WO2011078272A1 - Molding material, molded body, manufacturing method thereof, and casing for electrical or electronic equipment - Google Patents

Abstract

Disclosed are a molding material and a molded body having excellent rigidity, bending strength, and heat resistance, as well as impact resistance, molding processability, and low-temperature impact resistance, and, in addition, a molding material and a molded body with excellent falling ball impact strength and Vicat softening temperature. The molding material contains an aliphatic polyester elastomer with an average molecular weight of 10,000 or more, and a cellulose derivative containing at least one group in which the hydrogen atom of a hydroxyl group in the cellulose is substituted by A), below, and at least one group in which the hydrogen atom of a hydroxyl group in the cellulose is substituted by B), below. A) Hydrocarbon group: -R_A; B) Acyl group: -CO-R_B (R_B represents a hydrocarbon group).

Description

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

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

Various materials are used for members constituting electrical and electronic devices such as copiers and printers in consideration of the characteristics and functions required of 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.

Furthermore, Patent Document 7 discloses an example of a coating film containing acetylbutyl cellulose and an adipic acid-based polyester plasticizer.

Japanese Unexamined Patent Publication No. 56-55425 Japanese Unexamined Patent Publication No. 2008-24919 US Pat. No. 3,979,179 U.S. Pat. No. 3,940,384 International Publication No. 09/010837 Japanese Patent No. 3017412 specification Japanese Unexamined Patent Publication No. 2008-184603

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. In addition, the cellulose derivative described in Patent Document 5 is described as being poorly water-soluble, but only described in the text, and its synthesis method and usage form are specifically disclosed in Examples and the like. Absent.
Furthermore, the film formed using the cellulose derivative and the adipic acid-based polyester plasticizer described in Patent Document 7 can be used for specific applications as a coating film, but is not suitable for use as a general molding material. . Moreover, even if it can be set as a molded object, it is thought that it is inferior to impact resistance. Further, since the adipic acid-based polyester plasticizer has a low molecular weight, it is considered that bleed-out occurs when attempting to heat-mold.
In addition, improvement in impact resistance at low temperatures is also required for molding materials using cellulose derivatives.

The object of the present invention is to achieve performance such as rigidity (flexural modulus), bending strength, and heat resistance (thermal deformation temperature), and even better impact resistance (Charpy impact strength), excellent moldability, and low temperature. Another object is to provide a molding material and a molded body having impact resistance, and a molding material and a molded body having good falling ball impact strength and Vicat softening point temperature. Another object of the present invention is to provide a method for producing the molded body and a housing for electrical and electronic equipment composed of the molded body.

The present inventors paid attention to the molecular structure of cellulose, and made cellulose into a cellulose derivative having a specific structure having an ether structure and an ester structure, and the cellulose derivative having the specific structure and an aliphatic polyester elastomer having a number average molecular weight of 10,000 or more. Can provide a molding material and a molded body excellent in impact resistance, molding processability, and impact resistance at low temperature as well as performance such as good rigidity, bending strength and heat resistance. As a result, the present invention has been completed.
That is, the said subject can be achieved by the following means.

[1]
The hydrogen atom of the hydroxyl group contained in cellulose
A cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below;
A molding material containing an aliphatic polyester elastomer having a number average molecular weight of 10,000 or more.
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 to 4 carbon atoms. )
[3]
[Claim 2] The molding material according to [2], wherein the group containing C) an alkyleneoxy group and an acyl group is a group containing a structure represented by the following general formula (3).

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

[10]
The molding material according to any one of [1] to [9], wherein the cellulose derivative is substantially free of carboxyl groups, sulfonic acid groups, and salts thereof.
[11]
The molding material according to any one of [1] to [10], wherein the cellulose derivative is insoluble in water.
[12]
Any of [1] to [11], wherein the aliphatic polyester elastomer is a polyester obtained by a condensation reaction of an aliphatic polyhydric alcohol and an aliphatic polybasic acid, or an aliphatic polyester obtained by ring-opening polymerization of a cyclic ester. A molding material according to claim 1.
[13]
The aliphatic polyhydric alcohol is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentane. And at least one selected from diol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol 1,4-cyclohexanedimethanol, and 1,4-benzenedimethanol, Group polybasic acids are succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 1,4-phenylenediacetic acid, phenyl Succinic acid, and these At least one aliphatic polybasic acid selected from anhydride, the molding material according to [12].
[14]
The molding material according to [12], wherein the cyclic ester is ε-caprolactone.
[15]
The molding material according to any one of [1] to [14], further comprising rubber particles.
[16]
The molding material according to [15], wherein the rubber particles have a core-shell structure.
[17]
The molding material according to [16], wherein the core of the rubber particles is an acrylic rubber or a silicone / acrylic composite rubber, and the shell component is a vinyl polymer.
[18]
The cellulose derivative, the rubber particles and the aliphatic polyester elastomer are contained in a total amount of 40 to 90% by mass, the rubber particles are contained in an amount of 5 to 50% by mass and the aliphatic polyester elastomer is contained in an amount of 5 to 50% by mass [15]. The molding material according to any one of to [17].
[19]
The molding material according to any one of [1] to [17], further comprising at least one of a cellulose ester resin and a cellulose ether resin.
[20]
20 to 80% by mass of cellulose derivative, 5 to 40% by mass of rubber particles, and 5 to 5% of aliphatic polyester elastomer with respect to the total amount of the cellulose derivative, rubber particles, aliphatic polyester elastomer, cellulose ester resin and cellulose ether resin. The molding material according to [19], containing 40% by mass and 5 to 50% by mass as a total amount of the cellulose ester resin and the cellulose ether resin.
[21]
The molding material according to any one of [1] to [20], further comprising a compatibilizing agent.
[22]
The molding material according to [21], wherein the compatibilizer is a carboxylic acid anhydride or a compound having at least one selected from the group consisting of an epoxy group, an isocyanate group, and an oxazoline group.
[23]
[1] A molded product obtained by thermoforming the molding material according to any one of [22].
[24]
[1] A method for producing a molded body, comprising a step of heating and molding the molding material according to any one of [22].
[25]
[23] A casing for an electric and electronic device comprising the molded article according to [23].

Since the molding material of the present invention has excellent thermoplasticity, it can be molded by heat molding or the like. Further, the molding material and the molded body of the present invention are excellent in performance such as rigidity, bending strength, and heat resistance, and have good impact resistance, molding processability, and impact resistance at low temperature, for example, It can be suitably used as components such as automobiles, home appliances, electrical and electronic equipment, machine parts, housing / building materials, and the like. Moreover, since the molding material of this invention uses the cellulose derivative obtained from the cellulose which is plant-derived resin, it can substitute for the conventional petroleum-derived resin as a raw material which can contribute to global warming prevention.

In the present invention, the hydrogen atom of the hydroxyl group contained in cellulose is
A cellulose derivative (hereinafter also referred to as “cellulose derivative”) comprising at least one group substituted with A) below and at least one group substituted with B) below;
The present invention relates to a molding material containing an aliphatic polyester elastomer having a number average molecular weight of 10,000 or more.
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) Substituted by an acyl group: —CO—R _B (R _B represents a hydrocarbon group).
More specifically, the cellulose derivative in the present invention has a repeating unit represented by the following general formula (A).

In the general formula (A), R ² , R ³ and R ⁶ are each independently a hydrogen atom, A) hydrocarbon group: —R _A , B) acyl group: —CO—R _B (R _B is carbon 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 because at least part of the hydroxyl group of the β-glucose ring is etherified and esterified with A) a hydrocarbon group and B) an acyl group. It can be expressed and is suitable for molding.
Furthermore, since cellulose is a completely plant-derived component, it is carbon neutral and can greatly reduce the burden on the environment.

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

The cellulose derivative only needs to contain 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) At least one of R ² , R ³ and R ⁶ of one repeating unit is substituted with A) a hydrocarbon group, and at least one of the other is substituted with B) an acyl group ( That is, a cellulose derivative composed of the same type of repeating units having the substituents A) and B) in one repeating unit.
(3) A cellulose derivative in which repeating units having different substitution positions and different types of substituents are bonded at random.
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 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. In the case where R _A is an aromatic group, the preferred 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 moldability 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) Acyl group: In —CO—R _B , R _B represents a hydrocarbon group. R _B is an aliphatic group, and may be any aromatic group.
If R _B is an aliphatic group, straight chain, branched, and may be any of circular, it may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
If R _B is an aromatic group may be either monocyclic and condensed. Examples of the aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
R _B is preferably an alkyl group or an aryl group. R _B is more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group, still more preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms (preferably a methyl group). Group, ethyl group, propyl group), and most preferably an alkyl group having 1 or 2 carbon atoms (that is, a methyl group or an ethyl group).
Also, R _B, it is also preferably a hydrocarbon group having a branched structure having 3 to 10 carbon atoms, more preferably an alkyl group having a branched structure having 3 to 10 carbon atoms, having 7-9 carbon atoms More preferably, it is an alkyl group having a branched structure.
The R _B, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, 3-heptyl, 2-ethylhexyl group, tert- butyl Group, isoheptyl group, and the like. Preferably, R _B is methyl, ethyl, propyl, a 3-heptyl group, or a 2-ethylhexyl group, more preferably a methyl group, an ethyl group, 3-heptyl, or 2-ethylhexyl group.

The cellulose derivative in the molding material of the present invention is a cellulose derivative in which the hydrogen atom of the hydroxyl group contained in cellulose contains at least one group substituted with A) and at least one group substituted with B). However, it is preferable from the viewpoint of impact resistance that it further contains at least one group in which the hydrogen atom of the hydroxyl group contained in cellulose is substituted by the following C).
C) a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 to 4 carbon atoms. )

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

In the alkyleneoxy group (—R _C2 —O—) contained in C), R _C2 represents an alkylene group having 2 to 4 carbon atoms. R _C2 may be linear, branched or cyclic, but is preferably linear or branched, and more preferably branched.
The alkyleneoxy group (—R _C2 —O—) is preferably an alkyleneoxy group having 2 or 3 carbon atoms. Specific examples of the alkyleneoxy group preferably include the following structures.

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

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

In the general formula (3), R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 to 4 carbon atoms. The preferred ranges of R _C1 and R _C2 are the same as those described above. n is an integer of 1 or more. The upper limit of n is not particularly limited, and varies depending on the amount of alkyleneoxy group introduced, but is about 10, for example. n is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1. When a plurality of R _C2 are present, they may be the same or different, but are preferably the same.
In addition, the cellulose derivative in the present invention is a group of C) containing only one alkyleneoxy group (a group in which n is 1 in the general formula (3)) and C) containing two or more alkyleneoxy groups. And a group (a group in which n is 2 or more in the above general formula (3)).

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

R _A in A), R B in _B ), R _C1 and R _C2 in C) may have a further substituent or may be unsubstituted, but are preferably unsubstituted.
_{R A} in the A), _{R B} in the B), in the case where the _{where R C1} and _{R C2} in the C) has a further substituent, examples of the further substituent include a halogen atom (e.g. fluorine atom, chlorine atom, bromine Atoms, iodine atoms), hydroxy groups, alkoxy groups (the alkyl group preferably has 1 to 5 carbon atoms), alkenyl groups, and the like. However, even when a substituent is included, R _C2 has 2 or 3 carbon atoms. Note that when R _A , R _B , and R _C1 are other than an alkyl group, they may have an alkyl group (preferably having a carbon number of 1 to 5) as a substituent.

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

In addition, the cellulose derivative in the present invention is preferably insoluble in water. Here, “being insoluble in water” means that the solubility in 100 parts by mass of water at 25 ° C. is 5 parts by mass or less.

Specific examples of the cellulose derivative in the present invention include acetyl methyl cellulose, acetyl ethyl cellulose, acetyl propyl cellulose, acetyl butyl cellulose, acetyl pentyl cellulose, acetyl hexyl cellulose, acetyl cyclohexyl cellulose, acetyl phenyl cellulose, acetyl naphthyl cellulose, propionyl methyl cellulose, and propionyl ethyl cellulose. , Propionylpropylcellulose, propionylbutylcellulose, propionylpentylcellulose, propionylhexylcellulose, propionylcyclohexylcellulose, propionylphenylcellulose, propionylnaphthylcellulose, butyrylmethylcellulose, butyrylethylcellulose, butyrylpropylcellulose , Butyrylbutylcellulose, butyrylpentylcellulose, butyrylhexylcellulose, butyrylcyclohexylcellulose, butyrylphenylcellulose, butyrylnaphthylcellulose, methylcellulose-2-ethylhexanoate, ethylcellulose-2-ethylhexanoate, propylcellulose -2-ethylhexanoate, butylcellulose-2-ethylhexanoate, pentylcellulose-2-ethylhexanoate, hexylcellulose-2-ethylhexanoate, cyclohexylcellulose-2-ethylhexanoate, phenylcellulose -2-ethylhexanoate, naphthylcellulose-2-ethylhexanoate, acetoxyethylmethylacetylcellulose, acetoxyethylethylacetyl cell Acetoxyethylpropylacetylcellulose, acetoxyethylbutylacetylcellulose, acetoxyethylpentylacetylcellulose, acetoxyethylhexylacetylcellulose, acetoxyethylcyclohexylacetylcellulose, acetoxyethylphenylacetylcellulose, acetoxyethylnaphthylacetylcellulose, acetoxyethylmethylpropionylcellulose, Acetoxyethyl ethyl propionyl cellulose, Acetoxy ethyl propyl propionyl cellulose, Acetoxy ethyl butyl propionyl cellulose, Acetoxy ethyl pentyl propionyl cellulose, Acetoxy ethyl hexyl propionyl cellulose, Acetoxy ethyl cyclohexyl propionyl cellulose, Acetoxy Tylphenylpropionylcellulose, acetoxyethylnaphthylpropionylcellulose, acetoxyethylmethylcellulose-2-ethylhexanoate, acetoxyethylethylcellulose-2-ethylhexanoate, acetoxyethylpropylcellulose-2-ethylhexanoate, acetoxyethylbutylcellulose 2-ethylhexanoate, acetoxyethylpentylcellulose-2-ethylhexanoate, acetoxyethylhexylcellulose-2-ethylhexanoate, acetoxyethylcyclohexylcellulose-2-ethylhexanoate, acetoxyethylphenylcellulose-2-ethyl Hexanoate, acetoxyethyl naphthylcellulose-2-ethylhexanoate, propionyloxyethyl Acetylacetylcellulose, propionyloxyethylethylacetylcellulose, propionyloxyethylpropylacetylcellulose, propionyloxyethylbutylacetylcellulose, propionyloxyethylpentylacetylcellulose, propionyloxyethylhexylacetylcellulose, propionyloxyethylcyclohexylacetylcellulose, propionyloxyethylphenylacetyl Cellulose, propionyloxyethyl naphthylacetyl cellulose, propionyloxyethylmethylpropionylcellulose, propionyloxyethylethylpropionylcellulose, propionyloxyethylpropylpropionylcellulose, propionyloxyethylbutylpropionylcellulose, pro Onyloxyethylpentylpropionylcellulose, propionyloxyethylhexylpropionylcellulose, propionyloxyethylcyclohexylpropionylcellulose, propionyloxyethylphenylpropionylcellulose, propionyloxyethylnaphthylpropionylcellulose, propionyloxyethylmethylcellulose-2-ethylhexanoate, propionyloxyethyl Ethylcellulose-2-ethylhexanoate, propionyloxyethylpropylcellulose-2-ethylhexanoate, propionyloxyethylbutylcellulose-2-ethylhexanoate, propionyloxyethylpentylcellulose-2-ethylhexanoate, propionyloxy Ethyl hexyl cellulose -2-ethylhexanoate, propionyloxyethylcyclohexyl cellulose-2-ethylhexanoate, propionyloxyethylphenylcellulose-2-ethylhexanoate, propionyloxyethylnaphthylcellulose-2-ethylhexanoate, acetoxypropylmethyl Acetylcellulose, acetoxypropylethylacetylcellulose, acetoxypropylpropylacetylcellulose, acetoxypropylbutylacetylcellulose, acetoxypropylpentylacetylcellulose, acetoxypropylhexylacetylcellulose, acetoxypropylcyclohexylacetylcellulose, acetoxypropylphenylacetylcellulose, acetoxypropylnaphthylacetylcellulose , Propio Luoxypropylmethylacetylcellulose, propionyloxypropylethylacetylcellulose, propionyloxypropylpropylacetylcellulose, propionyloxypropylbutylacetylcellulose, propionyloxypropylpentylacetylcellulose, propionyloxypropylhexylacetylcellulose, propionyloxypropylcyclohexylacetylcellulose, propionyl Examples thereof include oxypropylphenylacetylcellulose, propionyloxypropylnaphthylacetylcellulose, valeroxypropylmethylvaleroylcellulose, valeroxybutylmethylvaleroylcellulose, and the like.

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

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

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

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

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 still more preferably 0 <MS <1.0. When MS is 1.5 or less (MS ≦ 1.5), heat resistance, moldability and the like can be improved, and a cellulose derivative suitable for a molding material can be obtained.

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

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

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

A preferred embodiment of a method for producing a cellulose derivative having the above A) hydrocarbon group: —R _A and B) acyl group: —CO—R _B (R _B represents a hydrocarbon group) includes cellulose ether, base It includes a step of esterification by reacting acid chloride or acid anhydride in the presence.
As the cellulose ether, for example, those in which at least a part of the hydrogen atoms of the hydroxyl groups at the 2nd, 3rd and 6th positions of the β-glucose ring contained in cellulose are substituted with hydrocarbon groups can be used. Specific examples include methyl cellulose, ethyl cellulose, propyl cellulose, 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 to 4 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 thereof include dimethyloctanoyl chloride, 2,3-dimethyloctanoyl chloride, 3,3-dimethyloctanoyl chloride, 2-ethyloctanoyl chloride, 2-propylheptanoyl chloride, 2-butylhexanoyl chloride and the like.

As the acid anhydride, for example, carboxylic acid anhydrides corresponding to the acyl group contained in the above B) acyl group and C) can be used. Examples of such carboxylic anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, 2-ethylhexanoic acid. An anhydride, nonanoic acid anhydride, etc. are mentioned.
As described above, since the cellulose derivative in the present invention preferably 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 manufacturing conditions can follow the usual method. For example, the method described in “Encyclopedia of Cellulose” pages 131 to 164 (Asakura Shoten, 2000) can be referred to.

3. Aliphatic polyester elastomer having a number average molecular weight of 10,000 or more The molding material of the present invention contains an aliphatic polyester elastomer having a number average molecular weight of 10,000 or more (hereinafter also referred to as “aliphatic polyester elastomer”).
Aliphatic polyester elastomers have the properties of low glass transition temperature, softness and high ductility, so when mixed with the specific cellulose derivative in the present invention to form a molding material, when a specific cellulose derivative is used alone In addition, impact resistance at low temperatures (about −50 ° C. to 0 ° C.) can be improved. Furthermore, since the specific cellulose derivative in the present invention includes an ether structure and an ester structure, it has an ether bond having a higher degree of freedom around the main chain than a conventional cellulose ester and the like. Excellent affinity. Therefore, the aliphatic polyester elastomer is excellent in dispersibility with respect to the specific cellulose derivative in the present invention, and both are mixed well, so that the impact resistance and moldability are higher than when the specific cellulose derivative is used alone. Further improvement. Moreover, it is excellent also in performance, such as rigidity, bending strength, and heat resistance.

The aliphatic polyester elastomer referred to in the present invention is not particularly limited as long as it is an aliphatic polyester elastomer having a number average molecular weight of 10,000 or more.
The aliphatic polyester elastomer in the present invention is preferably a polyester obtained by a condensation reaction of an aliphatic polyhydric alcohol and an aliphatic polybasic acid, or an aliphatic polyester obtained by ring-opening polymerization of a cyclic ester.

More preferred is an aliphatic polyester obtained by a condensation reaction of an aliphatic polyhydric alcohol and an aliphatic polybasic acid, such as polyethylene adipate, polyethylene succinate, polybutylene adipate, polybutylene succinate, polybutylene succinate adipate. Etc. Polybutylene succinate is preferable.

Examples of the aliphatic polybasic acid used in the condensation reaction of an aliphatic polyhydric alcohol and an aliphatic polybasic acid (or an ester thereof) include succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, octadecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid undecanedioic acid, dodecanedioic acid, and their anhydrides, or esters thereof are listed. Examples of the alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, 1,3-propanediol, 1,4-butanediol, 1,9 -Nonanji Lumpur, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexane dimethanol, polytetramethylene glycol 1,4-cyclohexane dimethanol, and the like are exemplified. Moreover, it is also possible to use polyoxyalkylene glycol as a part of the aliphatic polyhydric alcohol, and examples thereof include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and copolymers thereof. .
The aliphatic polyester elastomer may be used alone or in combination of two or more. In addition, when optical isomers exist in these, any of D-form, L-form, and racemate may be used, and the form may be any of solid, liquid, or aqueous solution.
Among these, the aliphatic polyhydric alcohol is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl- At least one selected from 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol and 1,4-cyclohexanedimethanol, the aliphatic polybasic At least one fat selected from succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and anhydrides thereof Be a polybasic acid Masui.

The aliphatic polyhydric alcohol is at least one selected from diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and the aliphatic More preferably, the polybasic acid is at least one aliphatic polybasic acid selected from succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, and anhydrides thereof.

In the production of the aliphatic polyester elastomer, the total amount of the aliphatic polybasic acid (or its ester) component and the aliphatic polyhydric alcohol component may be initially mixed and reacted, or added in portions as the reaction proceeds. It doesn't matter. The polycondensation reaction can be carried out by a common transesterification method or esterification method, or a combination of both. If necessary, the degree of polymerization can be increased by increasing or decreasing the pressure in the reaction vessel.

Examples of the cyclic ester used in the method for ring-opening polymerization of a cyclic ester include β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, and ε-caprolactone. Of these, ε-caprolactone is particularly preferred. The ring-opening polymerization can be carried out by a method such as polymerization in a solvent or bulk polymerization using a known ring-opening polymerization catalyst.

For the condensation reaction and the polymerization reaction, a vertical reactor, a batch reactor, a horizontal reactor, a twin screw extruder or the like is used, and the reaction is preferably carried out in bulk or in solution.

Lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead as esterification catalysts, ring-opening polymerization catalysts, and deglycolization catalysts in condensation reactions and polymerization reactions Metals such as antimony, cadmium, manganese, iron, zirconium, vanadium, iridium, lanthanum, selenium, and organic metal compounds thereof, salts of organic acids, metal alkoxides, metal oxides, etc. It can also be used in combination with a promoter such as an acid. These catalysts can be used singly or in combination of two or more, and the addition amount is preferably 0.1 mol or less, more preferably 0.8 mol or less, still more preferably with respect to 100 mol of all dicarboxylic acids. Is 0.6 mol or less.

Further, if necessary, the molecular weight can be increased using a chain extender. Examples of the chain extender include bifunctional or higher functional isocyanate compounds, epoxy compounds, aziridine compounds, oxazoline compounds, polyvalent metal compounds, polyfunctional acid anhydrides, phosphate esters, phosphites, and the like. Or you may combine 2 or more types.

The elastic modulus of the aliphatic polyester elastomer in the present invention is preferably 0.01 GPa or more and 1 GPa or less, and more preferably 0.1 GPa or more and 0.5 GPa or less.

The aliphatic polyester elastomer in the present invention has a number average molecular weight of 10,000 or more. Here, the number average molecular weight is a number average molecular weight measured by gel permeation chromatography (GPC). More specifically, N-methylpyrrolidone is used as a solvent, a polystyrene gel is used, and the molecular weight is obtained using a conversion molecular weight calibration curve obtained in advance from a standard monodisperse polystyrene constituent curve. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) can be used.
When the number average molecular weight is less than 10,000, the aliphatic polyester elastomer is not preferable because it bleeds out and acts as a plasticizer for the resin to be mixed, thereby significantly impairing the rigidity and heat resistance of the resin.
The number average molecular weight of the aliphatic polyester elastomer is preferably 10,000 to 500,000, more preferably 15,000 to 300,000, and still more preferably 20,000 to 200,000.
As the aliphatic polyester elastomer in the present invention, a commercially available product may be used. As polybutylene succinate, Bionore # 1001 (Mn = 70000) (manufactured by Showa Polymer Co., Ltd.), GSPla AD92W (Mn = 40000) (Mitsubishi) Chemical Co., Ltd.), Bionole # 3001 (Mn = 34000) (manufactured by Showa Polymer Co., Ltd.) as polybutylene succinate adipate, PH7 (Mn = 45000) as polycaprolactone (manufactured by Daicel Corporation) ) And the like.

When the molding material of the present invention further contains rubber particles, the falling ball impact strength becomes better and the molding material becomes more excellent.
The rubber particles may be composed of a polymer component and have rubber elasticity. Examples of rubber components include styrene butadiene rubber, acrylonitrile butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, ethylene propylene rubber, ethylene propylene diene copolymer rubber (DPDM), ethylene butene rubber, ethylene octene rubber, butyl rubber, and acrylic rubber. And chemically synthesized synthetic rubbers such as silicone rubber and chlorinated polyethylene. As will be described in detail later, these may be used alone or in combination of two or more.

By mixing the rubber particles with the specific cellulose derivative in the present invention, the specific cellulose derivative was used alone without reducing the material performance such as flexural modulus, bending strength, heat distortion temperature, and moldability as much as possible. As compared with the case, the impact resistance and the impact resistance after staying can be improved without significantly reducing the rigidity. This is derived from the remarkable elasticity of the rubber particles.
Further, since the rubber particles are in the form of particles, they are physically and uniformly diffused when mixed with the specific cellulose derivative in the present invention, so that even when the specific cellulose derivative is used alone, Performances such as flexural modulus, strength, heat distortion temperature, and moldability are not significantly reduced.

The shape of the rubber particles in the present invention is not particularly limited, but is preferably substantially spherical. The reason why the spherical shape is preferable is, for example, when rubber particles are mixed with a cellulose derivative in the production of a molding material, the dispersibility of the rubber particles is good and the impact resistance is easily improved, and the shape is not spherical. This is because the melt viscosity of the obtained resin composition is greatly increased in an indefinite shape, and the fluidity at the time of molding may be lowered. Here, the spherical shape is not limited to a single particle of rubber, and there is no problem at all even if the single or plural rubbers are aggregated or include other polymers.

Here, the spherical shape means that the maximum diameter and the minimum diameter are measured for each of 50 arbitrary particles with a transmission electron microscope (TEM), and the average of the 50 ratios (maximum diameter / minimum diameter) is 1 to 1. It can be in the range of 2. The average of this ratio is preferably 1 to 1.5, more preferably 1 to 1.3, and still more preferably 1 to 1.1.

The particle size of the rubber particles in the present invention is not particularly limited, but those having an average particle size of generally 10 to 1000 nm, preferably 30 to 500 nm, particularly preferably 40 to 350 nm are those having dispersibility in cellulose derivatives. From the viewpoint of improving impact resistance and rigidity.
Here, the measurement method of the particle size of the rubber particles is to measure the average particle size of the rubber-like polymer latex using a submicron particle size distribution analyzer CHDF-2000 manufactured by MATEC APPLIED SCIENCES or by TEM of the molding material. This can be done by cross-sectional observation.

The structure of the rubber particles in the present invention may be a structure formed of a single layer or a multiphase structure including a phase of a rubber elastic body. Examples of the rubber particles having a single phase structure include crosslinked rubber particles and composite rubber particles, and examples of the rubber particles having a multilayer structure include core-shell rubber particles.

The rubber particles are preferably cross-linked from the viewpoint of the development of impact resistance due to rubber elasticity and the excellent creep characteristics of the material. As such crosslinked rubber particles, for example, particles obtained by copolymerizing a single or plural unsaturated compounds and a crosslinkable monomer can be used.
Examples of unsaturated compounds include aliphatic olefins such as ethylene and propylene, aromatic vinyl compounds such as styrene and methylstyrene, conjugated diene compounds such as butadiene, dimethylbutadiene, isoprene, and chloroprene, methyl acrylate, propyl acrylate, and acrylic acid. Unsaturated carboxylic acid esters such as butyl, methyl methacrylate, propyl methacrylate and butyl methacrylate, vinyl cyanide such as acrylonitrile, and the like can be used.

Further, as the unsaturated compound, for example, an epoxy resin such as a carboxyl group, an epoxy group, a hydroxyl group, an amino group, an amide group, or a compound having a functional group reactive with a curing agent can be used. As examples, acrylic acid, glycidyl methacrylate, vinylphenol, vinylaniline, acrylamide and the like can be used.

Examples of crosslinkable monomers include compounds having a plurality of polymerizable double bonds in the molecule such as divinylbenzene, diallyl phthalate, ethylene glycol dimethacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate. Can do.

These particles can be produced by various conventionally known polymerization methods such as an emulsion polymerization method and a suspension polymerization method. Typical emulsion polymerization methods include unsaturated compounds and crosslinkable monomers such as radical polymerization initiators such as cumene hydroperoxide and peroxides such as tert-butyl hydroperoxide, tert-dodecyl mercaptan, n-octyl mercaptan and the like. Molecular weight regulators such as mercaptans and halogenated hydrocarbons, reducing agents such as dextrose and Rongalite, chelating agents such as sodium pyrophosphate and EDTA (ethylenediaminetetraacetic acid) and 2Na, metal catalysts such as iron and copper, and various known types The emulsion polymerization is carried out in the presence of the emulsifier, and after reaching a predetermined polymerization conversion rate, a polymerization stopper is added to stop the polymerization reaction, and then the unreacted monomer in the polymerization system is removed by steam distillation or the like. This is a method for obtaining a latex of a copolymer. Water is removed from the latex obtained by the emulsion polymerization method to obtain crosslinked rubber particles. Commercial products can also be used.

The rubber particles may be composite rubber particles in which two or more kinds of rubber components coexist. Examples of such composite rubber particles include composite rubber using two or more kinds of diene rubber, acrylic rubber, silicone rubber, polyolefin rubber, etc., preferably diene / acrylic composite rubber, silicone. / Acrylic composite rubber, particularly preferably silicone / acrylic composite rubber. The silicone / acrylic composite rubber has a structure in which polyorganosiloxane and polyalkyl (meth) acrylate are intertwined so that they cannot be separated from each other.

The polyorganosiloxane constituting the silicone / acrylic composite rubber is a polymer containing dimethylsiloxane units as constituent units. Examples of the dimethylsiloxane constituting the polyorganosiloxane include a dimethylsiloxane-based cyclic body having a 3-membered ring or more, and a 3- to 7-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These may be used alone or in combination of two or more. Among these, the main component is preferably octamethylcyclotetrasiloxane because the particle size distribution can be easily controlled.
Although there is no restriction | limiting in particular as polyorganosiloxane, Polyorganosiloxane which has a vinyl polymerizable functional group is preferable. Such a vinyl polymerizable functional group-containing siloxane is not limited as long as it contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond, but the reactivity with dimethylsiloxane is not limited. In consideration, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable.

Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and ∂-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane and γ-mercaptopropyl Examples include mercaptosiloxane such as dimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. These vinyl polymerizable functional group-containing siloxanes can be used alone or in combination of two or more.

In order to produce a polyorganosiloxane, first, a siloxane-based crosslinking agent is added to a siloxane mixture comprising dimethylsiloxane and a siloxane having a vinyl polymerizable functional group, if necessary, and then emulsified with an emulsifier and water. A siloxane mixture latex is obtained. Next, the siloxane mixture latex is made into fine particles by using a homomixer that makes fine particles by a shearing force generated by high-speed rotation, a homogenizer that makes fine particles by jetting power from a high-pressure generator, or the like. Here, it is preferable to use a high-pressure emulsifier such as a homogenizer because the particle size distribution of the polyorganosiloxane latex becomes small.
Next, the finely divided siloxane mixture latex is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. Then, the reaction solution is cooled and further neutralized with an alkaline substance such as caustic soda, caustic potash or sodium carbonate to stop the polymerization, thereby obtaining a polyorganosiloxane.

In the production of the polyorganosiloxane, the emulsifier is preferably an anionic emulsifier. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. Among these, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are particularly preferable. These emulsifiers are generally used in a range of about 0.05 to 5 parts by mass with respect to 100 parts by mass of the siloxane mixture.
Examples of the acid catalyst used for polyorganosiloxane polymerization include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts are used alone or in combination of two or more. Of these, aliphatic substituted benzene sulfonic acid is preferable and n-dodecyl benzene sulfonic acid is particularly preferable because of its excellent stabilizing effect of polyorganosiloxane latex.

The polyorganosiloxane preferably has an average particle diameter of less than 100 nm because the pigment colorability of the resulting molding material is excellent. Further, it is more preferably less than 90 nm, particularly preferably less than 80 nm. On the other hand, the lower limit of the average particle diameter is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, because it can prevent an increase in latex viscosity and coagulum (coagulum) generation during production.
As a method for controlling the particle diameter of the polyorganosiloxane, for example, a method described in JP-A-5-279434 can be employed.

The polyalkyl (meth) acrylate constituting the silicone / acrylic composite rubber is a polymer containing an alkyl (meth) acrylate unit and a polyfunctional alkyl (meth) acrylate unit as constituent components.

Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Methacrylate is mentioned, and n-butyl acrylate is particularly preferred. These alkyl (meth) acrylates can be used alone or in combination of two or more.

Examples of multiphase rubber particles include core-shell structured particles and salami structured particles. In the present invention, rubber particles having a core-shell structure are preferable from the viewpoints of impact resistance, impact resistance after residence, and rigidity.

The core-shell rubber particles are spherical polymer particles consisting of a polymer whose center and surface layers are different, and are simply composed of a two-phase structure of a core phase and a single shell phase, or, for example, soft core, hard shell, soft There are known multi-core shell rubber particles having a multi-phase multi-layer structure having a plurality of shell phases such as a shell and a hard shell. Here, “soft” means a rubber phase (having a glass transition temperature Tg of room temperature or lower), and “hard” means a resin phase that is not rubber (having a glass transition temperature Tg exceeding room temperature). .

As the rubber component forming the core of the core-shell rubber particles having a soft core / hard shell structure, the above-described crosslinked rubber particles and composite rubber particles can be used. The rubber component of the core-shell rubber particles in the present invention is preferably a diene rubber, an acrylic rubber, or a silicone / acrylic composite rubber because the resulting resin composition is excellent in impact resistance and impact resistance after residence. Acrylic rubber and silicone / acrylic composite rubber are particularly preferred.

Shell components include polymers having a glass transition temperature of room temperature or higher, for example, homopolymers such as polystyrene, acrylonitrile, methyl acrylate, methyl methacrylate, acrylonitrile / styrene, methyl methacrylate / styrene, methyl methacrylate / alkyl acrylate ester A copolymer such as methacrylic acid / acrylic acid or a polymer such as styrene / acrylonitrile / methyl methacrylate is used, and an acrylonitrile / styrene copolymer is particularly preferable. Acrylic acid, methacrylic acid, itaconic acid, glycidyl methacrylic acid, hydroxyethyl methacrylic acid, dimethylaminomethyl having functional groups reactive with epoxy resins such as carboxyl groups, epoxy groups, hydroxyl groups and amino groups, amide groups, or curing agents It is also possible to copolymerize unsaturated compounds such as methacrylic acid and methacrylamide.
As the shell component, the vinyl polymer as described above is preferable.

In the core-shell rubber particles, the core component content is preferably 10 to 95% by mass and the shell component content is preferably in the range of 90 to 5% by mass. If the content of the core component is 10% by mass or more, a sufficient impact resistance improvement effect can be obtained, and if it is 95% by mass or less, the core can be sufficiently covered with the shell, and the dispersibility into the cellulose derivative can be improved. It is preferable because it is excellent.

The core-shell rubber particles can be produced by a known method, for example, a method disclosed in US Pat. No. 4,419,496, European Patent 45,357, Japanese Patent Laid-Open No. 55-94917. Commercial products can also be used. Examples of commercially available core-shell rubber particles having a soft core / hard shell structure include “Paraloid (trademark) EXL-2655” (manufactured by Kureha Chemical Industry Co., Ltd.), -323A "(manufactured by Mitsubishi Rayon Co., Ltd.)," Staffyroid (trademark) AC-3355, TR-2122 "(manufactured by Takeda Pharmaceutical Company Limited) consisting of an acrylic ester / methacrylic ester copolymer, butyl acrylate / methacrylic acid "PARALOID (trademark) EXL-2611, EXL-3387" (Rohm & Haas), "Metablene W529" (Mitsubishi Rayon) made of methyl copolymer, "Silane / acrylic composite rubber / vinyl copolymer" METABLEN S2001, S2006, S2100, 2030, SX005, SX006, SRK200 "or the like can be used (manufactured by Mitsubishi Rayon Co., Ltd.). Among these, rubber particles in which the core is an acrylic rubber or silicone / acrylic composite rubber and the shell component is a vinyl polymer are preferable. For example, “Methbrene W529” (manufactured by Mitsubishi Rayon Co., Ltd.) Polymers obtained by grafting methyl), “Metablene S2001, S2006, S2100, S2030, SX005, SX006, SRK200” (polymer obtained by grafting methyl methacrylate on a silicone / acrylic composite rubber), etc. .

The molding material of the present invention comprises 40 to 90% by mass of cellulose derivative, 5 to 50% by mass of rubber particles, and 5 of aliphatic polyester elastomer with respect to 100 parts by mass in total of the cellulose derivative, rubber particles and aliphatic polyester elastomer. The cellulose derivative is preferably 50 to 85% by mass, more preferably 50 to 85% by mass of the cellulose derivative, 10 to 40% by mass of the rubber particles, and 5 to 40% by mass of the aliphatic polyester elastomer. More preferably, the cellulose derivative is 60 to 80% by mass, the rubber particles are 10 to 30% by mass, and the aliphatic polyester elastomer is 5 to 35% by mass. Most preferably, the cellulose derivative is 65 to 75% by mass, and the rubber particles are 15%. -25% by mass, aliphatic polyester elastomer 5-30% by mass.

By making cellulose derivatives, rubber particles, and aliphatic polyester elastomers within this range, the rigidity, bending strength, impact resistance, moldability, Charpy impact strength before and after residence, etc. are moderately improved. The Vicat softening point temperature is improved and the balance of physical properties as a molding material is improved.

The molding material of the present invention may further contain at least one of a cellulose ester resin and a cellulose ether resin in addition to the cellulose derivative. That is, both cellulose ester resin and cellulose ether resin may be included. The cellulose derivative is a cellulose ether ester and has a structure different from that of the cellulose ester resin and the cellulose ether resin.

The cellulose ester resin and the cellulose ether resin in the present invention are not particularly limited. Cellulose ester resins are usually produced by esterifying or etherifying cellulose such as wood pulp (conifer pulp, hardwood pulp) and cotton linter pulp.
Since the cellulose ester resin has a glucopyranose ring as a main chain skeleton and has a highly polar and bulky ester group as a side chain, it can be mixed with a specific cellulose derivative in the present invention. The impact resistance and repeated impact characteristics can be improved as compared with the case where the derivative is used alone. Furthermore, since the specific cellulose derivative and cellulose ester resin in the present invention have the same main chain structure, the affinity is high and the dispersibility is excellent. Therefore, it is excellent also in performance, such as rigidity, bending strength, heat resistance, and moldability.

The cellulose ester resin can be produced by a conventional esterification method in which cellulose is reacted with an acylating agent, and can be produced through a saponification or aging step as necessary. Cellulose ester resins are usually prepared by activating pulp (cellulose) with an activating agent (activation step), and then preparing an ester (such as a triester) with an acylating agent using a catalyst such as sulfuric acid (acylation) Step), and the degree of esterification can be adjusted by saponification (hydrolysis) / aging (saponification / aging process). In the case of cellulose acetate, it can be produced by a conventional method such as a sulfuric acid catalyst method, an acetic acid method, or a methylene chloride method.

The ratio of the acylating agent in the acylation step can be selected within a range that provides a desired degree of acylation (eg, degree of acetylation). For example, 230 to 300 parts by mass, preferably 240 parts per 100 parts by mass of pulp (cellulose). The amount is about 290 parts by mass, more preferably about 250-280 parts by mass. In the case of cellulose acetate, for example, acetic anhydride can be used as the acylating agent.
As the acylation or aging catalyst, sulfuric acid is usually used. The amount of sulfuric acid used is usually about 0.5 to 15 parts by mass, preferably about 5 to 15 parts by mass, and more preferably about 5 to 10 parts by mass with respect to 100 parts by mass of cellulose. The saponification / ripening temperature can be selected from the range of 40 to 160 ° C., for example, about 50 to 70 ° C.

Furthermore, in order to neutralize the remaining sulfuric acid, it may be treated with an alkali.
Examples of the cellulose ester resin include organic acid esters [cellulose C2-6 carboxylic acid esters such as cellulose acetate (cellulose acetate), cellulose propionate, cellulose butyrate, etc.], mixed esters (cellulose acetate propionate, cellulose acetate, etc.). Cellulose di-C2-6 carboxylates such as butyrate), grafts (polycaprolactone grafted cellulose acetate, etc.), inorganic acid esters (cellulose nitrate, cellulose sulfate, cellulose phosphate, etc.), mixed organic and inorganic acids Examples include esters (such as cellulose nitrate acetate).

In the present invention, among these cellulose ester resins, a cellulose organic acid ester modified with an organic acid is preferable, and a cellulose organic acid ester modified with an organic acid having 2 to 12 carbon atoms is more preferable. Specifically, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose butyrate, cellulose acetate butyrate, cellulose propionate butyrate and the like are preferable, and cellulose diacetate and cellulose acetate propionate are preferable. Nate and cellulose acetate butyrate are more preferable.

The average substitution degree of the acyl group of the cellulose ester resin is generally 1 to 3, preferably 1.5 to 3 (eg 1.7 to 3), more preferably 1.8 to 3 (eg 2 to 3). ) In the case of cellulose acetate, it can generally be selected from a range of an average degree of acetylation of about 30 to 62.5%, and usually an average degree of acetylation of 43.7 to 62.5% (average degree of substitution of acetyl groups 1.7 to 3), preferably 45 to 62.5% (average substitution degree 1.8 to 3), more preferably 48 to 62.5% (average substitution degree 2 to 3).
As the cellulose ether resin, for example, a cellulose ether resin in which a hydroxyl group contained in cellulose is substituted with a hydrocarbon group (which may be substituted with another group) can be used. Specific examples include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, allyl cellulose, benzyl cellulose and the like.

In the present invention, among these cellulose ether resins, methyl cellulose, ethyl cellulose, propyl cellulose and the like are preferable, and ethyl cellulose is more preferable. Examples of the cellulose ether resin include Etocel 100 (manufactured by Dow Chemical Company).
The average degree of substitution of the ether groups of the cellulose ether resin is generally 1 to 3, preferably 1.7 to 3, and more preferably about 2.0 to 3.
The polymerization degree of the cellulose ester resin and the cellulose ether resin is not particularly limited, and the viscosity average polymerization degree is, for example, about 200 to 400, preferably about 250 to 400, and more preferably about 270 to 350.

When the cellulose ester resin or cellulose ether resin is contained, the molding material of the present invention contains 20 to 80 mass of cellulose derivative with respect to the total amount of the cellulose derivative, rubber particles, aliphatic polyester elastomer, cellulose ester resin and cellulose ether resin. %, Rubber particles are contained in an amount of 5 to 40% by mass, aliphatic polyester elastomer is contained in an amount of 5 to 40% by mass, and the total amount of cellulose ester resin and cellulose ether resin is preferably contained in an amount of 5 to 50% by mass. More preferably, the rubber particles are 10% to 35% by weight, the aliphatic polyester elastomer is 5% to 30% by weight, and the total amount of the cellulose ester resin and the cellulose ether resin is 10% to 45% by weight. More preferably, the cellulose derivative is 20 to 60% by mass, the rubber particles are 10 to 30% by mass, the aliphatic polyester elastomer is 5 to 20% by mass, and the total amount of the cellulose ester resin and the cellulose ether resin is 15 to 40% by mass. Most preferably, the cellulose derivative is 30 to 50% by mass, the rubber particles are 15 to 25% by mass, the aliphatic polyester elastomer is 5 to 15% by mass, and the total amount of the cellulose ester resin and the cellulose ether resin is 20 to 40% by mass. is there.

Falling ball impact strength while exhibiting high flexural modulus and high Vicat softening point temperature by making at least one of cellulose derivatives, aliphatic polyester elastomers, rubber particles, cellulose ester resins and cellulose ether resins within this range. Can be improved.

4). Compatibilizer The molding material of the present invention preferably further contains a compatibilizer. As a result, the aliphatic polyester elastomer further improves dispersibility with respect to the cellulose derivative in the present invention. Therefore, compared to the case where a specific cellulose derivative is used alone, the aliphatic polyester elastomer has performance such as rigidity, bending strength, and heat resistance. Excellent.

The compatibilizing agent in the present invention may be a low molecular compound or a high molecular compound, but has reactivity with chain extension such as an epoxy group, a carbodiimide group, an isocyanate group, an oxazoline group, and an acid anhydride group. A polymer having a carboxylic acid anhydride group, an epoxy group, an isocyanate group, or an oxazoline group is particularly preferable.
Examples of such carboxylic acid anhydrides, epoxy group-containing compounds, isocyanate compounds, and oxazoline compounds include the following.

In the present invention, the compatibilizing agent preferably has a reactive group, and more preferably a carboxylic acid anhydride or a compound having at least one selected from an epoxy group, an isocyanate group, and an oxazoline group.
Preferred compatibilizers include polymers modified with carboxylic acid anhydrides, epoxy groups, isocyanate groups, and oxazoline groups, block copolymers, graft polymers, random copolymers, and various nonionic surfactants. Agents, coupling agents, and crosslinking agents.
The compatibilizing agent is not particularly limited as long as it satisfies the above conditions, and specifically, Nippon Oil & Fats Modiper Series, Sumitomo Chemical Co., Ltd., Bond First, Bondine Series, Nippon Oil Commercially available such as Lexpearl series manufactured by Co., Ltd., Reseda series manufactured by Toagosei Co., Ltd., Alfon series, Epocross series manufactured by Nippon Shokubai Co., Ltd., Duranate series manufactured by Asahi Kasei Chemicals Co., Ltd. The product is preferably used. In addition, the compatibilizer is not limited to these, and the compatibilizer described in “Plastic compatibilizer development / evaluation / recycling” (CMC Publishing Co., Ltd.) can also be suitably used.

5. Molding material and molded body The content ratio of the components contained in the molding material of the present invention is not particularly limited.
The content ratio of the cellulose derivative contained in the molding material of the present invention is not particularly limited. Preferably, the cellulose derivative is contained in an amount of 20% by mass or more, more preferably 35% by mass or more, further preferably 45% by mass or more and 99% by mass, and particularly preferably 60% by mass or more and 95% by mass with respect to the total solid content.
The content ratio of the aliphatic polyester elastomer contained in the molding material of the present invention is not particularly limited. Preferably, the aliphatic polyester elastomer is contained in an amount of 1 to 80% by mass, more preferably 1 to 65% by mass, and further preferably 5 to 50% by mass with respect to the total solid content.
Also, from the standpoint of impact resistance (room temperature / low temperature), molding processability, and heat resistance, the mass composition ratio of the cellulose derivative and the aliphatic polyester elastomer (cellulose derivative / aliphatic polyester elastomer) is 20/80 to 95. / 5 is preferable, 40/60 to 90/10 is more preferable, and 60/40 to 90/10 is still more preferable.

When the molding material of the present invention contains a compatibilizing agent, the content is not limited, but is preferably 0.1 to 30% by mass with respect to 100 parts by mass in total of the cellulose derivative and the aliphatic polyester elastomer, Preferably, the content is 0.5 to 20% by mass. By setting it within this range, a sufficient compatibility improvement effect can be obtained, and problems such as an increase in the viscosity of the molding material are unlikely to occur.

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

When the molding material of the present invention contains an antioxidant, its content is not limited, but it is usually 30% by mass or less, preferably 0.01 to 10% by mass in the molding material. By setting it within this range, the resin can obtain a sufficient stability improving effect against heating in the kneading or molding process, which is preferable.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like, and phenol-based antioxidants are preferable. As the phenolic antioxidant, Irganox 1010, Irganox 1076, Irganox 3114 manufactured by Ciba Specialty Chemicals Co., Ltd. can be suitably used.

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

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

When the molding material contains a filler, the content is not limited, but is usually 30 parts by mass or less, preferably 5 to 10 parts by mass with respect to a total of 100 parts by mass of the cellulose derivative and the aliphatic polyester elastomer. Good.

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

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

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

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

In addition, polyphosphates composed of salts of phosphoric acid, polyphosphoric acid and metals of Groups 1 to 14 of the periodic table, ammonia, aliphatic amines, and aromatic amines can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts and triazines.

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

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

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

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

When the molding material of the present invention contains a flame retardant, the content thereof 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 in total of the cellulose derivative and the aliphatic polyester elastomer. Part. By setting it as this range, a sufficient flame retardancy improving effect can be obtained, and the occurrence of pellet blocking can be suppressed.

The molding material of the present invention may contain other components other than those described above for the purpose of further improving various properties such as moldability and flame retardancy within the range not impairing the object of the present invention. .
Examples of other components include polymers other than the cellulose derivatives and the aliphatic polyester elastomers, plasticizers, stabilizers (ultraviolet absorbers, etc.), mold release agents (fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, fats) Partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone), antistatic agent, flame retardant aid Agents, processing aids, anti-drip agents, antibacterial agents, antifungal agents and the like. Further, a coloring agent containing a dye or a pigment can be added.

As the polymer other than the cellulose derivative and the aliphatic polyester elastomer, both a thermoplastic polymer other than the aromatic polyester and a thermosetting polymer can be used, but a thermoplastic polymer is preferable from the viewpoint of moldability. Specific examples of polymers other than cellulose derivatives and aliphatic polyester elastomers include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, ethylene-propylene copolymer, and 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, nylon 6, nylon 46, nylon 66, Polyamide such as nylon 610, nylon 612, nylon 6T, nylon 12, polystyrene, high impact polystyrene, polyacetal (including homopolymers and copolymers), polyurethane, aromatics and fats Group polyketone, polyphenylene sulfide, polyether ether ketone, thermoplastic starch resin, acrylic resin such as polymethyl methacrylate and methacrylate ester-acrylate ester copolymer, AS resin (acrylonitrile-styrene copolymer), polyvinyl chloride , Polyvinylidene chloride, vinyl ester resin, maleic anhydride-styrene copolymer, MS resin (methyl methacrylate-styrene copolymer), polycarbonate, polyarylate, polysulfone, polyethersulfone, phenoxy resin, polyphenylene ether, modified Thermoplastic polyimide such as polyphenylene ether and polyetherimide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene Copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, and other fluoropolymers, cellulose acetate , Polyvinyl alcohol, unsaturated polyester, melamine resin, phenol resin, urea resin, polyimide and the like.
Various acrylic rubbers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers), ethylene-acrylic acid alkyl ester copolymers (for example, ethylene-ethyl acrylate copolymer) Copolymer, ethylene-butyl acrylate copolymer), diene rubber (for example, 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (for example, Styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer Polymer, polybutadiene Styrene-grafted styrene, butadiene-acrylonitrile copolymer), polyisobutylene, copolymer of isobutylene and butadiene or isoprene, butyl rubber, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, nitrile rubber, poly Examples include ether rubber, epichlorohydrin rubber, fluoro rubber, silicone rubber, and other thermoplastic elastomers such as polyurethane, polyester, and polyamide.

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

When the molding material of the present invention contains a polymer other than the cellulose derivative and the aliphatic polyester elastomer, the content is preferably 30 parts by mass or less with respect to a total of 100 parts by mass of the cellulose derivative and the aliphatic polyester elastomer. More preferable is 10 parts by mass.

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

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

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

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

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

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

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

When the molding material of the present invention contains a plasticizer, the content thereof is usually 30 parts by mass or less, preferably 0.005 to 20 parts by mass with respect to 100 parts by mass in total of the cellulose derivative and the aliphatic polyester elastomer. More preferably, it is 0.01 to 10 parts by mass.

The molded body of the present invention can be obtained by molding a molding material containing the cellulose derivative and the aliphatic polyester elastomer. More specifically, the cellulose derivative and the aliphatic polyester elastomer, or the molding material containing the cellulose derivative and the aliphatic polyester elastomer and various additives as necessary are heated and molded by various molding methods. It is obtained by the manufacturing method including the process to do.
The method for producing a molded body of the present invention includes a step of heating and molding the molding material.
Examples of the molding method include injection molding, extrusion molding, blow molding and the like.
The heating temperature is usually 160 to 300 ° C, preferably 180 to 260 ° C.

The use of the molded product of the present invention is not particularly limited. For example, interior or exterior parts of electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.), automobiles, mechanical parts, etc. And materials for housing and construction. Among these, from the viewpoint of having excellent heat resistance 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.

[Examples 1 to 13 and Comparative Examples 1 to 5]
<Synthesis Example 1: Synthesis of acetoxypropylmethylacetylcellulose (C-1)>
In a 5 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, weigh 60 g of hydroxypropyl methylcellulose (trade name Metroze 90SH-100; manufactured by Shin-Etsu Chemical) and 2100 mL of N, N-dimethylacetamide and stir at room temperature. did. After confirming that the reaction system became transparent and completely dissolved, 101 mL of acetyl chloride was slowly added dropwise to raise the temperature of the system to 80 ° C. to 90 ° C. After stirring for 3 hours, the temperature of the reaction system was cooled to room temperature. When the reaction solution was added to 10 L of water with vigorous stirring, a white solid was precipitated. The white solid was filtered off by suction filtration and washed with a large amount of water three times. The obtained white solid was vacuum-dried at 100 ° C. for 6 hours to obtain the objective cellulose derivative (C-1) (acetoxypropylmethylacetylcellulose) as a white powder. The solubility of this cellulose derivative (C-1) in water at 25 ° C. was less than 0.1% by mass (insoluble).

<Synthesis Examples 2, 3, and 4: Synthesis of acetoxyethyl methyl acetyl cellulose (C-2), methyl acetyl cellulose (C-3), and ethyl acetyl cellulose (C-4)>
Hydroxypropyl methylcellulose (trade name Metrolose 90SH-100; manufactured by Shin-Etsu Chemical Co., Ltd.) in Synthesis Example 1 was replaced with hydroxyethylmethylcellulose (trade name Marporose ME-250T; manufactured by Matsumoto Yushi), methylcellulose (trade name Marporose M-4000: Matsumoto Yushi Co., Ltd.) And acetoxyethyl methyl acetyl cellulose (C-2), methyl acetyl cellulose (C-3), ethyl acetyl cellulose (C-3) in the same manner as in Synthesis Example 1 except that it was changed to ethyl cellulose (trade name Etcel 300CP: manufactured by Dow Chemical). C-4) was obtained. The solubility of these cellulose derivatives (C-2), (C-3), and (C-4) in water at 25 ° C. was less than 0.1% by mass (insoluble).

<Synthesis Example 5: Synthesis of methylcellulose-2-ethylhexanoate (C-5)>
In a 3 L three-necked flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel, 80 g of methylcellulose (manufactured by Wako Pure Chemical Industries, Ltd .: methyl substitution degree 1.8) and 1500 mL of pyridine were weighed and stirred at room temperature. Under water cooling, 173 mL of 2-ethylhexanoyl chloride was slowly added dropwise thereto, and the mixture was further stirred at 60 ° C. for 6 hours. After the reaction, the reaction solution was returned to room temperature and quenched by adding 200 mL of methanol under ice cooling. When the reaction solution was added to 12 L of water with vigorous stirring, a white solid was precipitated. The white solid was filtered off by suction filtration and washed 3 times with a large amount of methanol solvent. The resulting white solid was vacuum-dried at 100 ° C. for 6 hours to obtain methylcellulose-2-ethylhexanoate (C-5). The solubility of this cellulose derivative (C-5) in water at 25 ° C. was less than 0.1% by mass (insoluble).

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

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

Note that the types and substitution degrees of hydrocarbon groups, the types and molar substitutions of alkyleneoxy groups, the types of acyl groups, and the degrees of acylation of the cellulose derivatives obtained above are described in Cellulose Communication 6, 73-79 (1999). Was observed and determined by ¹ H-NMR using the method described in ¹ ). The degree of substitution of the hydrocarbon group is the number of moles of the hydrocarbon group substituted on the glucose ring unit, and takes a value of 0 or more and less than 3. The molar substitution degree of the alkyleneoxy group is the number of moles of the alkyleneoxy group substituted on the glucose ring unit, and takes a value of 0 or more. The degree of acylation indicates the degree of substitution with an acyl group by esterifying a hydroxyl group present in the glucose ring or ether substituent of cellulose, and is represented by 0 or more and 100 or less.

Further, a colloid titration method is performed, and the degree of substitution of carboxyl groups or sulfonic acid groups in the cellulose derivatives (C-1) to (C-7) is less than 0.02 (that is, the content of carboxyl groups or sulfonic acid groups is It was confirmed that it was less than 0.5% by mass with respect to the cellulose derivative.

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

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

[Production of molded body]
Cellulose derivatives (C-1 to C-7, H-1), aliphatic polyester elastomers, compatibilizers and antioxidants were mixed at the blending ratio (mass%) shown in Table 2 to prepare a cellulose resin composition. . This resin composition was supplied to a twin-screw kneading extruder (manufactured by Technobel Co., Ltd., Ultranano) to produce pellets, and then the obtained pellets were injected into an injection molding machine (FANUC Corporation Robot S-2000i, automatic injection molding). 4 × 10 × 80 mm multipurpose test pieces (impact test pieces and bending test pieces).

In Table 2, the aliphatic polyester elastomer, H-2, compatibilizer and antioxidant are as follows.
Polybutylene succinate (PBS): Bionore # 1001 (Mn = 70000), manufactured by Showa Polymer Co., Ltd. Polycaprolactone (PCL): PH7 (Mn = 45000), manufactured by Daicel Co., Ltd. H-2 : Adipic acid-based polyester plasticizer (“D-623” manufactured by JPLUS Co., Ltd., Mn = 1800)
・ Compatibilizer: Modiper A4400, manufactured by NOF Corporation (ethylene-glycidyl methacrylate-graft-acrylonitrile-styrene resin)
・ Antioxidant: Phenolic antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals)

[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 thermal deformation 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.
Two test temperatures, 23 ° C. and −30 ° C. (evaluation of impact resistance at low temperatures), were performed.

(Formability evaluation)
The moldability evaluation shows the moldability in an injection molding machine. A resin composition that is excellent in both mold transportability and injection property is indicated by ○, a resin composition that has a problem in either one, and a problem in both. A certain resin composition was set as x. The evaluation results are shown in Table 2.
In addition, the moldability is considered to be a problem when a measurement failure such as abnormal noise occurs at the time of resin measurement, and is excellent if measurement can be performed without any problem. Injectability is considered to be a problem if molding defects such as burrs, sink marks, silver skin, and bubbles occur in the molded product, and excellent if it can be molded without problems.

(Dispersibility evaluation)
As an index of dispersibility, an optical microscope (Nikon LV100) was used for evaluation. A microtome was sliced to 2 μm, observed at 1000 times, and evaluated according to the following criteria.
○: When aggregates are not observed Δ: When aggregates are slightly observed ×: When many aggregates are observed

From Table 2, the test pieces of Examples 1 to 13 made of a molding material containing a cellulose derivative and an aliphatic polyester elastomer in the present invention are rigid, bending strength, impact resistance, moldability, and impact resistance at low temperature. It turns out that it is excellent. Comparative Example 1 containing no aliphatic polyester elastomer was inferior in impact resistance at low temperatures to Example 1 containing aliphatic polyester. Further, Comparative Examples 2 to 4 which do not contain a cellulose derivative in the present invention cannot achieve both rigidity / heat resistance and impact resistance (room temperature / low temperature), and lack a balance of physical properties as a structural material. Further, Comparative Example 5 using an adipic acid-based polyester having a number average molecular weight of 1800 caused a significant decrease in rigidity and heat resistance as compared with Example 1 containing a polyester elastomer having a number average molecular weight of 10,000 or more.

[Examples 14 to 42 and Comparative Examples 6 to 10]
<Synthesis Example 8: Preparation of rubbery polymer R-1>
In a glass reactor equipped with a stirrer and a heating device, 50 parts by mass of polybutadiene rubber latex (solid content, mass average particle diameter 300 nm, gel content 80%), 0.5 parts by mass of potassium rosinate (solid content), Dextrose 0 .2 parts by mass, ion-exchanged water (hereinafter abbreviated as water; 145 parts by mass of rubber latex and water in potassium rosinate) were added, and the temperature was raised to 60 ° C. under a nitrogen stream and stirring. A mixture comprising 0.003 parts by mass of ferrous sulfate, 0.1 parts by mass of sodium pyrophosphate and 5 parts by mass of ion-exchanged water was added thereto, followed by 15 parts by mass of acrylonitrile, 35 parts by mass of styrene monomer, and tert-dodecyl mercaptan. A mixture consisting of 0.5 parts by mass and 0.5 parts by mass of cumene hydroperoxide was added dropwise over 3 hours, during which time the internal temperature was controlled so as not to exceed 70 ° C., and graft polymerization was carried out. Further, cumene hydroperoxide An additional 0.1 parts by mass was added and maintained at 70 ° C. for an additional hour before cooling.
The obtained latex was coagulated, washed with water and dried with a 0.5% sulfuric acid aqueous solution 1.2 times the amount of latex to obtain a rubber polymer (R-1) having polybutadiene as a core as a white powder. .

<Synthesis Example 9: Preparation of rubbery polymer R-2>
In a glass reactor equipped with a stirrer and a heating device, 0.5 parts by mass of dipotassium alkenyl succinate (solid content), 175 parts by mass of water (including water in dipotassium alkenyl succinate), 0.2 parts by mass of Rongalite, n − 50 parts by weight of butyl acrylate, 0.2 parts by weight of allyl methacrylate, 0.1 parts by weight of 1,3-butylene glycol dimethacrylate and 0.1 parts by weight of tert-butyl hydroperoxide were added, and the atmosphere was replaced with nitrogen under stirring. The internal temperature was raised to 60 ° C. Thereafter, a mixture of 0.0009 parts by mass of EDTA (disodium ethylenediaminetetraacetate), 0.0003 parts by mass of ferrous sulfate and 5 parts by mass of water was added to initiate polymerization of n-butyl acrylate, and the internal temperature was increased. The temperature reached 83 ° C., and the polymerization of n-butyl acrylate was terminated to obtain a poly n-butyl acrylate rubber latex. The mass average particle diameter was 200 nm.
Subsequently, the internal temperature was cooled to 70 ° C., 0.5 parts by mass of dipotassium alkenyl succinate, 15 parts by mass of acrylonitrile, 35 parts by mass of styrene monomer, 0.02 parts by mass of n-octyl mercaptan, tert-butyl hydroperoxide 0. Graft polymerization was carried out by supplying a mixture of 1 part by mass over 3 hours, and the internal temperature was controlled not to exceed 80 ° C. during that time. After completion of the dropwise addition, 0.05 part by mass of tert-butyl hydroperoxide was further added, and the mixture was further maintained at 80 ° C. for 1 hour, and then cooled.
The obtained latex was coagulated with 0.6% sulfuric acid aqueous solution 1.4 times the amount of latex, washed with water, and dried to give a rubber polymer (R-2) having poly n-butyl acrylate as a white powder. Got as a body.

<Synthesis Example 10: Preparation of rubbery polymer R-3>
98 parts by mass of octamethylcyclotetrasiloxane and 2 parts by mass of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts by mass of a siloxane-based mixture. An aqueous solution consisting of 0.67 parts by mass of sodium dodecylbenzenesulfonate and 300 parts by mass of water was added thereto, and the mixture was stirred at 10000 rpm for 2 minutes with a homomixer, and then passed once through the homogenizer at a pressure of 20 MPa. A stable premixed organosiloxane latex was obtained.
On the other hand, 10 parts by weight of dodecylbenzenesulfonic acid and 90 parts by weight of water were charged into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. . While this aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and the temperature was maintained for 1 hour after the completion of the dropwise addition, followed by cooling. The reaction was then neutralized with an aqueous caustic soda solution. The polyorganosiloxane latex thus obtained was dried at 170 ° C. for 30 minutes and the solid content was determined to be 17.7%. Moreover, the mass average particle diameter of the polyorganosiloxane in the latex was 50 nm.

In a glass reactor equipped with a reagent injection container, a cooling tube, a jacket heater, a thermometer, and a stirrer, 15 parts by mass of the above polyorganosiloxane (solid content), dipotassium alkenyl succinate (solid content) 0.2 mass And 410 parts by weight of water (including water in the polyorganosiloxane) were added to this, and at room temperature, with stirring, 85 parts by weight of n-butyl acrylate, 0.3 parts by weight of allyl methacrylate, 1,3-butylene glycol diester A mixture consisting of 0.15 parts by weight of methacrylate and 0.2 parts by weight of tert-butyl hydroperoxide was added. The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reactor, and the jacket was heated to 60 ° C. When the internal liquid temperature reaches 50 ° C., it consists of 0.00015 parts by mass of ferrous sulfate heptahydrate salt, 0.00044 parts of ethylenediaminetetraacetic acid disodium salt salt, 0.4 parts by weight of Rongalite salt, and 10 parts by weight of water. An aqueous solution was added to initiate radical polymerization, and the internal temperature was raised to 75 ° C. This state was maintained for 1 hour to complete the polymerization of n-butyl acrylate to obtain a composite rubbery polymer latex. The mass average particle diameter was 60 nm.

Subsequently, in a glass reactor equipped with a reagent injection container, a cooling tube, a jacket heater, a thermometer, and a stirring device, 50 parts by mass of the composite rubber-like polymer latex (solid content), water (composite rubber-like polymer) 210 parts by mass (including water in the latex), 0.7 parts by mass of dipotassium alkenyl succinate and 0.15 parts by mass of Rongalite were mixed with stirring, and the internal temperature was raised to 70 ° C. Thereafter, a mixture of 3 parts by mass of acrylonitrile, 9 parts by mass of styrene and 0.1 part by mass of tert-butyl hydroperoxide was supplied dropwise over 30 minutes for polymerization. After holding for 15 minutes, add an aqueous solution consisting of 0.15 parts Rongalite 、, 0.001 parts by mass of ferrous sulfate heptahydrate, 0.003 parts by mass of disodium ethylenediaminetetraacetate, 5 parts by mass of water, A mixture of 9.5 parts by weight of acrylonitrile, 28.5 parts by weight of styrene, and 0.3 parts by weight of tert-butyl hydroperoxide was dropped and polymerized over 120 minutes, and the content was maintained at 70 ° C. for 30 minutes. The thing was cooled. The obtained graft copolymer latex was poured into a 1.5-fold 1% aluminum sulfate aqueous solution at 50 ° C. under examination, further heated to 70 ° C. and held for 5 minutes, and further 90 The temperature was raised to 0 ° C. and held for another 5 minutes. Dehydration and washing were repeated, and finally, it was dried for a whole day and night under an air stream to obtain a rubber polymer (R-3) in the form of a white powder.

In addition, the following rubbery polymers were prepared.
・ (R-4): “Metablene C-323A” (MBS resin) manufactured by Mitsubishi Rayon Co., Ltd.
・ (R-5): “Paraloid EXL-2602” (MBS resin) manufactured by Kureha Chemical Co., Ltd.
・ (R-6): “Methbrene W529” manufactured by Mitsubishi Rayon Co., Ltd. (polymer obtained by grafting methyl methacrylate to acrylic rubber)
(R-7): “Metblene S2001” (polymer obtained by grafting methyl methacrylate onto a silicone / acrylic composite rubber) manufactured by Mitsubishi Rayon Co., Ltd.

The following aliphatic polyester elastomer was prepared.
(S-1) Polybutylene succinate (PBS): GSPla AD92W (Mn = 40000), manufactured by Mitsubishi Chemical Corporation (S-2) Polybutylene succinate adipate (PBSA): Bionore # 3001 (Mn = 34000), manufactured by Showa High Polymer Co., Ltd. (S-3) Polycaprolactone (PCL): PH7 (Mn = 45000), manufactured by Daicel Co., Ltd. The following were prepared as cellulose ether resins.
(H-3) Cellulose ether: Etocel 100, manufactured by Dow Chemical

[Production of molded body]
Cellulose derivatives (C-1 to C-7), rubbery polymers (R-1 to R-7), aliphatic polyester elastomers (S-1 to S-3), cellulose ester resins (H— 1) Using a cellulose ether resin (H-3), blended at the blending ratio (mass%) shown in Table 3, and with respect to 100 parts by weight of these total amounts, an antioxidant (Ciba Specialty Chemicals) was further added. After adding 0.5 parts by mass of “Irganox 1010” manufactured by the company, a mixture for molding material was prepared by mixing with a Henschel mixer. This mixture was supplied to a twin-screw kneading extruder (manufactured by Technobel Co., Ltd., Ultrano) set at a barrel temperature of 210 ° C. to produce pellets. Subsequently, the obtained pellets were supplied to a small injection molding machine (FANUC ROBOSHOT S-2000i, automatic injection molding machine), and a multi-purpose test piece (impact test piece and bending test piece) of 4 mm × 10 mm × 80 mm And 8 cm × 5 cm × 2 mm plate-shaped test pieces, 10 mm × 10 mm × 4 mm Vicat softening point temperature measurement test pieces were molded.

(Falling ball impact test)
In accordance with JIS K7211-1, both ends of the plate-shaped test piece (1 cm each in width 8 cm) are fixed, and a 500 g steel ball is used using a cylindrical guide (if the height exceeds 2.5 m, the weight Was changed to 1,000 g) from a predetermined height to the center of the test piece, and it was observed whether or not a crack penetrated the test piece. A test was performed on a plurality of test pieces, and the height when the probability that a crack penetrates the test piece was 50% was obtained. From the results, the fracture energy (50% fracture energy: unit J) was determined and shown in Table 3. The test was conducted at 23 ° C.

(Vicat softening temperature)
Using the above test piece and a heat distortion tester manufactured by Yasuda Seiki Seisakusho Co., Ltd., measurement was performed at a temperature increase rate of 50 ° C./h in accordance with ISO306.

From the results shown in Table 3, the molding materials of Examples 14 to 42 containing rubber particles together with the cellulose derivative and the aliphatic polyester elastomer in the present invention have good flexural modulus, falling ball impact strength and Vicat softening point temperature. It turns out that it shows performance. In addition, it can be seen that the molding materials of Examples 38 to 42 further containing a cellulose ester resin or a cellulose ether resin are more excellent in falling ball impact strength.

Since the molding material of the present invention has excellent thermoplasticity, it can be molded by heat molding or the like. Further, the molding material and the molded body of the present invention are excellent in performance such as rigidity, bending strength, and heat resistance, and have good impact resistance, molding processability, and impact resistance at low temperature, for example, It can be suitably used as components such as automobiles, home appliances, electrical and electronic equipment, machine parts, housing / building materials, and the like. Moreover, since the molding material of this invention uses the cellulose derivative obtained from the cellulose which is plant-derived resin, it can substitute for the conventional petroleum-derived resin as a raw material which can contribute to global warming prevention.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on December 25, 2009 (Japanese Patent Application No. 2009-295061) and a Japanese patent application filed on September 29, 2010 (Japanese Patent Application No. 2010-220083). Incorporated herein by reference.

Claims (25)

1. The hydrogen atom of the hydroxyl group contained in cellulose
   A cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below;
   A molding material containing an aliphatic polyester elastomer having a number average molecular weight of 10,000 or more.
   A) Hydrocarbon group: —R _A
   B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)
2. The molding material according to claim 1, wherein the cellulose derivative further comprises at least one group in which a hydrogen atom of a hydroxyl group contained in cellulose is substituted by the following C).
   C) a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 to 4 carbon atoms. )
3. The molding material according to claim 2, wherein the C) group containing an alkyleneoxy group and an acyl group is a group containing a structure represented by the following general formula (3).
   

   

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

   
10. The molding material according to any one of claims 1 to 9, wherein the cellulose derivative has substantially no carboxyl group, sulfonic acid group, or salt thereof.
11. The molding material according to any one of claims 1 to 10, wherein the cellulose derivative is insoluble in water.
12. The aliphatic polyester elastomer is a polyester obtained by a condensation reaction of an aliphatic polyhydric alcohol and an aliphatic polybasic acid, or an aliphatic polyester obtained by ring-opening polymerization of a cyclic ester. The molding material according to one item.
13. The aliphatic polyhydric alcohol is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentane. At least one selected from diol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol 1,4-cyclohexanedimethanol, and 1,4-benzenedimethanol,
    The aliphatic polybasic acid is succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 1,4-phenylenediacetic acid The molding material of Claim 12 which is an at least 1 type of aliphatic polybasic acid chosen from these, phenyl succinic acid, and these anhydrides.
14. The molding material according to claim 12, wherein the cyclic ester is ε-caprolactone.
15. The molding material according to any one of claims 1 to 14, further comprising rubber particles.
16. The molding material according to claim 15, wherein the rubber particles have a core-shell structure.
17. The molding material according to claim 16, wherein the core in the rubber particles is an acrylic rubber or a silicone / acrylic composite rubber, and the shell component is a vinyl polymer.
18. The cellulose derivative, the rubber particles and the aliphatic polyester elastomer are contained in an amount of 40 to 90% by mass, the rubber particles are contained in an amount of 5 to 50% by mass and the aliphatic polyester elastomer is contained in an amount of 5 to 50% by mass with respect to the total amount of the cellulose derivative, rubber particles and aliphatic polyester elastomer. 18. The molding material according to any one of items 17 to 17.
19. The molding material according to any one of claims 1 to 17, further comprising at least one of a cellulose ester resin and a cellulose ether resin.
20. 20 to 80% by mass of cellulose derivative, 5 to 40% by mass of rubber particles, and 5 to 5% of aliphatic polyester elastomer with respect to the total amount of the cellulose derivative, rubber particles, aliphatic polyester elastomer, cellulose ester resin and cellulose ether resin. The molding material according to claim 19, wherein 40% by mass and 5 to 50% by mass of the total amount of the cellulose ester resin and the cellulose ether resin are contained.
21. The molding material according to any one of claims 1 to 20, further comprising a compatibilizing agent.
22. The molding material according to claim 21, wherein the compatibilizer is a carboxylic acid anhydride or a compound having at least one selected from the group consisting of an epoxy group, an isocyanate group and an oxazoline group.
23. A molded body obtained by thermoforming the molding material according to any one of claims 1 to 22.
24. A method for producing a molded body, comprising a step of heating and molding the molding material according to any one of claims 1 to 22.
25. An electrical and electronic equipment casing comprising the molded body according to claim 23.