JP2011132445A - Molding material, molded article, production method of the same, and chassis for electric and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding material having good thermoplasticity, molding property, antifouling property, shock resistance, bending strength, flame retardancy and moisture absorption resistance. <P>SOLUTION: The molding material contains: a cellulose derivative having at least one group produced by substituting a hydrogen atom of a hydroxyl group included in the cellulose with (A) a hydrocarbon group -R<SB>A</SB>and at least one group produced by substituting a hydrogen atom in a hydroxyl group in the cellulose with (B) an acyl group -CO-R<SB>B</SB>(where R<SB>B</SB>represents a hydrocarbon group); and a silicon-containing compound. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a molding material, a molded body, a manufacturing method thereof, and a casing for electric and electronic equipment.

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

As known cellulose derivatives, hydroxypropylmethylacetylcellulose is described in Patent Document 3 and Patent Document 4. Patent Document 3 and Patent Document 4 describe that this hydroxypropylmethylacetylcellulose is useful as an additive for reducing the vapor pressure of an organic solvent that easily volatilizes. In addition, the substitution degree of each substituent in hydroxypropylmethylacetylcellulose described in Patent Document 3 and Patent Document 4 is, for example, a molar substitution degree (MS) of hydroxypropyl group in a range of about 2 to 8, a substitution degree of methyl group Is in the range of about 0.1 to 1 and the degree of substitution of the acetyl group is in the range of about 0.8 to 2.5.
Further, hydroxypropylmethylpropylcellulose, hydroxypropylmethylbutylcellulose and the like (Patent Document 5), hydroxypropylmethylserose phthalate and the like (Patent Document 6) are disclosed as uses such as drug coating.
Patent Document 7 discloses that a film containing a cellulose derivative contains fine particles such as silicon dioxide, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate and magnesium silicate as a matting agent. It states that it can be added.

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 2009-114397 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.
In addition, Patent Document 7 does not demonstrate the effect by adding those fine particles as a specific example, and there is no suggestion of adding a molecular silicon-containing compound. There is no description of the usage as a molding material.

  An object of the present invention is to provide a molding material having good thermoplasticity, moldability, antifouling property, impact resistance, bending strength, flame retardancy and moisture absorption resistance. Another object of the present invention is to provide a molded body obtained by molding the molding material, a method for producing the molded body, and an electric / electronic device composed of the molded body.

The inventors focused on the molecular structure of cellulose, and made cellulose a cellulose derivative having a specific structure having an ether structure and an ester structure, and the molding material containing the cellulose derivative having the specific structure and a silicon-containing compound was superior. It has been found that thermoplasticity, moldability, antifouling properties, impact resistance, bending strength, flame retardancy, and moisture absorption resistance can be imparted, 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 a silicon-containing compound.
A) Hydrocarbon group: -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 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). The molding material in any one of said 1-3 whose said _RA is a C1-C4 alkyl group.
5. The molding material in any one of said 1-4 whose said _RA is a methyl group or an ethyl group.
6). 6. The molding material according to any one of 1 to 5, wherein R _B and R _C1 are each independently an alkyl group or an aryl group.
7). 7. The molding material according to any one of 1 to 6, wherein R _B and R _C1 are each independently a methyl group, an ethyl group, or a propyl group.
8). 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 1-6.

9. The molding material in any one of said 2-8 whose said alkyleneoxy group is group represented by following formula (1) or (2).

10. 10. The molding material according to any one of 1 to 9 above, wherein the cellulose derivative does not substantially contain a carboxyl group, a sulfonic acid group, and salts thereof.
11. The molding material in any one of said 1-10 whose said cellulose derivative is insoluble in water.
12 The silicon-containing compound is an organosilicon compound having a structural unit represented by the following general formula 1; polydimethylsiloxane; a polydimethylsiloxane side chain or terminal methyl group is a hydrogen atom, substituted or unsubstituted aliphatic carbonization The molding material according to any one of the above 1 to 11, which is a silicone oil substituted or modified with a hydrogen group or an aromatic hydrocarbon group; a silicone powder; a modified silicone oil or a combination thereof.
General formula 1: R _m Si _{(4-m) / 2}
(M is an integer of 1 to 3 and R is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or an aromatic hydrocarbon group)
13. The molding material in any one of said 1-12 whose content of the said silicon-containing compound is 0.1-50 mass%.
14 In addition to the silicon-containing compound, 0.1 to 50% by mass of any one of magnesium hydroxide, aluminum hydroxide, chlorinated polystyrene, chlorinated paraffin, zinc borate and a combination thereof is contained. The molding material in any one of -13.

15. The molded object obtained by shape | 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 formed into a molded body by heat molding or the like. In addition, the molded body formed by the molding material of the present invention has good thermoplasticity, moldability, antifouling properties, impact resistance, bending strength, flame retardancy, moisture absorption resistance, such as automobiles, home appliances, It can be suitably used as a component part such as an electric / electronic device, a machine part, a house / building material, or the like. Moreover, since it is a plant-derived resin, it can be replaced with a conventional petroleum-derived resin as a material that can contribute to the prevention of global warming.

In the present invention, the hydrogen atom of the hydroxyl group contained in cellulose is
A cellulose derivative 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 a silicon-containing compound.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)
Hereinafter, the present invention will be described in detail.

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

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

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

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

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

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

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

The cellulose derivative in the 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 resulting resin composition has excellent bending elastic modulus.

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

In the general formula (3), R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms. The preferred ranges of R _C1 and R _C2 are the same as those described above. n is an integer of 1 or more. The upper limit of n is not particularly limited, and varies depending on the amount of alkyleneoxy group introduced, but is about 10, for example. n is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1. When a plurality of R _c2 are present, they may be the same or different, but are preferably the same.
In addition, the cellulose derivative in the present invention is a group of C) containing only one alkyleneoxy group (a group in which n is 1 in the general formula (3)) and C) containing two or more alkyleneoxy groups. And a group (a group in which n is 2 or more in the above general formula (3)).

Further, the bonding direction of the alkyleneoxy group to the cellulose derivative in the group C) is not particularly limited, but it is preferable that the alkylene group part (R _C2 ) of the alkyleneoxy group is bonded to the 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 portion preferably has 1 to 5 carbon atoms), alkenyl groups, and the like. However, even when a substituent is included, R _C2 has 2 or 3 carbon atoms. In _the case R A, _{R B,} and _{R C1} is other than alkyl group, an alkyl group (preferably having from 1 to 5 carbon atoms) may have as a substituent.

In particular, when R _B and R _C1 have a further substituent, it is preferable that they substantially have no carboxyl group, sulfonic acid group, and salts thereof. 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, acetyl butyl cellulose, acetyl pentyl cellulose, acetyl hexyl cellulose, acetyl cyclohexyl cellulose, acetyl phenyl cellulose, acetyl naphthyl cellulose,

Propionylmethylcellulose, propionylethylcellulose, propionylpropylcellulose, propionylbutylcellulose, propionylpentylcellulose, propionylhexylcellulose, propionylcyclohexylcellulose, propionylphenylcellulose, propionylnaphthylcellulose,

Butyrylmethylcellulose, butyrylethylcellulose, butyrylpropylcellulose, butyrylbutylcellulose, butyrylpentylcellulose, butyrylhexylcellulose, butyrylcyclohexylcellulose, butyrylphenylcellulose, butyrylnaphthylcellulose,

Methylcellulose-2-ethylhexanoate, ethylcellulose-2-ethylhexanoate, propylcellulose-2-ethylhexanoate, butylcellulose-2-ethylhexanoate, pentylcellulose-2-ethylhexanoate, hexylcellulose -2-ethylhexanoate, cyclohexylcellulose-2-ethylhexanoate, phenylcellulose-2-ethylhexanoate, naphthylcellulose-2-ethylhexanoate,

Acetoxyethylmethylacetylcellulose, acetoxyethylethylacetylcellulose, acetoxyethylpropylacetylcellulose, acetoxyethylbutylacetylcellulose, acetoxyethylpentylacetylcellulose, acetoxyethylhexylacetylcellulose, acetoxyethylcyclohexylacetylcellulose, acetoxyethylphenylacetylcellulose, acetoxyethylnaphthyl Acetylcellulose,

Acetoxyethylmethylpropionylcellulose, acetoxyethylethylpropionylcellulose, acetoxyethylpropylpropionylcellulose, acetoxyethylbutylpropionylcellulose, acetoxyethylpentylpropionylcellulose, acetoxyethylhexylpropionylcellulose, acetoxyethylcyclohexylpropionylcellulose, acetoxyethylphenylpropionylcellulose, acetoxyethylnaphthyl Propionyl cellulose,

Acetoxyethylmethylcellulose-2-ethylhexanoate, acetoxyethylethylcellulose-2-ethylhexanoate, acetoxyethylpropylcellulose-2-ethylhexanoate, acetoxyethylbutylcellulose-2-ethylhexanoate, acetoxyethylpentylcellulose 2-ethylhexanoate, acetoxyethylhexylcellulose-2-ethylhexanoate, acetoxyethylcyclohexylcellulose-2-ethylhexanoate, acetoxyethylphenylcellulose-2-ethylhexanoate, acetoxyethylnaphthylcellulose-2- Ethyl hexanoate,

Propionyloxyethyl methyl acetylcellulose, propionyloxyethyl ethyl acetylcellulose, propionyloxyethylpropyl acetylcellulose, propionyloxyethyl butylacetylcellulose, propionyloxyethylpentylacetylcellulose, propionyloxyethylhexylacetylcellulose, propionyloxyethylcyclohexylacetylcellulose, propionyloxy Ethylphenylacetylcellulose, propionyloxyethylnaphthylacetylcellulose,

Propionyloxyethylmethylpropionylcellulose, propionyloxyethylethylpropionylcellulose, propionyloxyethylpropylpropionylcellulose, propionyloxyethylbutylpropionylcellulose, propionyloxyethylpentylpropionylcellulose, propionyloxyethylhexylpropionylcellulose, propionyloxyethylcyclohexylpropionylcellulose, Ethylphenylpropionylcellulose, propionyloxyethylnaphthylpropionylcellulose,

Propionyloxyethylmethylcellulose-2-ethylhexanoate, propionyloxyethylethylcellulose-2-ethylhexanoate, propionyloxyethylpropylcellulose-2-ethylhexanoate, propionyloxyethylbutylcellulose-2-ethylhexanoate, Propionyloxyethylpentylcellulose-2-ethylhexanoate, propionyloxyethylhexylcellulose-2-ethylhexanoate, propionyloxyethylcyclohexylcellulose-2-ethylhexanoate, propionyloxyethylphenylcellulose-2-ethylhexanoate , Propionyloxyethyl naphthylcellulose-2-ethylhexanoate,

Acetoxypropylmethylacetylcellulose, acetoxypropylethylacetylcellulose, acetoxypropylpropylacetylcellulose, acetoxypropylbutylacetylcellulose, acetoxypropylpentylacetylcellulose, acetoxypropylhexylacetylcellulose, acetoxypropylcyclohexylacetylcellulose, acetoxypropylphenylacetylcellulose, acetoxypropyl Naphthylacetylcellulose,

Propionyloxypropylmethylacetylcellulose, propionyloxypropylethylacetylcellulose, propionyloxypropylpropylacetylcellulose, propionyloxypropylbutylacetylcellulose, propionyloxypropylpentylacetylcellulose, propionyloxypropylhexylacetylcellulose, propionyloxypropylcyclohexylacetylcellulose, propionyl Oxypropylphenylacetylcellulose, propionyloxypropylnaphthylacetylcellulose,

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 may contain two or more kinds.

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

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

Further, the number of unsubstituted hydroxyl groups present in the cellulose derivative is not particularly limited. The degree of substitution DS _{H of} hydrogen atoms (ratio in which the hydroxyl groups at the 2nd, 3rd and 6th positions in the repeating unit are unsubstituted) can be in the range of 0 to 1.5, preferably 0 to 0.6. And it is sufficient. By the DS _H and 0.6 or less, or to improve the fluidity of the 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 may have a substituent other than A) a hydrocarbon group, B) an acyl group, and C) a group containing an alkyleneoxy group and an acyl group. Examples of the substituent that may be included include a hydroxyethyl group, a hydroxypropyl group, a hydroxyethoxyethyl group, a hydroxypropoxypropyl group, a hydroxyethoxyethoxyethyl group, and a hydroxypropoxypropoxypropyl group. Therefore, the sum of the degree of substitution of all the substituents of the cellulose derivative is 3, but (DS _A + DS _B + DS _C + DS _H ) is 3 or less.

  The amount of alkyleneoxy group introduced in the group C) is expressed in terms of molar substitution (MS: number of moles of substituent introduced per glucose residue) (edited by Cellulose Society, Cellulose Dictionary P142). The molar substitution degree MS of the alkyleneoxy group is preferably 0 <MS, more preferably 0 <MS ≦ 1.5, and further preferably 0 <MS <1.0. When MS is 1.5 or less (MS ≦ 1.5), heat resistance, moldability and the like can be improved, and a cellulose derivative suitable for a 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 preferred embodiment of the method for producing a cellulose derivative having the above-mentioned A) hydrocarbon group: -R _A and B) acyl group: -CO-R _B (R _B represents a hydrocarbon group) includes cellulose ether, It includes a step of esterification by reacting acid chloride or acid anhydride in the presence.
As the cellulose ether, for example, one in which at least a part of the hydrogen atoms of the hydroxyl groups at the 2nd, 3rd and 6th positions of the β-glucose ring contained in cellulose is substituted with a hydrocarbon group can be used. Specific examples include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, allyl cellulose, and benzyl cellulose.

A) hydrocarbon group: —R _A , B) acyl group: —CO—R _B (R _B represents a hydrocarbon group), and C) alkyleneoxy group: —R _C2 —O— and an acyl group: A preferred embodiment of a method for producing a cellulose derivative having a group containing —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms) is a hydrocarbon group. And hydroxyethyl cellulose ether having a hydroxyethyl group or hydroxypropyl cellulose ether having a hydroxypropyl group are reacted by an acid chloride or an acid anhydride to react with the esterification (acylation). is there.
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. Silicon-containing compound The molding material of the present invention contains a silicon-containing compound. By including a silicon-containing compound, the impact resistance, flame retardancy, and moisture absorption resistance can be improved compared with the case where a specific cellulose derivative is used alone without reducing the performance such as rigidity, bending strength, and heat resistance. Can be improved.
In addition, a silicon-containing compound shall include both the compound which consists only of silicon, and the compound which consists of a silicon element and another element.
The silicon-containing compound is not particularly limited, and those commonly used can be used. For example, silane compounds, silicone compounds, silicon tetrachloride, and the like are generally known as silicon-based flame retardants. Can be mentioned.

Among them, preferable examples of the silicon-containing compound used in the present invention include the formula: R _m Si _{(4-m) / 2} (m is an integer of 1 or more, preferably 1 or more and 3 or less, and R is a hydrogen atom. A substituted or unsubstituted aliphatic hydrocarbon group or an aromatic hydrocarbon group), a two- or three-dimensional organosilicon compound having a main structural unit as a structural unit; polydimethylsiloxane, or poly Examples thereof include those in which the methyl group at the side chain or terminal of dimethylsiloxane is substituted or modified with a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group or an aromatic hydrocarbon group, so-called silicone oil, or modified silicone oil. . 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 compounds may be used alone or in combination of two or more.

  Commercially available silicon-containing compounds can also be used in the present invention. For example, Dow Corning Co., Ltd. 4-7105, 4-7051 (all are silicone powder), L-7001 (silicone oil), Aldrich fumed silica, Daihachi Chemical Co., Ltd. TPP (triphenyl phosphate), Japanese Examples include decabromodiphenyl ether manufactured by Kojun Pharmaceutical Co., Ltd.

4). Molding Material and Molded Body The molding material of the present invention contains the cellulose derivative and silicon-containing compound described above, and may contain other additives as necessary.
The content rate of the component contained in the molding material of this invention is not specifically limited. Preferably, the cellulose derivative is contained in an amount of 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 70 to 90% by mass.
The content ratio of the silicon-containing compound contained in the molding material of the present invention is preferably 0.1 to 50% by mass, more preferably 10 to 40% by mass.
The ratio of the cellulose derivative and the silicon-containing compound is preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass, based on the total mass of both.

  In addition to the cellulose derivative and the silicon-containing compound, the molding material of the present invention may contain various additives such as a filler (reinforcing material) and a flame retardant as necessary.

  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 the specific cellulose derivative can be suppressed, and flame retardancy, antifouling property, and moisture absorption 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.
As the antioxidant in the present invention, a phosphorus-based antioxidant, a hindered phenol-based antioxidant (for example, “Irganox 1010” manufactured by Ciba Specialty Chemicals, “Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd., etc.) is used. It is preferable.
0.01-10 mass% is preferable in a molding material, and, as for the compounding quantity of antioxidant, 0.03-8 mass% is more preferable. If it is 0.01% by mass or more, the effect of adding an antioxidant can be obtained, and if it is 10% by mass or less, the impact resistance, moldability, rigidity, bending strength, heat resistance, etc. of the cellulose derivative are reduced. Since it can suppress, it 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 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, nitrogen compound-based flame retardants, inorganic flame retardants, etc. 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 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, condensed phosphate 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 flame retardant other than the phosphorus-containing flame retardant include 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, metal salt of tungstic acid, Complex oxides of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, swellable graphite and other inorganic flame retardants, chlorinated polystyrene, chlorinated paraffin, etc. These organic flame retardants can be used. These other flame retardants may be used alone or in combination of two or more.
In the present invention, it is preferable to use any one of magnesium hydroxide, aluminum hydroxide, chlorinated polystyrene, chlorinated paraffin, zinc borate and combinations thereof from the viewpoint of the effect.

  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. In addition, when using any one of magnesium hydroxide, aluminum hydroxide, chlorinated polystyrene, chlorinated paraffin, zinc borate and a combination thereof as a flame retardant, the amount used is 0.1 to 50 in the molding material. It is good to use the mass%, Preferably 5-20 mass%.

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 derivatives, plasticizers, stabilizers (ultraviolet absorbers, etc.), mold release agents (fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, aliphatic partially saponified esters, paraffins) 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, Examples include anti-drip agents, antibacterial agents, and antifungal agents. Furthermore, a coloring agent containing a dye or a pigment can be added.

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

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

  When the molding material of this invention contains polymers other than a cellulose derivative, 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, its content is usually 5% by mass or less, preferably 0.005 to 5% by mass, more preferably 0.01 to 1% by mass in the molding material. It is.

The molded body of the present invention can be obtained by molding a molding material containing the cellulose derivative and the silicon-containing compound. 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 and impact resistance and low environmental load, for example, exterior parts for electric and electronic devices such as copiers, printers, personal computers, televisions (especially casings) ) Can be suitably used.

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

(Synthesis Example 1)
<Synthesis 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 to 90 ° C. After stirring for 3 hours, the temperature of the reaction system was cooled to room temperature. When the reaction solution was added to 10 L of water with vigorous stirring, a white solid was precipitated. The white solid was filtered off by suction filtration and washed with a large amount of water three times. The obtained white solid was vacuum-dried at 100 ° C. for 6 hours to obtain the objective cellulose derivative (C-1) (acetoxypropylmethylacetylcellulose) as a white powder.

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

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

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

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

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

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

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

[Production of molded body]
Cellulose derivatives (C-1 to C-7, H-2), a silicon-containing compound, and an antioxidant were mixed at a blending ratio shown in Table 2 to prepare a molding material. This molding material is supplied to a twin-screw kneading extruder (manufactured by Technobel Co., Ltd., ULTRANONO) to produce pellets. As supplied, 4 × 10 × 80 MM multi-purpose test pieces (impact test pieces and bending test pieces) and 3.1 × 13 × 127 MM flame retardant test pieces were molded.

In Table 2, additives and phenolic antioxidants are as follows.
Additive 1 (silicone powder): Dow Corning Co., Ltd. 4-7105
Additive 2 (silicone powder): Dow Corning Co., Ltd. 4-7051
・ Additive 3 (fumed silica): manufactured by Aldrich ・ Additive 4 (silicone oil): Dow Corning L-7001
・ Additive 5 (triphenyl phosphate): Daihachi Chemical Co., Ltd. TPP
Additive 6 (decabromodiphenyl ether): manufactured by Wako Pure Chemical Industries, Ltd. Antioxidant: (phenolic antioxidant): Ciba Specialty Chemicals Co., Ltd., Irganox 1010

[Evaluation]
The following items were evaluated using the obtained multipurpose test pieces or flame retardant evaluation test pieces. 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.

(Bending strength)
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) A bending test was conducted at 64 mm and a test speed of 2 mm / min, and the maximum stress during the test was defined as the bending strength. The measurement is an average of three measurements.

(Heat deformation temperature (HDT))
In accordance with ISO75, a constant bending load (1.8 MPa) is applied to the center of the test piece (in the flatwise direction), the temperature is raised at a constant speed, and the temperature when the strain at the center reaches 0.34 mm ( ° C). As the heat distortion temperature measuring device, HDT tester 6M-2 manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. 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.

(Flame retardant test)
As a flame retardant index, a vertical combustion test based on UL94 was conducted. The number of tests is five. V-not for non-self-extinguishing material, drip of resin composition during combustion test with two ignitions, V-2 for resin that self-extinguishes within specified time (within 30 seconds after each ignition), resin for combustion V-1 which does not have a flaming drip of the composition and self-extinguishes within a predetermined time (within 30 seconds after each ignition), within a predetermined time without a flaming drip of the resin composition during combustion (within 10 seconds after each ignition) ) Was self-extinguishing V-0.

(Formability evaluation)
Moldability evaluation shows molding suitability with an injection molding machine. Molding materials with excellent molding transportability and injection properties are marked with ◯, molding materials with problems in either one, and molding with problems in both. The material was crossed.

(Anti-fouling test)
As an index of antifouling properties, the above multipurpose test piece was used, and 1 g of carbon powder was sprinkled on the test piece and allowed to stand for 1 minute. After 1 minute, dry air was passed over the surface of the test piece for 3 minutes, and the test surface was visually observed. The test piece surface was evaluated as ◯ when the surface was not black at all, Δ when a slightly blackened place was found, and x when there was a clear black discoloration.

(Hygroscopic)
Using the above-mentioned multi-purpose test piece as an index of moisture absorption resistance, the molded test piece was dried at 50 ° C. for 24 hours, and then cooled at 30 ° C. 85% ± 5% with a low-temperature constant temperature and humidity machine μ-351R (made by Isuzu Seisakusho) The test piece was left to stand for 2 weeks, and the test piece was evaluated visually as ◯ when the specimen was not deformed at all, x when the deformation was confirmed to be large, and Δ when the change was slightly observed.

  The results are shown in Table 2. In addition, the compounding quantity of each component in a table | surface is a mass part.

From Table 2, the molded body formed of the molding material of the example has better thermoplasticity, moldability, antifouling property, impact resistance, bending strength, flame resistance, and moisture absorption resistance than those of the comparative example. It became clear that it has sex.
As can be seen from the comparison between Examples 1 to 13 and Comparative Example 1, when the cellulose derivative specified in the present invention was used, the impact resistance was higher than when the cellulose derivative other than specified in the present invention was used. It was excellent in bending strength, bending elasticity and flame retardancy.
Moreover, as can be seen from the comparison between Examples 1 to 4 and Comparative Examples 2 to 3, when the silicon-containing compound is used, the impact resistance, bending strength, and bending are higher than when the silicon-containing compound is not used. It was excellent in elasticity, flame retardancy, moldability, antifouling property, and moisture absorption 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 a silicon-containing compound.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.) 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 C1-C4 alkyl group. The molding material in any one of Claims 1-4 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. Wherein R _B and R _C1 are each independently a methyl group, an ethyl group, or propyl group, molding material according to any of claims 1 to 6. Wherein R _B is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms, molding material according to any one of claims 1 to 6. The molding material in any one of Claims 2-8 whose said alkyleneoxy group is group represented by following formula (1) or (2).

  The molding material in any one of Claims 1-9 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 1-10 whose said cellulose derivative is insoluble in water. The silicon-containing compound is an organosilicon compound having a structural unit represented by the following general formula 1; polydimethylsiloxane; a polydimethylsiloxane side chain or terminal methyl group is a hydrogen atom, substituted or unsubstituted aliphatic carbonization The molding material according to any one of claims 1 to 11, which is a silicone oil substituted or modified with a hydrogen group or an aromatic hydrocarbon group; a silicone powder; a modified silicone oil or a combination thereof.
General formula 1: R _m Si _{(4-m) / 2}
(M is an integer of 1 to 3 and R is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, or an aromatic hydrocarbon group)   The molding material in any one of Claims 1-12 whose content of the said silicon-containing compound is 0.1-50 mass%.   In addition to the silicon-containing compound, 0.1 to 50% by mass of any one of magnesium hydroxide, aluminum hydroxide, chlorinated polystyrene, chlorinated paraffin, zinc borate and a combination thereof is contained. The molding material in any one of 1-13.   The molded object obtained by shape | 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.