WO2011078276A1 - Molding material, molded article and process for production thereof, and housing for electric/electronic device - Google Patents

Abstract

Disclosed is a molding material which are excellent with respect to all of Charpy impact strength, bending elastic modulus and dispersibility, can retain good impact resistance, and has good scratch resistance. The molding material comprises: a cellulose derivative which contains at least one group that is produced by substituting a hydrogen atom in a hydroxy group contained in a cellulose by (A) a C_1-3 hydrocarbon group -R_A and at least one group that is produced by substituting a hydrogen atom in a hydroxy group contained in the cellulose by (B) an acyl group -CO-R_B (wherein R_B represents a hydrocarbon group); and an α,β-unsaturated carboxylic acid ester polymer.

Description

MOLDING MATERIAL, MOLDED BODY, ITS MANUFACTURING METHOD, AND ELECTRIC ELECTRONIC DEVICE CASE

The present invention relates to a molding material, a molded body, a manufacturing method thereof, and a casing for electrical 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 that a cellulose ester and a thermoplastic resin, α, β-unsaturated carboxylic acid ester polymer (acrylic resin) can be used in combination.

Japanese Unexamined Patent Publication No. 56-55425 Japanese Unexamined Patent Publication No. 2008-24919 US Pat. No. 3,979,179 U.S. Pat. No. 3,940,384 International Publication No. 2009/010837 Japanese Patent No. 3017412 specification Japanese Unexamined Patent Publication No. 2006-111858 Japanese Unexamined Patent Publication No. 2005-336379

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 insufficient in strength, which is not preferable as a molding material. In addition, the cellulose derivative described in Patent Document 5 is described as being poorly water-soluble, but only described in the text, and its synthesis method and usage form are specifically disclosed in Examples and the like. Absent.
Further, a combination of a cellulose ester and an α, β-unsaturated carboxylic acid ester polymer described in Patent Documents 7 and 8 is inferior in Charpy impact strength and scratch resistance, and needs to be improved.

An object of the present invention is to provide a molding material having good scratch resistance while maintaining good impact resistance (particularly Charpy impact strength). 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 pay attention to the molecular structure of cellulose, and use cellulose as a cellulose derivative having a specific structure having an ether structure and an ester structure, and the cellulose derivative having the specific structure and an α, β-unsaturated carboxylic acid ester polymer. It is found that the molding material contained is excellent in all aspects of Charpy impact strength, flexural modulus and dispersibility, and exhibits good scratch resistance while maintaining good impact resistance, and completes the present invention. It came to.
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 α, β-unsaturated carboxylic acid ester polymer.
A) Hydrocarbon group having 1 to 3 carbon atoms: —R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)

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 to 4 carbon atoms. )

3. 3. The molding material according to 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 to 4 carbon atoms, and n represents an integer of 1 or more.)

4). 4. The molding material according to any one of the above 1 to 3, wherein R _A is a methyl group or an ethyl group.
5. The molding material according to any one of 2 to 4, wherein R _B and R _C1 are each independently an alkyl group or an aryl group.
6). 6. The molding material according to any one of 2 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 one 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. 9. The molding material according to any one of 1 to 8, wherein the cellulose derivative has substantially no carboxyl group, sulfonic acid group, or 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. 11. The molding material according to any one of 1 to 10 above, wherein the α, β-unsaturated carboxylic acid ester polymer is a polymethyl methacrylate polymer.
12 The molding material according to any one of the above 1 to 11, further comprising 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. 15. A molded product obtained by thermoforming the molding material according to any one of 1 to 14 above.
16. 15. A method for producing a molded body, comprising a step of heating and molding the molding material according to any one of 1 to 14 above.
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. In addition, the molding material and the molded body of the present invention have good scratch resistance while maintaining good impact resistance. It can be suitably used as a house / building material. 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 α, β-unsaturated carboxylic acid ester polymer.
A) Hydrocarbon group having 1 to 3 carbon atoms: —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 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) Hydrocarbon group having 1 to 3 carbon atoms: —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 }
A) Hydrocarbon group having 1 to 3 carbon atoms: —R _A , B) Acyl group: —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 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: —R _A , B) an acyl group: —CO— R _B (R _B represents a hydrocarbon group) or other substituents. Provided that at least part of R ² , R ³ , and R ⁶ is A) a hydrocarbon group having 1 to 3 carbon atoms, and at least part of R ² , R ³ , and R ⁶ is B) acyl group Represents.

The cellulose derivative in the present invention is etherified and esterified by A) a hydrocarbon group having 1 to 3 carbon atoms, and B) an acyl group, as described above. As a result, thermoplasticity can be exhibited, and it is suitable for molding.
Furthermore, since cellulose is a completely 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 and B) an acyl group in any part of the whole, and consists of the same repeating unit. Alternatively, it may be composed of a plurality of types of repeating units. The cellulose derivative need not contain all of A) a hydrocarbon group having 1 to 3 carbon atoms and B) an 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 having 1 to 3 carbon atoms, and at least one of R ² , R ³ and R ⁶ is B) A cellulose derivative composed of a repeating unit substituted with an acyl group.
(2) At least 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, and at least one of the other repeating units is B) acyl A cellulose derivative composed of the same type of repeating unit substituted with a group (that is, having the above-mentioned 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)).
The cellulose derivative may have a hydrogen atom, A) a hydrocarbon group having 1 to 3 carbon atoms, and B) other substituents other than the acyl group.

A) A hydrocarbon group having 1 to 3 carbon atoms: —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) The hydrocarbon group having 1 to 3 carbon atoms is molded such as impact resistance, melt flow rate, etc. of the obtained molding material (hereinafter sometimes referred to as “cellulose resin composition” or “resin composition”). From the viewpoint of excellent processability, an alkyl group is preferred. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group or an ethyl group is particularly preferable.

B) 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 (preferably a methyl group). Group, ethyl group, propyl group), and most preferably an alkyl group having 1 or 2 carbon atoms (that is, a methyl group or an ethyl group).
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 7-9 carbon atoms 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, 3-heptyl, 2-ethylhexyl group, tert- butyl Group, isoheptyl group, and the like. Preferably, R _B is methyl, ethyl, propyl, a 3-heptyl group, or a 2-ethylhexyl group, more preferably a methyl group, an ethyl group, 3-heptyl, or 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 to 4 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 to 4 carbon atoms. R _C2 may be linear, branched or cyclic, but is preferably linear or branched, and more preferably branched.
The alkyleneoxy group (—R _C2 —O—) is preferably an alkyleneoxy group having 2 or 3 carbon atoms. Specific examples of the alkyleneoxy group preferably include the following structures.

Among them, a group represented by the following formula (1) or (2) in which —R _C2 —O— is branched is preferable because the obtained molding material has excellent bending elastic modulus.

The group of 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 to 4 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 _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 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. Note that when R _A , R _B , and R _C1 are other than an alkyl group, they may have an alkyl group (preferably having a carbon number of 1 to 5) 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. 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, the cellulose as a raw material may contain a carboxyl group, and the cellulose derivative using the above-described substituents A) to C) introduced therein 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.

In addition, the cellulose derivative in the present invention is preferably 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 specific examples of the cellulose derivative in the present invention,

Acetylmethylcellulose, acetylethylcellulose, acetylpropylcellulose

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

Propionyloxyethyl methyl acetylcellulose, propionyloxyethyl ethyl acetylcellulose, propionyloxyethylpropyl acetylcellulose

Propionyloxyethyl methylpropionylcellulose, propionyloxyethylethylpropionylcellulose, propionyloxyethylpropylpropionylcellulose

Propionyloxyethylmethylcellulose-2-ethylhexanoate, propionyloxyethylethylcellulose-2-ethylhexanoate, propionyloxyethylpropylcellulose-2-ethylhexanoate

Acetoxypropylmethylacetylcellulose, acetoxypropylethylacetylcellulose, acetoxypropylpropylacetylcellulose

Propionyloxypropylmethylacetylcellulose, propionyloxypropylethylacetylcellulose, propionyloxypropylpropylacetylcellulose

Valeroxypropyl methyl valeroyl cellulose, valeroxybutyl methyl valeroyl cellulose

Etc.

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

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

For example, a hydrocarbon group of A) the number of carbon atoms of 1 to 3: in degree of substitution DS _A (repeating units -R _A, 2-position of the β- glucose ring, the number of _{R A} for 3-position and the 6-hydroxyl group) is 1.0 <DS _A is preferable, and 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 ) (the 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.

The cellulose derivative in the present invention may have a substituent other than A) a hydrocarbon group having 1 to 3 carbon atoms, 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 still more 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.

The cellulose derivative in the molding material of the present invention is a cellulose derivative in which a hydrogen atom of a hydroxyl group contained in cellulose contains at least one group substituted with the above A) and at least one group substituted with the above B). However, when a hydrogen atom of a hydroxyl group contained in cellulose is substituted, from the viewpoint of moldability, it is substituted only by A) and B) or A), B), and C. ) Is preferred. That is, in the cellulose derivative in the present invention, it is preferable that the hydrogen atom of the hydroxyl group contained in the cellulose is not substituted with a group other than the above A), B), and C).

The molecular weight of the cellulose derivative in the present invention is preferably such that the number average molecular weight (Mn) is 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, and 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, a polystyrene gel is used, and the molecular weight can be determined using a conversion molecular weight calibration curve obtained in advance from a standard monodisperse polystyrene constituent curve.

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 a method for producing a cellulose derivative having A) a hydrocarbon group having 1 to 3 carbon atoms: —R _A , and B) an acyl group: —CO—R _B (R _B represents a hydrocarbon group) Includes an esterification step by reacting cellulose ether with acid chloride or acid anhydride in the presence of a base.
As the cellulose ether, for example, those 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 are substituted with hydrocarbon groups can be used. Specific examples include methyl cellulose, ethyl cellulose, propyl cellulose, and allyl cellulose.

A) a hydrocarbon group having 1 to 3 carbon atoms: —R _A , B) an acyl group: —CO—R _B (R _B represents a hydrocarbon group), and C) an alkyleneoxy group: —R _C2 A preferred method for producing a cellulose derivative having a group containing —O— and an acyl group: —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 to 4 carbon atoms). In the embodiment of the present invention, the esterification (acylation) is carried out by reacting a hydroxypropyl cellulose ether having a hydrocarbon group and a hydroxyethyl cellulose ether having a hydroxyethyl group or a hydroxypropyl group with an acid chloride or an acid anhydride. Is performed by a method including:
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 thereof 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 manufacturing conditions can follow the usual method. For example, the method described in “Encyclopedia of Cellulose” pages 131 to 164 (Asakura Shoten, 2000) can be referred to.

3. α, β-Unsaturated carboxylic acid ester polymer The molding material of the present invention contains an α, β-unsaturated carboxylic acid ester polymer.
The α, β-unsaturated carboxylic acid ester polymer is mixed with the specific cellulose derivative in the present invention, thereby improving dispersibility and imparting good scratch resistance while maintaining impact resistance. .
The α, β-unsaturated carboxylic acid ester polymer is obtained by polymerizing an α, β-unsaturated carboxylic acid ester. Examples of the α, β-unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Examples include n-butyl methacrylate and isobutyl methacrylate. Of these, methyl methacrylate is preferred.

The molecular weight of the α, β-unsaturated carboxylic acid ester polymer in the present invention is not particularly limited, but the mass average molecular weight is preferably in the range of 5 × 10 ³ to 10000 × 10 ³ , more preferably 10 × 10 ^3. The range is from ˜5000 × 10 ³ , and more preferably from 30 × 10 ³ to 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, a polystyrene gel is used, and the molecular weight can be obtained using a converted molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene. it can.

Also, commercially available α, β-unsaturated carboxylic acid ester polymers can be used in the present invention. Examples include Parapet G (polymethyl methacrylate) manufactured by Kuraray Co., Ltd., Delpet 560F (polymethyl methacrylate) manufactured by Asahi Kasei Chemicals Corporation, Sumipex MG55 (polymethyl methacrylate) manufactured by Sumitomo Chemical Co., Ltd., and the like. .

These α, β-unsaturated carboxylic acid ester polymers can be used singly or in combination of two or more.

4). Molding Material and Molded Body The molding material of the present invention contains the cellulose derivative described above and an α, β-unsaturated carboxylic acid ester polymer, and may contain other additives as necessary. it can.
The content rate of the component contained in the molding material of this invention is not specifically limited. The cellulose derivative is preferably contained in an amount of 30% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and particularly preferably 45 to 80% by mass.
The content of the α, β-unsaturated carboxylic acid ester polymer contained in the molding material of the present invention is preferably 10 to 70% by mass, more preferably 20 to 60% by mass.
In the molding material of the present invention, the content ratio of the cellulose derivative and the α, β-unsaturated carboxylic acid ester polymer is preferably a mass ratio of cellulose derivative / α, β-unsaturated carboxylic acid ester polymer. Is 90/10 to 40/60, more preferably 80/20 to 45/55.

The molding material of the present invention contains a cellulose derivative and an α, β-unsaturated carboxylic acid ester polymer, and various additives such as a compatibilizing agent, a filler (reinforcing material), and a flame retardant as necessary. You may do it.

The molding material of the present invention preferably contains a compatibilizing agent. The compatibilizing agent is for compatibilizing the cellulose derivative and the α, β-unsaturated carboxylic acid ester polymer in the present invention. When a compatibilizing agent is added to the molding material of the present invention, the dispersibility of the α, β-unsaturated carboxylic acid ester polymer in the cellulose derivative in the present invention is further improved, and the fluidity (molding processability) and resistance of the molding material are improved. Performance such as impact and scratch resistance is further 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 polymer, a styrene-α, β-unsaturated carboxylic acid ester copolymer, and an α, β-unsaturated carboxylic acid ester copolymer as the main skeleton are preferred.

Examples of such modified polymers that are commercially available include Tafmer MP-0610 (maleic anhydride modified-ethylene propylene copolymer) and Tafmer MH-7020 (maleic anhydride modified) manufactured by Mitsui Chemicals, Inc. -Ethylenebutene copolymer), Tuftec M1913 (maleic anhydride modified-hydrogenated styrene-butadiene-styrene block polymer) manufactured by Asahi Kasei Co., Ltd., Bondfast E (ethylene-methyl glycidyl acrylate copolymer) manufactured by Sumitomo Chemical Co., Ltd. Bond Fast 2B (ethylene-methyl glycidyl acrylate-vinyl acetate copolymer), Bond Fast 7M (ethylene-methyl glycidyl acrylate-methyl acrylate copolymer) HPR AR201 manufactured by Mitsui DuPont Polychemical Co., Ltd. (Maleic anhydride modification (Ethylene acrylate copolymer), Himiran 1557 (ethylene-zinc acrylate copolymer), Himiran 1555 (ethylene-sodium acrylate copolymer), ARAFON UG-4070 (styrene-glycidylacrylic) manufactured by Toa Gosei Co., Ltd. Methyl methacrylate-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. ).

The content of the compatibilizer in the molding material of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the cellulose derivative and the α, β-unsaturated carboxylic acid ester polymer in the present invention. More preferably, it is 0.5 to 20 parts 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-tris 3,5-di -t- butyl-4-hydroxybenzyl) benzene, and the like.
Phosphorous 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 sulfur-based antioxidants include sulfur-containing compounds such as thioethers, dithioacid salts such as nickel dithiocarbamate, mercaptobenzimidazoles, thiocarbanilides, 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 silicate, feldspar, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide Beam, 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 thereof 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 -2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate Can be mentioned.

Examples of the phosphoric acid condensed ester 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.

In addition, polyphosphates composed of salts of phosphoric acid, polyphosphoric acid and metals of Groups 1 to 14 of the periodic table, ammonia, aliphatic amines, and aromatic amines 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 organic silicon 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, its 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 α, β-unsaturated carboxylic acid ester polymer, plasticizers, stabilizers (such as UV absorbers), mold release agents (fatty acids, fatty acid metal salts, Oxy fatty acid, fatty acid ester, 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 agents, flame retardant aids, processing aids, anti-drip agents, antibacterial agents, antifungal agents and the like can be mentioned. Further, a coloring agent containing a dye or a pigment can be added.

As the polymer other than the cellulose derivative and the α, β-unsaturated carboxylic acid ester polymer, 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, polyacetate (Including homopolymers and copolymers), polyurethane, aromatic and aliphatic polyketones, polyphenylene sulfide, polyether ether ketone, thermoplastic starch 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 Thermoplastic polymer such as copolymer, MS resin (methyl methacrylate-styrene copolymer), polycarbonate, polyarylate, polysulfone, polyethersulfone, phenoxy resin, polyphenylene ether, modified polyphenylene ether, polyetherimide , Polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoro Fluoropolymers such as ethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, cellulose acetate, polyvinyl alcohol, unsaturated polyester, melamine resin, phenol resin, urea resin, polyimide and the like can be mentioned.
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, poly Examples include ether rubber, epichlorohydrin rubber, fluoro 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 molding material of the present invention contains a polymer other than the cellulose derivative and the α, β-unsaturated carboxylic acid ester polymer, the content thereof is preferably 30% by mass or less, preferably 2 to 10% by mass in the molding material. 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, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebashi Dibutyl, and include 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, and bisphenols. And a polyalkylene glycol such as a propylene oxide addition polymer, a tetrahydrofuran addition polymer of bisphenol, or a terminal epoxy-modified compound thereof, a terminal ester-modified compound, a terminal ether-modified compound, and the like.

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 thereof is usually 30 parts by mass or less with respect to 100 parts by mass of the total amount of the cellulose derivative and the α, β-unsaturated carboxylic acid ester polymer. 0.005 to 20 parts by mass is preferable, and 0.01 to 10 parts by mass is more preferable.

The molded article of the present invention can be obtained by molding a molding material containing the cellulose derivative and the α, β-unsaturated carboxylic acid ester polymer. 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 electrical 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 electric and electronic devices such as copiers, printers, personal computers, televisions, etc. It can be suitably used as (especially a housing).

Hereinafter, the present invention will be specifically described 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)>
In a 5 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, weigh 60 g of hydroxypropyl methylcellulose (trade name Metroze 90SH-100; manufactured by Shin-Etsu Chemical) and 2100 mL of N, N-dimethylacetamide 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. The solubility of this cellulose derivative (C-1) in water at 25 ° C. was less than 0.1% by mass (insoluble).

<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 hydroxyethylmethylcellulose (trade name Marporose ME-250T; manufactured by Matsumoto Yushi), methylcellulose (trade name Marporose M-4000: Matsumoto Yushi Co., Ltd.) And acetoxyethyl methyl acetyl cellulose (C-2), methyl acetyl cellulose (C-3), ethyl acetyl cellulose (C-3) in the same manner as in Synthesis Example 1 except that it was changed to ethyl cellulose (trade name Etcel 300CP: manufactured by Dow Chemical). C-4) was obtained. The solubility of these cellulose derivatives (C-2), (C-3), and (C-4) in water at 25 ° C. was less than 0.1% by mass (insoluble).

<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 methylcellulose (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1.8) and 1500 mL of pyridine were weighed and stirred at room temperature. Under water cooling, 173 mL of 2-ethylhexanoyl chloride was slowly added dropwise thereto, and the mixture was further stirred at 60 ° C. 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 resulting white solid was vacuum-dried at 100 ° C. for 6 hours to obtain methylcellulose-2-ethylhexanoate (C-5). The solubility of this cellulose derivative (C-5) in water at 25 ° C. was less than 0.1% by mass (insoluble).

<Synthesis Example 6: Synthesis of valeroxypropyl methyl valeroyl cellulose (C-6)>
In place of methyl cellulose in Synthesis Example 5 (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1.8), hydroxypropylmethyl cellulose (trade name Metroze 90SH-100; manufactured by Shin-Etsu Chemical Co., Ltd.) and valeroyl in place of 2-ethylhexanoyl chloride Valeroxypropylmethylvaleroylcellulose (C-6) was obtained in the same manner as in Synthesis Example 5 except that chloride was used. The solubility of this cellulose derivative (C-6) in water at 25 ° C. was less than 0.1% by mass (insoluble).

<Synthesis Example 7: Synthesis of valeroxybutyl methyl valeroyl cellulose (C-7)>
Valeroxybutylmethylvaleroylcellulose (C-7) was obtained in the same manner as in Synthesis Example 6 except that hydroxybutylmethylcellulose was used as the hydroxypropylmethylcellulose (trade name Metroze 90SH-100; manufactured by Shin-Etsu Chemical) in Synthesis Example 6. . The solubility of this cellulose derivative (C-7) in water at 25 ° C. was less than 0.1% by mass (insoluble).

<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 butylcellulose 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 desired cellulose derivative (H-2) (acetylbutyl cellulose) as a white powder.

Note that the types and substitution degrees of hydrocarbon groups, the types and molar substitutions of alkyleneoxy groups, the types of acyl groups, and the degrees of acylation of the cellulose derivatives obtained above are described in Cellulose Communication 6, 73-79 (1999). Was observed and determined by ¹ H-NMR using the method described in ¹ ). 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.
Further, a colloid titration method is performed, and the degree of substitution of carboxyl groups or sulfonic acid groups in the cellulose derivatives (C-1) to (C-7) is less than 0.02 (that is, the content of carboxyl groups or sulfonic acid groups is It was confirmed that it was less than 0.5% by mass with respect to the cellulose derivative.

<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 a molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene was used. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) was used.

The type and degree of substitution of hydrocarbon groups, the type and molar substitution of alkyleneoxy groups, the type and degree of acylation of acyl groups, the number average molecular weight (Mn), and the mass average molecular weight (Mw) of the obtained cellulose derivative These are summarized in Table 1. Table 1 also shows the cellulose derivative (H-1) used in the comparative example.

<Examples 1 to 14, Comparative Examples 1 to 4>
[Production of molded body]
Cellulose derivatives (C-1 to C-7, H-1 to H-2), α, β-unsaturated carboxylic acid ester polymer, compatibilizer, and antioxidant are shown in Table 2 in the mixing ratio (parts by mass). ) To prepare a cellulose resin composition (molding material). This resin composition was supplied to a twin-screw kneading extruder (manufactured by Technobel Co., Ltd., Ultranano) to produce pellets, and then the obtained pellets were injected into an injection molding machine (FANUC Corporation Robot 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, the α, β-unsaturated carboxylic acid ester polymer, the compatibilizing agent and the antioxidant are as follows.
[Α, β-unsaturated carboxylic acid ester polymer]
Parapet G: Polymethyl methacrylate, manufactured by Kuraray Co., Ltd. [Compatibilizer]
TAFMER MP-0610: Maleic anhydride modified-ethylene propylene copolymer, Mitsui Chemicals, Inc. HPR AR201: Maleic anhydride modified ethylene ethyl acrylate copolymer, 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.
The impact strength of a resin composition comprising a cellulose resin (99.5 parts by mass) and an antioxidant (0.5 parts by mass) was also measured by the above method and contained an α, β-unsaturated carboxylic acid ester polymer. The impact strength retention was determined by calculating the ratio with the impact strength in this case.

(Dispersibility evaluation)
Evaluation was made using an optical microscope (Nikon LV100) as an index of dispersibility. When the microtome was sliced to 2 μm and observed at 1000 times, the case where aggregates were observed was marked as x, and the case where aggregates were not observed was marked as ◯.

(Scratch resistance)
The film which consists of a cellulose resin composition of an Example and a comparative example is used for a stainless steel board, a cutter blade is applied to a 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 100 g load is applied, ◎,
When the film is cut within a load range of less than 100 g and 50 g or more,
When the film is cut within a load range of less than 50 g and 30 g or more, Δ,
When the film is cut with a load of less than 30 g
It was.

The resin compositions of Examples 1 to 14 using the cellulose derivative defined in the present invention were excellent in dispersibility and had good scratch resistance while maintaining good impact resistance.

According to the molding material of the present invention, since it has excellent thermoplasticity, it can be molded by heat molding or the like, and the molding material and the molding obtained from the molding material have good impact resistance. It has good scratch resistance and can be suitably used as, for example, components such as automobiles, home appliances, electric and electronic equipment, mechanical parts, housing / building materials, and 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.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on Dec. 25, 2009 (Japanese Patent Application No. 2009-295067), the contents of which are incorporated herein by reference.

Claims (17)

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 α, β-unsaturated carboxylic acid ester polymer.
   A) Hydrocarbon group having 1 to 3 carbon atoms: —R _A
   B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)
2. 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 to 4 carbon atoms. )
3. The molding material according to claim 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 to 4 carbon atoms, and n represents an integer of 1 or more.)
4. The molding material according to any one of claims 1 to 3, wherein R _A is a methyl group or an ethyl group.
5. The molding material according to any one of claims 2 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 claims 2 to 5, wherein R _B and R _C1 are each independently a methyl group, an ethyl group, or a propyl group.
7. 6. The molding material according to claim 1, wherein R _B is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms.
8. The molding material according to any one of claims 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 claims 1 to 8, wherein the cellulose derivative has substantially no carboxyl group, sulfonic acid group, or salt thereof.
10. The molding material according to any one of claims 1 to 9, wherein the cellulose derivative is insoluble in water.
11. The molding material according to any one of claims 1 to 10, wherein the α, β-unsaturated carboxylic acid ester polymer is a polymethyl methacrylate polymer.
12. The molding material according to any one of claims 1 to 11, further comprising a compatibilizing agent.
13. The molding material according to claim 12, wherein the compatibilizer 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 claim 13, wherein the main skeleton is an α, β-unsaturated carboxylic acid ester copolymer or an α, β-unsaturated carboxylic acid ester copolymer.
15. A molded body obtained by thermoforming the molding material according to any one of claims 1 to 14.
16. A method for producing a molded body, comprising a step of heating and molding the molding material according to any one of claims 1 to 14.
17. A housing for electrical and electronic equipment comprising the molded body according to claim 15.