JP2011132467A - Molding material, molded body and manufacturing method therefor, and housing for electrical and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding material having good thermoplasticity, strength, heat resistance, dimensional stability, and moldability. <P>SOLUTION: The molding material includes: a cellulose derivative containing at least one group in which a hydrogen atom of a hydroxyl group contained in the cellulose is substituted with the following (A) and at least one group in which the hydrogen atom is substituted with the following (B); and glass fibers. (A) is a hydrocarbon group: -R<SB>A</SB>; and (B) is an acyl group: -CO-R<SB>B</SB>(R<SB>B</SB>represents a hydrocarbon group). <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.

  On the other hand, Patent Document 5 describes that a glass fiber can be added to a thermoplastic resin composition for the purpose of improving the transparency of a conductive paint and controlling the conductivity. Patent Document 6 describes that glass fiber can be added as a fiber reinforcement to a thermoplastic resin composition containing cellulose ester.

JP-A-56-55425 JP 2008-24919 A US Pat. No. 3,979,179 U.S. Pat. No. 3,940,384 Japanese Patent Application Laid-Open No. 07-106617 JP 2006-11858 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 and 4 are water-soluble or swellable and insufficient in strength, which is not preferable as a molding material.

  An object of the present invention is to provide a molding material having good thermoplasticity, strength, heat resistance, dimensional stability, and moldability. 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 present inventors pay attention to the molecular structure of cellulose, and make cellulose a cellulose derivative having a specific structure having an ether structure and an ester structure, and by using a molding material containing the cellulose derivative having the specific structure and glass fiber, thermoplasticity, The inventors have found that excellent performance is exhibited from all viewpoints of strength, heat resistance, dimensional stability, and moldability, and have completed the present invention.
That is, the said subject can be achieved by the following means.
[1]
The hydrogen atom of the hydroxyl group contained in cellulose
A cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below;
Molding material containing glass fiber.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)
[2]
The molding material according to [1], wherein the cellulose derivative further contains 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]
[Claim 1] The molding material according to [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.)
[4]
The molding material according to any one of [1] to [3], wherein R _A is an alkyl group having 1 to 4 carbon atoms.
[5]
The molding material according to any one of [1] to [4], wherein R _A is a methyl group or an ethyl group.
[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]
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 one of [1] to [6].
[9]
The molding material in any one of [2]-[8] whose said alkyleneoxy group is group represented by following formula (1) or (2).

[10]
The molding material in any one of [1]-[9] in which the said cellulose derivative does not have a carboxyl group, a sulfonic acid group, and these salts substantially.
[11]
The molding material according to any one of [1] to [10], wherein the cellulose derivative is insoluble in water.
[12]
Molding material in any one of [1]-[11] whose fiber length of the glass fiber is 100 micrometers or more.
[13]
The molding material according to any one of [1] to [12], wherein the glass fiber is an organic glass fiber.
[14]
The molding material according to any one of [1] to [13], wherein the glass fiber surface treating agent is an isocyanate compound.
[15]
The molding material according to any one of [1] to [14], wherein the isocyanate compound is toluene diisocyanate or hexamethylene diisocyanate.
[16]
Molding material in any one of [1]-[15] whose content of the said glass fiber is 1-30 mass% in a molding material.
[17]
[1] A molded article obtained by molding the molding material according to any one of [16].
[18]
The manufacturing method of a molded object including the process of heating and molding the molding material in any one of [1]-[16].
[19]
[17] A casing for an electric and electronic device comprising the molded article according to [17].

  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. Further, the molded body formed by the molding material of the present invention has good strength, heat resistance, dimensional stability, moldability, for example, components such as automobiles, home appliances, electrical and electronic equipment, mechanical parts, It can be suitably used as a house / building material. 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 glass fiber.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)
Hereinafter, the present invention will be described in detail.

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

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

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

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

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

A) Hydrocarbon group: -R _A may be either an aliphatic group or an aromatic group.
When R _A is an aliphatic group, it may be linear, branched, or cyclic, and may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
When R _A is an aromatic group, it may be either a single ring or a condensed ring. When R _A is an aromatic group, the preferable carbon number is 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. Examples of the aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
A) The hydrocarbon group is preferably an aliphatic group because the resulting 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,

Examples include valeroxypropylmethyl valeroyl cellulose and valeroxybutyl methyl valeroyl cellulose.

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

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 has no carboxylic acid as a substituent, for example, a dicarboxylic acid such as phthalic anhydride, maleic anhydride, or the like, and a compound that generates a carboxyl group by reacting with cellulose. It is preferable not to use.

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

3. Glass fiber The molding material of this invention contains glass fiber.
The glass fiber used in the present invention is added mainly for the purpose of improving mechanical properties, and improves strength, heat resistance, dimensional stability, and moldability as compared with the case where a specific cellulose derivative is used alone. Can do. Moreover, glass fiber has high safety and is useful at the time of production and when formed into a molded body. The size of the respirable fiber that is inhaled into the lung is 3 μm or less in diameter, and if it is a glass fiber with a thickness of 4 to 8 μm, even if it is almost removed by the nose or bronchus and enters the lung This is because it has the property of being dissolved in body fluids or taken up by macrophages and discharged in a short period of time.

  The glass fiber used in the present invention is not particularly limited as long as it is generally used for reinforcing a resin, for example, selected from long fiber type or short fiber type chopped strand, cut fiber, milled fiber, and the like. be able to.

Regarding the cross-sectional shape of the glass fiber in the present invention, any shape such as a circle, a rectangle, and a flat shape can be used, but a flat shape is preferable. In general, a composition containing glass fiber is oriented in the flow direction during molding, so the anisotropy of molding shrinkage (percentage of dimensional difference between the resin molded product and the mold) increases and deformation increases. Become. However, when the cross-sectional shape of the glass fiber is flat as in the present invention, the anisotropy of the molding shrinkage rate tends to be small and deformation and warping tend to be improved.
The flat cross section is a cross section perpendicular to the length direction, and the ratio of the long diameter (longest straight line distance in the cross section) to the short diameter (long straight line and the longest straight line distance in the right direction) is 1.3 to 10, preferably Is 1.5-5, more preferably 1.5-4. If the ratio of the major axis to the minor axis is 1.3 or more, the effect on deformation is greater, and if the ratio is 10 or less, it is easily available. Specific shapes include eyebrows, ovals, ovals, semicircles or arcs, rectangles, or similar shapes that belong to ovals, particularly from the viewpoint of fluidity and low warpage. preferable. Moreover, in order to make specific gravity small, it can also be made hollow.
Such a cross-sectional shape is to be spun using a nozzle having an appropriate hole shape such as an oval, an ellipse, a rectangle, or a slit as a bushing used for discharging molten glass when producing glass fibers. It is prepared by. Also prepared by spinning molten glass from a plurality of adjacent nozzles having various cross-sectional shapes (including circular cross-sections), and joining the spun molten glass into a single filament it can.

Although the cross-sectional area of the glass fiber in the present invention is not particularly limited, a range of 2 × 10 ⁻⁵ to 8 × 10 ⁻³ mm ² is preferable, and a range of 8 × 10 ⁻⁵ to 8 × 10 ⁻³ mm ² is more preferable. Preferably, the range of 8 * 10 < ^-5 > -8 * 10 <^-4> mm < ² > is still more preferable. If it is 2 × 10 ⁻⁵ or more, it is easy to handle, and if it is 8 × 10 ⁻³ mm ² or less, the effect is more easily obtained.

  The length of the glass fiber in the present invention can be set to, for example, 1 to 1000 μm, usually 100 to 1000 μm, depending on the balance between the mechanical properties and deformation of the molded body and the performance required for the molded body. Are appropriately selected. Thus, in order to reduce the deformation amount of the molded body, the shorter one is preferable, and the average fiber length is preferably 30 μm or more from the viewpoint of mechanical strength.

  Although the Mohs hardness of the glass fiber in this invention is not specifically limited, From a viewpoint of a strength improvement, it is preferable to set it as 5-8, for example. As the type of glass, E glass is preferably used from the viewpoints of mechanical properties and environmental durability.

  In using these glass fibers, if necessary, a sizing agent or a surface treatment agent can be used to make it organic. Examples of the sizing agent or the surface treatment agent include functional compounds such as an epoxy compound, an isocyanate compound, a silane compound, and a titanate compound. In order to increase the affinity with the cellulose derivative, it is preferable to perform surface treatment with an isocyanate compound, and among them, toluene diisocyanate or hexamethylene diisocyanate is preferably used. These compounds may be used after being subjected to surface treatment or convergence treatment in advance, or may be added at the same time as material preparation.

4). Molding material and molded body The molding material of the present invention contains the cellulose derivative and glass fiber 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. In the molding material, the cellulose derivative is preferably contained in an amount of 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 85 to 98% by mass.

The content ratio of the glass fiber contained in the molding material of the present invention is preferably 1 to 30% by mass, more preferably 5 to 20% by mass in the molding material, from the viewpoint of improvement in strength, heat resistance, dimensional stability, and moldability. %. If it is 1 mass% or more, the effect of addition of glass fiber can be obtained more remarkably, and if it is 30 mass% or less, it is difficult to affect the fluidity during molding, which is preferable.
In addition, the ratio of the cellulose derivative and the glass fiber is preferably 95/5 to 80/20, particularly preferably 90/10 to 80/20, based on the total mass of both. .

  The molding material of the present invention may contain various additives such as a filler (reinforcing material), a flame retardant, and an antioxidant, as necessary, in addition to the cellulose derivative and the glass fiber.

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

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

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

  When the molding material of the present invention contains a flame retardant, its content is not limited, but is usually 30 parts by mass or less, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the cellulose derivative. 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 preferably further contains an antioxidant. Thereby, since the said fluororesin can be suppressed, even if the addition amount to a 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-to Scan (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.

  Examples of amine-based antioxidants include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2, 6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2, 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2 , 2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2, , 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (2,2,6,6- Tetramethyl-4-piperidyl) terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) ethane, bis (2,2,6,6-tetramethyl-4-piperidyl) Hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate, phenyl-α-naphthyl Amine, phenyl-β-naphthylamine, N, N′-diphenyl-p-phenylenediamine, N-phenyl-N′-cyclohexyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, etc. It is done.

  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, it is preferable to use a hindered phenol-based antioxidant.

  When the molding material of the present invention contains an antioxidant, the content thereof is not limited, but is preferably 0.01 to 1% by mass, more preferably 0.1 to 0.5% by mass in the molding material. . If it is 0.01% by mass or more, the effect of adding an antioxidant can be obtained, and if it is 1% 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 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, the content is 30 mass% or less with respect to 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 this invention contains a plasticizer, the content is 5 mass% or less normally with respect to a molding material, 0.005-5 mass% is preferable, More preferably, 0.01-1 mass %.

The molded body of the present invention can be obtained by molding a molding material containing the cellulose derivative and the glass fiber. More specifically, it includes a step of heating the cellulose derivative and the glass fiber, or the molding material containing the cellulose derivative and the glass fiber and various additives as necessary, and molding by various molding methods. Obtained by the manufacturing method.
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.

  Hereinafter, examples and comparative examples according to the present invention and results of evaluation tests using these will be described, and the present invention will be described in more detail. The present invention is not limited to these examples.

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

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

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

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

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

In addition, the kind and substitution degree of the hydrocarbon group contained in the cellulose derivative obtained above, the kind and molar substitution degree of the alkyleneoxy group, and the kind of functional group substituted with a hydroxyl group (R ² , R ³ and R ⁶ ) The acylation degree was observed and determined by ¹ H-NMR using the method described in Cellulose Communication 6, 73-79 (1999). 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-1), glass fibers, surface treatment agents, and antioxidants were mixed at a blending ratio (% by mass) 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., Ultranano) to produce pellets, and then the obtained pellets are injected into an injection molding machine (FANUC Corporation Robot S-2000i, automatic injection molding machine). ) To form 4 × 10 × 80 mm multipurpose test pieces (impact test pieces and bending test pieces).

In Table 2, glass fiber 1, glass fiber 2, surface treatment agent 1, surface treatment agent 2, and phenolic antioxidant indicate the following.
Glass fiber 1: NITTOBO PF E-101, diameter 10 μm, length 300 μm
Glass fiber 2: NITTOBO PF E-101 ground product, diameter 10 μm, average length 60 μm
Surface treatment agent 1: hexamethylene diisocyanate, Asahi Kasei Duranate E402-100
-Surface treatment agent 2: Toluene diisocyanate, Mitsui Chemicals Polyurethane Cosmonate T80
・ Antioxidants: phenolic antioxidants, Irganox 1010, Ciba Specialty Chemicals Co., Ltd.

[Evaluation]
The following items were evaluated using the obtained multipurpose 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.

(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 performed 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 increased at a constant speed, and the temperature when the strain at the center reaches 0.34 mm ( ° C). As a heat distortion temperature measuring device, HDT tester 6M-2 manufactured by Toyo Seiki Seisakusho 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.

(Dimension evaluation)
In accordance with JIS K7209, the molded specimens were dried at 50 ° C. for 24 hours, then weighed, and the sample was immersed in a constant temperature water bath at 23 ° C. for 24 hours to remove moisture other than water content. Changes (length, width, thickness) were measured. The dimensional change rate (%) is {(length after immersion / length before immersion-1) × 100}, and the dimensional change rate (%) is {(width after immersion / width before immersion). −1) × 100}, and the dimensional change rate (%) of the thickness was determined by {(thickness after immersion / thickness before immersion−1) × 100} This time, the dimensional change rate in the length direction is shown as dimensional stability, <0.3% is indicated by ○, 0.3-0.5% is indicated by Δ, and> 0.5% is indicated by ×.

(Formability)
The moldability evaluation in Table 2 shows the moldability of an injection molding machine. A molding material that is excellent in both molding transportability and injection performance is indicated by ○, a molding material that has a problem in either one, and a problem in both. A molding material having x was marked as x.

  The results are shown in Table 2.

As can be seen from Table 2, Examples 1 to 13 are superior to Comparative Examples 1 and 2 in strength, heat resistance, dimensional stability, moldability, and a good balance of physical properties. In particular, in Examples 3 to 6, the physical property values shown in the table are all maintained at a high level.
From the above results, it is apparent that a molding material having excellent strength, heat resistance, dimensional stability, and moldability can be realized by satisfying the requirements of the present invention.

Claims (19)

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;
Molding material containing glass fiber.
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 molding material according to claim 1, wherein the glass fiber has a fiber length of 100 μm or more.   The molding material according to claim 1, wherein the glass fiber is an organic glass fiber.   The molding material according to claim 1, wherein the glass fiber surface treatment agent is an isocyanate compound.   The molding material according to claim 1, wherein the isocyanate compound is toluene diisocyanate or hexamethylene diisocyanate. The molding material according to any one of claims 1 to 15, wherein a content of the glass fiber is 1 to 30% by mass in the molding material.   The molded object obtained by shape | molding the molding material in any one of Claims 1-16.   The manufacturing method of a molded object including the process of heating and shape | molding the molding material in any one of Claims 1-16.   A housing for electrical and electronic equipment comprising the molded body according to claim 17.