JP5238684B2 - Textile materials and fibers - Google Patents

Description

  The present invention relates to fiber materials and fibers.

Conventionally, synthetic fibers typified by polyester fibers and the like have been widely used as clothing, bedding and interior goods because they are excellent in various properties such as strength, heat resistance, chemical resistance, and wash and wear properties. On the other hand, synthetic fibers have a very high durability and do not easily decompose in the natural environment. Therefore, the synthetic fibers remain semi-permanently unless incineration is performed.
Cellulosic fibers, on the other hand, have a variety of advantages such as higher biodegradability in the natural environment, higher water absorption, and better skin feel compared to synthetic fibers. ing. However, it has the disadvantage that it is inferior in terms of fiber strength and fiber elongation compared to synthetic fibers.

By the way, fossil resources such as petroleum, which is a material for synthetic fibers, 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, synthetic fibers made from petroleum, which is a fossil resource, have excellent characteristics as raw materials for textile products, but are made from petroleum, which is a fossil resource. From the viewpoint of prevention, it is desirable to reduce the amount used.
On the other hand, plant-derived cellulosic fibers are originally produced by photosynthetic reactions of plants using carbon dioxide and water in the atmosphere as raw materials. Therefore, even if plant-derived cellulosic fibers are 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 positive. There is an idea that the total amount of CO _{2 in} the atmosphere is not increased after all, minus zero. From this idea, plant-derived cellulosic fibers can be said to be a so-called “carbon neutral” material. Therefore, reducing the use of petroleum-derived fibers and using carbon-neutral materials contributes significantly to the prevention of global warming, which has become an urgent task in recent years.

For example, in the field of resin materials, a method for reducing petroleum-derived resources by using plant-derived resources such as starch as a part of petroleum-derived raw materials for PC (Polycarbonate) polymers using petroleum as a raw material has been proposed. (Patent Document 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, Patent Document 5 discloses a membrane used for dialysis and the like using a cellulose derivative, and Patent Documents 6 and 7 disclose acrylic fibers containing a cellulose derivative such as cellulose acetate.

JP-A-56-55425 JP 2008-24919 A US Pat. No. 3,979,179 U.S. Pat. No. 3,940,384 Japanese Patent Publication No. 64-36601 JP 2002-309440 A JP 2006-152475 A

  Thus, the cellulose fiber which is an excellent material as a carbon neutral fiber is used in various forms. However, for example, in Patent Document 6 and Patent Document 7, cellulose derivatives are used, but since acrylic fibers are included as necessary components, the characteristics of cellulose fibers such as biodegradability are impaired, and the advantages are completely alive. It has not been. Therefore, what is desired now is a property with a low environmental impact that is improved in terms of fiber strength and fiber elongation, which are considered to be inferior to synthetic fibers, while having a good texture and texture which are the advantages of cellulose fibers. It is an excellent fiber.

  An object of the present invention is to provide a fiber material excellent in spinning and spinning properties that can obtain fibers having good fiber strength, fiber elongation, and texture. Another object of the present invention is to provide a fiber obtained by spinning and spinning the fiber material.

The present inventors paid attention to the molecular structure of cellulose, made cellulose a cellulose derivative having a specific structure having an ether structure and an ester structure, and the fiber obtained from the fiber material containing the cellulose derivative having the specific structure has a fiber strength. The present inventors have found that excellent properties are expressed in all aspects of fiber elongation and texture, and have completed the present invention.
That is, the said subject can be achieved by the following means.
[1]
The hydrogen atom of the hydroxyl group contained in cellulose
A fiber material comprising a cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.)
[2]
The fiber material according to [1], wherein the cellulose derivative further includes at least one group in which a hydrogen atom of a hydroxyl group contained in cellulose is substituted by the following C).
C) a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms. )
[3]
The fiber material according to [1] or [2], wherein the group C) containing an alkyleneoxy group and an acyl group is a group containing a structure represented by the following general formula (3).

(Wherein R _C1 represents a hydrocarbon group, R _C2 represents an alkylene group having 2 or 3 carbon atoms, and n represents an integer of 1 or more.)
[4]
The fiber material according to any one of [1] to [3], wherein R _A is an alkyl group having 1 to 4 carbon atoms.
[5]
The fiber material according to any one of [1] to [4], wherein R _A is a methyl group or an ethyl group.
[6]
The fiber material according to any one of [1] to [5], wherein R _B and R _C1 are each independently an alkyl group or an aryl group.
[7]
The fiber material according to any one of [1] to [6], wherein R _B and R _C1 are each independently a methyl group, an ethyl group, or a propyl group.
[8]
Wherein _{R B} is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms, fiber material according to any one of [1] to [6].
[9]
The fiber 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 fiber material according to any one of [1] to [9], wherein the cellulose derivative does not substantially have a carboxyl group, a sulfonic acid group, and a salt thereof.
[11]
The fiber material according to any one of [1] to [10], wherein the cellulose derivative is insoluble in water.
[12]
Furthermore, the fiber material in any one of [1]-[11] containing a plasticizer.
[13]
A fiber obtained by spinning the fiber material according to any one of [1] to [12].
[14]
The fiber according to [13], wherein the shape is a thread shape, a cotton shape, a cloth shape, or a non-woven fabric shape.

  The fiber obtained from the fiber material of the present invention is excellent in fiber strength, fiber elongation, and texture, and can be suitably used for various clothing, miscellaneous goods, material goods, interior goods, nursing care goods, and the like. Moreover, since it is a plant-derived fiber, it can be replaced with a conventional petroleum-derived synthetic fiber as a material that can contribute to prevention of global warming.

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

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

As described above, the cellulose derivative in the present invention has thermoplasticity due to etherification and esterification of at least part of the hydroxyl group of the β-glucose ring by A) a hydrocarbon group and B) an acyl group. It can be expressed and is suitable for processing.
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) Any one of R ² , R ³ and R ⁶ of one repeating unit is substituted with A) a hydrocarbon group, and B) an acyl group (that is, the above A) and B in one repeating unit A cellulose derivative composed of the same type of repeating unit.
(3) A cellulose derivative in which repeating units having different substitution positions and different types of substituents are bonded at random.
The cellulose derivative may contain an unsubstituted repeating unit (that is, a repeating unit in which R ² , R ³ and R ⁶ are all hydrogen atoms in the general formula (A)).
Moreover, the cellulose derivative may have other substituents other than a hydrogen atom, A) a hydrocarbon group, and B) an acyl group.

A) Hydrocarbon group: -R _A may be either an aliphatic group or an aromatic group.
When R _A is an aliphatic group, it may be linear, branched, or cyclic, and may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
When R _A is an aromatic group, it may be either a single ring or a condensed ring. When _RA is an aromatic group, the preferable carbon number is 6-18, More preferably, it is 6-14, More preferably, it is 6-10. 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 fiber strength of the resulting fiber is excellent, more preferably an alkyl group, and more preferably an alkyl group, and even more preferably a carbon number. 1 to 4 alkyl groups (lower alkyl groups). Specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, tert-butyl group, isoheptyl group, and the like. A group or an ethyl group is particularly preferred.

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

The cellulose derivative in the fiber material of the present invention is a cellulose derivative in which a hydrogen atom of a hydroxyl group contained in cellulose includes at least one group substituted with the above A) and at least one group substituted with the above B). However, it is further preferable from the viewpoint of fiber strength to contain at least one group in which the hydrogen atom of the hydroxyl group contained in cellulose is substituted by the following C).
C) a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms. )

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

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

Among them, a group represented by the following formula (1) or (2) in which —RC ₂ —O— is branched is preferable because the fiber elongation of the obtained fiber is excellent.

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

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

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

R _A in A), R B in _B ), R _C1 and R _C2 in C) may have a further substituent or may be unsubstituted, but are preferably unsubstituted.

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

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

  Moreover, it is preferable that the cellulose derivative in this invention is insoluble in water. Here, “being insoluble in water” means that the solubility in 100 parts by mass of water at 25 ° C. is 5 parts by mass or less.

As a specific example of the cellulose derivative in the present invention,
Acetyl methyl cellulose, acetyl ethyl cellulose, acetyl propyl cellulose, acetyl butyl cellulose, acetyl pentyl cellulose, acetyl hexyl cellulose, acetyl cyclohexyl cellulose, acetyl phenyl cellulose, acetyl naphthyl cellulose,

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

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

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

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

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

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

Propionyloxyethyl methyl acetylcellulose, propionyloxyethyl ethyl acetylcellulose, propionyloxyethylpropyl acetylcellulose, propionyloxyethylbutylacetylcellulose, propionyloxyethylpentylacetylcellulose, propionyloxyethylhexylacetylcellulose, propionyloxyethylcyclohexylacetylcellulose, propionyloxy Ethylphenylacetylcellulose, propionyloxyethyl naphthylacetylcellulose, propionyloxyethyl methylpropionylcellulose, propionyloxyethyl

Ethyl propionylcellulose, propionyloxyethylpropylpropionylcellulose, propionyloxyethylbutylpropionylcellulose, propionyloxyethylpentylpropionylcellulose, propionyloxyethylhexylpropionylcellulose, propionyloxyethylcyclohexylpropionylcellulose, propionyloxyethylphenylpropionyloxyethylpropionylcellulose cellulose,

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

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

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

Examples include valeroxypropylmethyl valeroyl cellulose and valeroxybutyl methyl valeroyl cellulose.

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

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

For example, A) Hydrocarbon group: Degree of substitution DS _{A of} -R _A (number of R _A with respect to hydroxyl groups at the 2nd, 3rd and 6th positions of the β-glucose ring in the repeating unit) is 1.0 <DS _A It is preferable that 1.0 <DS _A <2.5. Further, DS _A is preferably 1.1 or more.
B) Degree of substitution DS _{B of} acyl group (—CO—R _B ) (number of —CO—R _B with respect to hydroxyl groups at the 2nd, 3rd and 6th positions of the cellulose structure of the β-glucose ring in the repeating unit) 0.1 <DS _B is preferable, and 0.1 <DS _B <2.0 is more preferable.
C) Degree of substitution DS _C of a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (in the repeating unit, the 2nd, 3rd and 6th positions of the cellulose structure of the β-glucose ring) position of C to the hydroxyl group) alkyleneoxy _{group: -R} C2 -O- acyl group: the number of groups containing a _{-CO-R C1)} is preferably _{0 <DS C, 0 <DS} C <1 0.0 is more preferable. By 0 is <DS _C, it is possible to lower the melting initiation temperature of the cellulose derivative, can be carried out spinning more readily.
By setting the degree of substitution within the above range, fiber strength, spinnability, 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. The DS _H by 0.6 or less, or to improve the flowability of the fibrous material, a foam or the like due to water absorption of the fiber material during acceleration and spinning of 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, spinnability, etc. can be improved, and a cellulose derivative suitable for a fiber material can be obtained.

The molecular weight of the cellulose derivative in the present invention is preferably a number average molecular weight (Mn) 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 spinnability and spinnability of the fiber material, the mechanical strength of the fiber, and the like.
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, it is possible to improve the spinnability and the spinning property.
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 can be used as a solvent, a polystyrene gel can be used, and the molecular weight can be obtained using a conversion molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene.

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

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

A) hydrocarbon group: —R _A , B) acyl group: —CO—R _B (R _B represents a hydrocarbon group), and C) alkyleneoxy group: —R _C2 —O— and an acyl group: A preferred embodiment of a method for producing a cellulose derivative having a group containing —CO—R _C1 (R _C1 represents a hydrocarbon group and R _C2 represents an alkylene group having 2 or 3 carbon atoms) is a hydrocarbon group. And hydroxyethyl cellulose ether having a hydroxyethyl group or hydroxypropyl cellulose ether having a hydroxypropyl group are reacted by an acid chloride or an acid anhydride to react with the esterification (acylation). is there.
Further, as another embodiment, for example, after etherification with cellulose ether such as methyl cellulose or ethyl cellulose with propylene oxide or the like, alkyl chloride such as methyl chloride or ethyl chloride / alkylene oxide having 3 carbon atoms or the like is allowed to act on cellulose. Furthermore, a method including a step of esterification by reacting an acid chloride or an acid anhydride is also included.
As a method for reacting acid chloride, for example, the method described in Cellulose 10; 283-296, 2003 can be used.
Specific examples of the cellulose ether having a hydrocarbon group and a hydroxyethyl group include hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl propyl cellulose, hydroxyethyl allyl cellulose, and hydroxyethyl benzyl cellulose. Preferred are hydroxyethyl methyl cellulose and hydroxyethyl ethyl cellulose.
Specific examples of the cellulose ether having a hydrocarbon group and a hydroxypropyl group include hydroxypropylmethylcellulose, hydroxypropylethylcellulose, hydroxypropylpropylcellulose, hydroxypropylallylcellulose, hydroxypropylbenzylcellulose, and the like. Preferred are hydroxypropylmethylcellulose and hydroxypropylethylcellulose.

  As the acid chloride, B) acyl group and carboxylic acid chloride corresponding to the acyl group contained in C) can be used. Examples of the carboxylic acid chloride include acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, pentanoyl chloride, 2-methylbutanoyl chloride, 3-methylbutanoyl chloride, pivaloyl chloride, hexanoyl chloride, 2-methylpentanoyl chloride, 3-methylpentanoyl chloride, 4-methylpentanoyl chloride, 2,2-dimethylbutanoyl chloride, 2,3-dimethylbutanoyl chloride, 3,3-dimethylbutanoyl chloride, 2- Ethylbutanoyl chloride, heptanoyl chloride, 2-methylhexanoyl chloride, 3-methylhexanoyl chloride, 4-methylhexanoyl chloride, 5-methylhexanoyl chloride, 2,2-dimethylpentanoyl chloride, , 3-dimethylpentanoyl chloride, 3,3-dimethylpentanoyl chloride, 2-ethylpentanoyl chloride, cyclohexanoyl chloride, octanoyl chloride, 2-methylheptanoyl chloride, 3-methylheptanoyl chloride, 4-methyl Heptanoyl chloride, 5-methylheptanoyl chloride, 6-methylheptanoyl chloride, 2,2-dimethylhexanoyl chloride, 2,3-dimethylhexanoyl chloride, 3,3-dimethylhexanoyl chloride, 2-ethylhexanoyl Chloride, 2-propylpentanoyl chloride, nonanoyl chloride, 2-methyloctanoyl chloride, 3-methyloctanoyl chloride, 4-methyloctanoyl chloride, 5-methyloctanoyl chloride, 6-methyloctanoy Chloride, 2,2-dimethylheptanoyl chloride, 2,3-dimethylheptanoyl chloride, 3,3-dimethylheptanoyl chloride, 2-ethylheptanoyl chloride, 2-propylhexanoyl chloride, 2-butylpentanoyl chloride, Decanoyl chloride, 2-methylnonanoyl chloride, 3-methylnonanoyl chloride, 4-methylnonanoyl chloride, 5-methylnonanoyl chloride, 6-methylnonanoyl chloride, 7-methylnonanoyl chloride, 2,2- Examples include dimethyloctanoyl chloride, 2,3-dimethyloctanoyl chloride, 3,3-dimethyloctanoyl chloride, 2-ethyloctanoyl chloride, 2-propylheptanoyl chloride, 2-butylhexanoyl chloride and the like.

As the acid anhydride, for example, carboxylic acid anhydrides corresponding to the acyl group contained in the above B) acyl group and C) can be used. Examples of such carboxylic anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, 2-ethylhexanoic acid. An anhydride, nonanoic acid anhydride, etc. are mentioned.
As described above, since the cellulose derivative in the present invention preferably has no carboxylic acid as a substituent, for example, a dicarboxylic acid such as phthalic anhydride, maleic anhydride, or the like, and a compound that generates a carboxyl group by reacting with cellulose. It is preferable not to use.

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

3. Plasticizer The fiber material of the present invention may contain a plasticizer.
By containing the plasticizer, the thermal fluidity of the fiber material becomes good, contributes to the improvement of productivity at the time of melt spinning, and the spinnability can be made better.
As the plasticizer used in the present invention, any known plasticizer that is generally used as a plasticizer at the time of spinning a polymer can be used as long as it is miscible with the cellulose derivative in the present invention. For example, a polyester plasticizer And glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers and epoxy plasticizers. These plasticizers can be used alone or in combination of two or more.

  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 Examples thereof include 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, sebacin Dibutyl, and sebacic acid esters such as 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. Polyalkylene glycols such as propylene oxide addition polymers, tetrahydrofuran addition polymers of bisphenols, or terminal-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

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

  Specific examples of other plasticizers include benzoic acid 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, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, polyacrylic acid esters, and paraffins.

4). Fiber Material The fiber material of the present invention contains the cellulose derivative described above. Moreover, a plasticizer can be contained as needed, and other additives can be further contained.
The content rate of the component contained in the fiber material of this invention is not specifically limited. Preferably, the cellulose derivative is contained in an amount of 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 85 to 98% by mass.

  Although the content rate of the plasticizer contained in the fiber material of this invention is not specifically limited, It is preferable to contain 0.1-30 mass% with respect to a fiber material. By containing 0.1% by mass or more of a plasticizer, the thermal fluidity of the composition is improved, and the productivity at the time of melt spinning is more easily improved. Moreover, by setting it as the amount of plasticizers of 30 mass% or less, it becomes easy to suppress bleed-out of the plasticizer to the fiber surface, and troubles, such as sticking at room temperature, become fewer. The plasticizer content in the fiber material of the present invention is more preferably 1% by mass or more, and most preferably 5% by mass or more from the viewpoint of productivity during melt spinning. Further, from the viewpoint of suppressing bleed out, the content is more preferably 25% by mass or less, and most preferably 20% by mass or less.

  The fiber material of the present invention may contain various additives such as a filler (reinforcing material) and a flame retardant as required in addition to the cellulose derivative. Each additive is described in detail below.

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

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

  When the fiber material contains a filler, the content is not limited, but is usually 30% by mass or less, preferably 5 to 10% by mass with respect to the fiber material.

The fiber 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 compounding with resin or during spinning to corrode processing machines and molds, and the working environment is not deteriorated. The phosphorus-containing flame retardant and the silicon-containing flame retardant are preferred because they are less likely to be diffused or decomposed to adversely affect the environment due to generation of harmful substances such as dioxins.

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

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

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

  Moreover, the polyphosphate which consists of a salt of phosphoric acid, polyphosphoric acid, a periodic table group 1-14 group metal, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts and triazines.

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

  Examples of the silicon-containing flame retardant include an 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.

  As the flame retardant used in the fiber material of the present invention, a phosphoric acid ester compound is preferable from the viewpoint of plasticizing the cellulose derivative.

  When the fiber material of the present invention contains a flame retardant, its content is not limited, but is usually 30% by mass or less, preferably 2 to 10% by mass with respect to the fiber material. By setting it as this range, the fall of fiber strength or fiber elongation can be suppressed.

  The fiber material of the present invention preferably further contains an antioxidant. Thereby, since the molecular weight reduction by thermal decomposition can be suppressed, even if the addition amount to a cellulose derivative is small, a sufficient effect can be exhibited. Accordingly, it is possible to suppress the decrease in fiber strength, fiber elongation, spinnability, heat resistance, and the like possessed by the specific cellulose derivative.

  The antioxidant in the present invention may be a low molecular compound or a high molecular compound, for example, a hindered phenol antioxidant, a phosphorus antioxidant, an amine antioxidant, a sulfur oxidation. An inhibitor can be used.

  Specific examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], 1.6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadodecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide, 3,5 -Di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester and 1,3,5-trimethyl-2,4,6-tris 3,5-di -t- butyl-4-hydroxybenzyl) benzene, and the like.

  Phosphorus antioxidants include calcium hypophosphite, 2,6-di-t-butyl-4-methylphenol, tetrakis (methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ) Phenol compounds such as methane, tris (3,5-di-t-butyl-4-hydroxybenzidine) isocyanurate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropio Examples thereof include sulfur compounds such as nates, phosphorus compounds such as trisnonylphenyl phosphite and distearyl pentaerythritol diphosphite, among which calcium hypophosphite is preferable.

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

  Specific examples of sulfur-based antioxidants include sulfur-containing compounds such as thioethers, dithioacid salts such as nickel dithiocarbamate, mercaptobenzimidazoles, thiocarbanilides, and thiodipropion ester. Among these, the use of a thiodipropion ester-based compound is particularly preferable.

  As the antioxidant in the present invention, it is preferable to use a hindered phenol-based antioxidant.

  When the fiber material of the present invention contains an antioxidant, the content thereof is not limited, but is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass with respect to the fiber material. . If it is 0.01% by mass or more, the effect of adding an antioxidant can be obtained, and if it is 5% by mass or less, a decrease in fiber strength, fiber elongation, spinnability, heat resistance, etc. of the cellulose derivative is suppressed. Is preferable.

In addition to those described above, the fiber material of the present invention may contain other components for the purpose of further improving various properties such as yarn-making property and flame retardancy, as long as the object of the present invention is not impaired. .
Examples of other components include polymers other than the cellulose derivatives, stabilizers (ultraviolet absorbers, etc.), mold release agents (fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, aliphatic partially saponified esters, paraffin, low molecular weight Polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone), antistatic agent, flame retardant aid, processing aid, anti-drip agent , Antibacterial agents, fungicides and the like. Further, a coloring agent containing a dye or a pigment can be added.

As the polymer other than the cellulose derivative, either a thermoplastic polymer or a thermosetting polymer can be used, but a thermoplastic polymer is preferable from the viewpoint of spinnability. Specific examples of polymers other than cellulose derivatives include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene- 1 copolymer, polypropylene homopolymer, polypropylene copolymer (such as ethylene-propylene block copolymer), polyolefin such as polybutene-1 and poly-4-methylpentene-1, polybutylene terephthalate, polyethylene terephthalate and other aromatic polyesters, etc. Polyamide such as polyester, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 12, etc., polystyrene, high impact polystyrene, polyacetate (Including homopolymers and copolymers), polyurethanes, aromatic and aliphatic polyketones, polyphenylene sulfide, polyetheretherketone, thermoplastic starch resins, polymethyl methacrylate and methacrylate-acrylate copolymers Acrylic resin, AS resin (acrylonitrile-styrene copolymer), ABS resin, AES resin (ethylene rubber reinforced AS resin), ACS resin (chlorinated polyethylene reinforced AS resin), ASA resin (acrylic rubber reinforced AS resin) ), Polyvinyl chloride, polyvinylidene chloride, vinyl ester resin, maleic anhydride-styrene copolymer, MS resin (methyl methacrylate-styrene copolymer), polycarbonate, polyarylate, polysulfone, polyethersulfone, phenoxy resin Thermoplastic polyimide such as polyphenylene ether, modified polyphenylene ether, polyetherimide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether Fluoropolymers such as polymers, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, cellulose acetate, polyvinyl alcohol, unsaturated polyester, melamine resin, phenol resin, A urea resin, a polyimide, etc. can be mentioned.
In addition, various acrylic rubbers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers), ethylene-acrylic acid alkyl ester copolymers (for example, ethylene-ethyl acrylate copolymer) Copolymer, ethylene-butyl acrylate copolymer), diene rubber (for example, 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, polychloroprene), copolymer of diene and vinyl monomer (for example, Styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer Polymer, polybutadiene Styrene-grafted styrene, butadiene-acrylonitrile copolymer), polyisobutylene, copolymer of isobutylene and butadiene or isoprene, butyl rubber, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, nitrile rubber, 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 fiber material of this invention contains polymers other than a cellulose derivative, 30 mass parts or less are preferable with respect to 100 mass parts of cellulose derivatives, and 2-10 mass parts is more preferable.

5. Fiber The fiber of the present invention is obtained by spinning and spinning a fiber material containing the cellulose derivative. More specifically, it is obtained by a production method including a step of heating the cellulose derivative or the fiber material containing the cellulose derivative and various additives as necessary, and spinning them by various spinning methods.

  The spinning method is not particularly limited, but it is preferable to apply the melt spinning method. Manufactured by melt spinning method, easy to control fiber structure, high productivity, precise and arbitrary control of fiber cross section, core-sheath composite, eccentric core-sheath composite, side-by-side composite, etc. In addition, various types of composite fibers can be obtained, no organic solvent is used, which has an environmental impact during production, energy costs are low, and the good thermoplasticity of cellulose derivatives is used to draw spun yarn. Advantages such as easy thread processing such as twisting can be obtained.

  Specifically, the fiber material of the present invention can be produced by a method in which the fiber material of the present invention is heated and melted in a known melt extrusion spinning machine, extruded from a die, spun, and stretched and wound up as necessary. At this time, the spinning temperature is preferably 180 to 260 ° C, more preferably 190 to 250 ° C. By setting the spinning temperature to 180 ° C. or higher, the melt viscosity is lowered and the melt spinnability is improved. Moreover, the thermal decomposition of a cellulose derivative is suppressed by making spinning temperature 260 degrees C or less.

  Further, the cross-sectional shape of the fiber after spinning is not particularly limited, but any of round cross-section, triangular cross-section, multi-lobe cross-section, hollow cross-section, flat cross-section, W-type cross-section, X-type cross-section, and other irregular cross-sections. It can be selected as appropriate according to the intended use and the intended function / tactile sensation. For example, in the case of a modified cross-sectional shape having convex portions and concave portions such as triangles and six leaves, an elegant gloss can be obtained in the fibers.

Although the single fiber fineness of the fiber is not particularly limited, for example, 0.5 dtex or more is preferable from the viewpoint of creating a sense of sharpness, and 50 dtex or less is preferable from the viewpoint of obtaining a soft texture.
Further, it is preferably 1 dtex or more from the viewpoint of maintaining strength, and preferably 40 dtex or less from the viewpoint of obtaining a soft texture.

  Furthermore, the fiber of this invention can be made into arbitrary shapes according to a use other than a thread form, such as cotton form, cloth form, or nonwoven fabric form.

  Although the use of the fiber of the present invention is not particularly limited, for example, as clothing, sportswear, homewear, coat, blouson, sweater, blouse, shirt, skirt, slacks, indoor sportswear, pajamas, Sleepwear, underwear, office wear, work clothes, food lab coats, nursing lab coats, patient garments, nursing clothes, school uniforms, kitchen garments, and the like. Examples of miscellaneous goods include an apron, towel, gloves, muffler, socks, hat, shoes, sandals, bag, umbrella, and the like. Interior items include curtains, carpets, mats, kotatsu covers, sofa covers, cushion covers, sofa lands, toilet seat covers, toilet seat mats, tablecloths, and the like. Examples of bedding products include futon side, futon stuffed blanket, blanket side, pillow filling, sheets, waterproof sheets, duvet covers, pillow covers, and the like. Examples of nursing supplies include supporters, corsets, rehabilitation shoes, underwear, diaper covers, and accessories.

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

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

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

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

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

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

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

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

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

<Example 1>
Using a kneader, 88% by mass of the cellulose polymer (C-1) obtained in Synthesis Example 1 and 12% by mass of a plasticizer (dioctyl adipate) obtained by vacuum drying at 100 ° C. for 12 hours. The mixture was kneaded at 200 ° C. to obtain a pellet-shaped composition.
This composition was melted at a melter temperature of 230 ° C. using a single-screw melt spinning machine, and introduced into a melt spinning pack having a spinning temperature of 230 ° C., and a discharge rate of 6.3 g / min. Spinning was performed from a die having 6 holes of 23 mmφ−0.30 mmL. The spun yarn is cooled by a chimney wind at 25 ° C., applied with an oil agent, converged, taken up by a first godet roller rotating at 450 m / min, and rotated at the same speed as the first godet roller. It wound up with the winder which rotates at the speed | rate from which winding tension | tensile_strength becomes 0.1 cN / dtex via 2 godet rollers. The yarn-making property was extremely good, and no yarn breakage was observed (evaluation ○).
The obtained fiber had a strength of 1.5 cN / dtex, an elongation of 29%, and a single yarn fineness of 22 dtex.
An attempt was made to fabricate the obtained fiber with a tubular knitting machine (cylinder knitting machine MR1 type, Maruzen Sangyo Co., Ltd., 27 gauge). As a result, the knitting fabric had good knitting properties and a soft texture. Obtained (evaluation ○).

<Example 2>
In the production example of Example 1, the cellulose polymer used was changed from (C-1) to (C-2) to obtain a pellet-shaped composition.
In the same manner, melt spinning was carried out, the yarn making property was extremely good, and no yarn breakage was observed (evaluation ○). The obtained fiber had a strength of 1.4 cN / dtex, an elongation of 25%, and a single yarn fineness of 24 dtex.
An attempt was made to fabricate the obtained fiber with a tubular knitting machine (cylinder knitting machine MR1 type, Maruzen Sangyo Co., Ltd., 27 gauge). As a result, the knitting fabric had good knitting properties and a soft texture. Obtained (evaluation ○).

<Example 3>
In the production example of Example 1, the cellulose polymer to be used was changed from (C-1) to (C-3) to obtain a pellet-shaped composition.
In the same manner, melt spinning was carried out, the yarn making property was extremely good, and no yarn breakage was observed (evaluation ○). The obtained fiber had a strength of 1.1 cN / dtex, an elongation of 30%, and a single yarn fineness of 21 dtex.
An attempt was made to fabricate the obtained fiber with a tubular knitting machine (cylinder knitting machine MR1 type, Maruzen Sangyo Co., Ltd., 27 gauge). As a result, the knitting fabric had good knitting properties and a soft texture. Obtained (evaluation ○).

<Example 4>
In the production example of Example 1, the cellulosic polymer used was changed from (C-1) to (C-4) to obtain a pellet-shaped composition.
In the same manner, melt spinning was carried out, the yarn making property was extremely good, and no yarn breakage was observed (evaluation ○). The obtained fiber had a strength of 1.2 cN / dtex, an elongation of 30%, and a single yarn fineness of 22 dtex.
An attempt was made to fabricate the obtained fiber with a tubular knitting machine (cylinder knitting machine MR1 type, Maruzen Sangyo Co., Ltd., 27 gauge). As a result, the knitting fabric had good knitting properties and a soft texture. Obtained (evaluation ○).

<Example 5>
In the production example of Example 1, the cellulosic polymer used was changed from (C-1) to (C-5) to obtain a pellet-shaped composition.
In the same manner, melt spinning was carried out, the yarn making property was extremely good, and no yarn breakage was observed (evaluation ○). The obtained fiber had a strength of 1.0 cN / dtex, an elongation of 39%, and a single yarn fineness of 20 dtex.
An attempt was made to produce the knitted fabric with the obtained fiber using a cylinder knitting machine (cylinder knitting machine MR1 type, 27 gauge manufactured by Maruzen Sangyo Co., Ltd.). As a result, knitting has good knitting properties and a very soft texture. The ground was obtained (evaluation ○).

<Example 6>
In the production example of Example 1, the cellulose polymer used was changed from (C-1) to (C-6) to obtain a pellet-shaped composition.
Similarly, melt spinning was carried out, and the yarn-making property was good, but yarn breakage occurred frequently (evaluation Δ). The obtained fiber had a strength of 1.0 cN / dtex, an elongation of 24%, and a single yarn fineness of 22 dtex.
An attempt was made to fabricate the obtained fiber with a tubular knitting machine (cylinder knitting machine MR1 type, Maruzen Sangyo Co., Ltd., 27 gauge). The knitting fabric had good knitting properties and a soft texture but had some wrinkles. The ground was obtained (evaluation △).

<Example 7>
In the production example of Example 1, the cellulose polymer used was changed from (C-1) to (C-7) to obtain a pellet-shaped composition.
Similarly, melt spinning was carried out, and the yarn-making property was good, but yarn breakage occurred frequently (evaluation Δ). The obtained fiber had a strength of 1.0 cN / dtex, an elongation of 21%, and a single yarn fineness of 20 dtex.
An attempt was made to fabricate the obtained fiber with a tubular knitting machine (cylinder knitting machine MR1 type, Maruzen Sangyo Co., Ltd., 27 gauge). The knitting fabric had good knitting properties and a soft texture but had some wrinkles. The ground was obtained (evaluation △).

<Example 8>
A pellet-like cellulose derivative was obtained in the same manner as in the production example of Example 1, except that the plasticizer was not used and only the cellulose polymer (C-5) was changed to 100% by mass.
Similarly, melt spinning was carried out, and the yarn-making property was good, but yarn breakage occurred frequently (evaluation Δ). The obtained fiber had a strength of 1.1 cN / dtex, an elongation of 35%, and a single yarn fineness of 21 dtex.
An attempt was made to fabricate the obtained fiber with a cylinder knitting machine (Cylinder knitting machine MR1 type, 27 gauge manufactured by Maruzen Sangyo Co., Ltd.), but the knitting property was somewhat difficult but has a soft texture. A knitted fabric was obtained (evaluation ○).

<Comparative Example 1>
In the production example of Example 1, the cellulose polymer to be used was changed from (C-1) to (H-1) to obtain a pellet-shaped composition.
In the same manner, melt spinning was carried out, the yarn making property was extremely good, and no yarn breakage was observed (evaluation ○). The obtained fiber had a strength of 0.8 cN / dtex, an elongation of 18%, and a single yarn fineness of 21.0 dtex.
An attempt was made to fabricate the obtained fiber with a cylinder knitting machine (Cylinder knitting machine MR1 type, 27 gauge manufactured by Maruzen Sangyo Co., Ltd.). The knitted fabric was good, but it was stiff and stiff. A knitted fabric having a texture was obtained (evaluation x).

(Strength and elongation)
Using Tensilon UCT-100 manufactured by Orientec Co., Ltd., a tensile test was performed under the conditions of a sample length of 20 cm and a tensile speed of 20 cm / min, and the stress at the point indicated by the maximum load was defined as the fiber strength (cN / dtex). The elongation at break was defined as the fiber elongation (%).
(Single yarn fineness)
This is a value obtained by dividing the fineness of the multifilament obtained by melt spinning by the number of die holes.
(Spinning property)
When fiberizing by the melt spinning method, ○ that can be produced stably without yarn breakage, ○ that the running yarn is not stable and yarn breakage frequently occurs ×, yarn breakage frequently occurs What to do is marked with △.
(Texture)
A 27-gauge circular knitting was produced using the obtained fiber, and the texture was evaluated by sensory survey. A high-quality product having a soft texture was rated as “◯”, a low-quality product that had a slimy feeling, or was stiff or colored, and “×”, and an intermediate product was evaluated as “△”.

As is clear from the above results, Examples 1 to 8 are superior to Comparative Example 1 in terms of fiber strength and fiber elongation, as well as good spinning and spinning properties and texture. Especially Examples 1-5 are kept at a high level for all evaluated.
From the above results, it is clear that, by satisfying the requirements of the present invention, a fiber material excellent in fiber strength and fiber elongation and excellent in spinning and spinning can be realized without impairing the inherent texture of cellulose. is there.

Claims (14)

The hydrogen atom of the hydroxyl group contained in cellulose
A fiber material comprising a cellulose derivative comprising at least one group substituted in A) below and at least one group substituted in B) below.
A) Hydrocarbon group: -R _A
B) Acyl group: —CO—R _B (R _B represents a hydrocarbon group.) The fiber material according to claim 1, wherein the cellulose derivative further contains at least one group in which a hydrogen atom of a hydroxyl group contained in cellulose is substituted by the following C).
C) a group containing an alkyleneoxy group: —R _C2 —O— and an acyl group: —CO—R _C1 (R _C1 represents a hydrocarbon group, and R _C2 represents an alkylene group having 2 or 3 carbon atoms. ) The fiber material according to claim 1 or 2, wherein the C) group containing an alkyleneoxy group and an acyl group is a group containing a structure represented by the following general formula (3).

(Wherein R _C1 represents a hydrocarbon group, R _C2 represents an alkylene group having 2 or 3 carbon atoms, and n represents an integer of 1 or more.) The fiber material in any one of Claims 1-3 whose said _RA is a C1-C4 alkyl group. The fiber material according to any one of claims 1 to 4, wherein the _RA is a methyl group or an ethyl group. The fiber material according to any one of claims 1 to 5, wherein R _B and R _C1 are each independently an alkyl group or an aryl group. The fiber material according to any one of claims 1 to 6, wherein R _B and R _C1 are each independently a methyl group, an ethyl group, or a propyl group. Wherein R _B is a hydrocarbon group having a branched structure having 3 to 10 carbon atoms, fiber material according to any one of claims 1 to 6. The fiber 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).

  The fiber material in any one of Claims 1-9 in which the said cellulose derivative does not have a carboxyl group, a sulfonic acid group, and these salts substantially.   The fiber material according to any one of claims 1 to 10, wherein the cellulose derivative is insoluble in water.   Furthermore, the fiber material in any one of Claims 1-11 containing a plasticizer.   A fiber obtained by spinning the fiber material according to claim 1.   The fiber according to claim 13, wherein the shape is a thread, cotton, cloth or non-woven fabric.