less than 50 g
It was.

(Calcium chloride aqueous solution resistance)
It was conducted as an accelerated test for weather resistance.
The test piece was placed in a constant temperature and humidity chamber set to 50 ° C. and 95% RH, and 3% by mass of water was contained. Next, a 50 mass% calcium chloride aqueous solution was brushed on the surface of the test piece, and drying was performed under the conditions of 100 ° C. × 2 hours as one cycle, and the number of cycles in which cracks were generated was determined by repeating. If no cracks were generated in the test piece even after 5 cycles or more, 5 cycles were completed and the test was terminated.

Hydroxypropyl cellulose phthalate 1: Hydroxypropyl cellulose phthalate having a degree of phthalic acid substitution = 1.4 Hydroxypropyl cellulose phthalate 2: Hydroxypropyl cellulose 1 further esterified with propylene oxide. Phthalic acid substitution degree = 1.4, propylene oxide substitution degree = 2.4

  The resin compositions of Examples 1 to 14 using the cellulose derivative defined in the present invention had good dispersibility, thereby achieving both good scratch resistance and weather resistance.

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 molding material containing an aromatic polyamide.
A) A hydrocarbon group having 1 to 3 carbon atoms consisting of only carbon and hydrogen: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group consisting of only carbon and hydrogen.) The molding material 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 molding material 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 molding material in any one of Claims 1-3 whose said _RA is a methyl group or an ethyl group. The molding material according to claim 1, wherein R _B and R _C1 are each independently an alkyl group or an aryl group. The molding material according to claim 1, wherein R _B and R _C1 are each independently a methyl group, an ethyl group, or a propyl group. Wherein R _B is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms, molding material according to any of claims 1 to 5. The molding material in any one of Claims 2-7 whose said alkyleneoxy group is group represented by following formula (1) or (2).

  The molding material in any one of Claims 1-8 in which the said cellulose derivative does not have a carboxyl group, a sulfonic acid group, and these salts substantially.   The molding material in any one of Claims 1-9 whose said cellulose derivative is insoluble in water.   The molding material according to any one of claims 1 to 10, wherein the aromatic polyamide is a condensation polymer of metaxylenediamine and adipic acid or adipic acid halide.   Furthermore, the molding material in any one of Claims 1-11 containing a compatibilizing agent.   The molding material according to claim 12, wherein the compatibilizing agent is a modified polymer containing at least one functional group selected from an acid anhydride group, an epoxy group, and an organic acid metal base.   The modified polymer is an ethylene-α olefin copolymer, an ethylene-α, β-unsaturated carboxylic acid copolymer, an ethylene-α, β-unsaturated carboxylic acid and / or a metal salt copolymer, styrene-α. The molding material according to claim 13, wherein the main skeleton is an α, β-unsaturated carboxylic acid ester copolymer or an α, β-unsaturated carboxylic acid ester copolymer.   The molded object obtained by heat-molding the molding material in any one of Claims 1-14.   The manufacturing method of a molded object including the process of heating and shape | molding the molding material in any one of Claims 1-14.   A housing for electrical and electronic equipment comprising the molded body according to claim 15.