JP6002440B2 - Method for producing polysaccharide solid, polysaccharide solid, cord, fiber-rubber composite, film-rubber composite, and tire - Google Patents

Description

  The present invention relates to a method for producing a polysaccharide solid, a polysaccharide solid, a cord, a fiber-rubber composite, a film-rubber composite, and a tire.

Cellulose fibers have advantages such as good dimensional stability, high adhesiveness, and low temperature dependency of elastic modulus (elastic modulus change with respect to temperature change), and are widely used in tires as rayons.
However, rayon emits carbon disulfide in the manufacturing process and has a very high environmental impact, so it does not meet the modern needs of manufacturing products with raw materials with low environmental impact.

The characteristics such as good dimensional stability, high adhesion, and low temperature dependence of elastic modulus largely depend on the fiber material being cellulose. Synthetic fibers such as polyester and nylon are also used as tire reinforcing cords, but it is difficult to obtain dimensional stability, adhesiveness, and elastic modulus comparable to cellulose fibers.
Therefore, the present situation is that rayon is used for some tires despite the high environmental load.

  In recent years when environmental preservation of the earth is screamed, it is desired to use cellulose that does not depend on fossil fuels as a raw material. The necessity of using carbon disulfide, which has a high environmental impact in the production of rayon, which is the above-mentioned problem, is to melt or dissolve cellulose when it is made into a film or fiber (spun). In order to melt or dissolve the cellulose raw material, it is necessary to break hydrogen bonds in and between the hydroxyl groups at three positions per one repeating unit of cellulose. In the production of rayon, the hydroxyl raw material can be chemically modified with carbon disulfide to break the hydrogen bond, so that the cellulose raw material can be melted or dissolved. Thus, the cellulose fiber spun by chemically modifying the hydroxyl group is generally called regenerated cellulose. Currently, the reason why cellulose fibers other than rayon are not widely used for tire reinforcement is that, in addition to the difficulty of melting and dissolving cellulose raw materials in an industrially established manner, high strength when fiberized, The method for obtaining the cut elongation is in a difficult point.

  On the other hand, according to the method for producing purified cellulose fiber using N-methylmorpholine-N-oxide (NMMO) as a solvent, cellulose is not accompanied by chemical modification of cellulose itself and without discharging carbon disulfide. It is possible to dissolve the raw material, and the purified cellulose fiber obtained by dry-wet spinning cellulose using the cellulose solution produced by this method has a low environmental impact and has a chemically modified hydroxyl group. It is excellent in that it does not remain (Patent Document 1).

  However, purified cellulose fibers produced using NMMO as a solvent do not satisfy the physical properties necessary for application to tires such as strength and cut elongation.

  On the other hand, it has been reported that several types of ionic liquids efficiently dissolve cellulose raw materials (Patent Documents 2 to 4). Dissolution of the cellulose raw material by the ionic liquid is due to solvation, and does not discharge harmful substances such as carbon disulfide in the manufacturing process of the purified cellulose fiber. The production of the purified cellulose fiber is easily achieved by passing the dissolved cellulose raw material through water, alcohol, or an aqueous solution of water and an ionic liquid. The spinning of cellulose using such an ionic liquid is reported in Patent Documents 5 and 6.

JP 2006-188806 A U.S. Pat. No. 1,943,176 JP 60-144322 A Japanese Patent No. 4242768 US Patent Application Publication No. 2008/0269477 Chinese Patent No. 101382626 Specification

However, since a polysaccharide solution obtained by dissolving a polysaccharide raw material containing a polysaccharide such as cellulose in an ionic liquid has a high viscosity, unless the step of dissolving the polysaccharide raw material is performed under vacuum In the polysaccharide solution, gas components such as air are included.
Then, when the polysaccharide solution containing the gas component is brought into contact with the solidified liquid to solidify the polysaccharide and produce the polysaccharide solid, the gas component remains in the polysaccharide solid and the physical properties of the product This causes a problem of lowering.

  In the case of producing fibers from a polysaccharide solution, if the fiber component is spun while the gas component is encapsulated in the polysaccharide solution, the gas component is encapsulated in the fiber, and the mechanical properties of the fiber are inferior. Many yarn breaks occur during production, greatly affecting productivity.

  In the case of producing a film from a polysaccharide solution, if the film is produced with the gas component contained in the polysaccharide solution, the gas component is included in the film, and the mechanical properties of the film are inferior. At the same time, since the gas component contained in the film becomes a scatterer, the optical properties of the film are inferior.

  For such problems, if the polysaccharide raw material is dissolved in the ionic liquid under vacuum or reduced pressure, the gas component will not be included, but the elongation fluidity of the polysaccharide solution will decrease, and the product will Physical properties and productivity are reduced.

  The present invention has been made in view of the above circumstances, and has a low environmental impact with suppressed carbon disulfide emissions, a method for producing a polysaccharide solid material with excellent productivity, and without including a gas component, An object is to provide a solid polysaccharide, cord, fiber-rubber composite, film-rubber composite, and tire having good physical properties.

［式中、Ｒ^１は、炭素数１〜４のアルキル基、又は炭素数２〜４のアルケニル基を示し、Ｒ^２は、水素原子又はメチル基を示し、Ｒ^３は、炭素数１〜８のアルキル基、又は炭素数２〜８のアルケニル基を示す。］
（５）前記多糖類溶解液を前記固形化液体中に吐出させて、前記多糖類固形物として繊維を得る（１）から（４）のいずれか一つの多糖類固形物の製造方法。
（６）前記多糖類溶解液を前記固形化液体中にシート状に吐出させて、前記多糖類固形物としてフィルムを得る（１）から（４）のいずれか一つの多糖類固形物の製造方法。
（７）（１）から（６）のいずれか一つの多糖類固形物の製造方法を用いて製造したことを特徴とする多糖類固形物。
（８）（７）の多糖類固形物が繊維形状であって、前記多糖類固形物の繊維を撚り加工してなることを特徴とするコード。
（９）（７）の多糖類固形物が繊維形状であって、前記多糖類固形物の繊維又は（８）のコードを用いたことを特徴とする繊維−ゴム複合体。
（１０）（９）の繊維−ゴム複合体を用いたことを特徴とするタイヤ。
（１１）（７）の多糖類固形物がフィルム形状であって、前記多糖類固形物のフィルムを用いたことを特徴とするフィルム−ゴム複合体。
（１２）（１１）のフィルム−ゴム複合体を用いたことを特徴とするタイヤ。 The present invention provides a method for producing a polysaccharide solid having the following characteristics, the polysaccharide solid, a cord, a fiber-rubber composite, a film-rubber composite, and a tire.
(1) A method for producing a polysaccharide solid, wherein a polysaccharide solution obtained by dissolving a polysaccharide raw material in a liquid containing an ionic liquid is brought into contact with a solidifying liquid to solidify the polysaccharide. method for producing a polysaccharide solids, characterized in that after degassing the saccharide solution under pressure into contact with the solidified liquid.
(2) The ionic liquid includes a cation portion and an anion portion, and the cation portion is one or more selected from the group consisting of an imidazolium ion, a pyridinium ion, an ammonium ion, and a phosphonium ion. A method for producing a saccharide solid.
(3) The said solidification liquid is a manufacturing method of the polysaccharide solid of (1) or (2) which is 1 or more types chosen from the group which consists of water, a polar solvent, and the said ionic liquid.
(4) The method for producing a polysaccharide solid according to (2) or (3), wherein the cation moiety is an imidazolium ion represented by the following general formula (1).

[Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents 1 to 8 carbon atoms. Or an alkenyl group having 2 to 8 carbon atoms. ]
(5) The method for producing a polysaccharide solid according to any one of (1) to (4), wherein the polysaccharide solution is discharged into the solidified liquid to obtain fibers as the polysaccharide solid.
(6) The method for producing a polysaccharide solid according to any one of (1) to (4), wherein the polysaccharide solution is discharged into the solidified liquid in a sheet form to obtain a film as the polysaccharide solid. .
(7) A polysaccharide solid produced by using the method for producing a polysaccharide solid according to any one of (1) to (6).
(8) The cord is characterized in that the polysaccharide solid material of (7) has a fiber shape and is formed by twisting the fibers of the polysaccharide solid material .
(9) A fiber-rubber composite , wherein the polysaccharide solid of (7) is in the form of a fiber, and the fiber of the polysaccharide solid or the cord of (8) is used.
(10) A tire using the fiber-rubber composite of (9).
(11) A film-rubber composite , wherein the polysaccharide solid of (7) is in the form of a film and the film of the polysaccharide solid is used.
(12) A tire using the film-rubber composite of (11).

Since the method for producing a polysaccharide solid according to the present invention can produce a polysaccharide solid without producing harmful substances such as carbon disulfide, the environmental load can be reduced.
Furthermore, the method for producing a polysaccharide solid according to the present invention is excellent in productivity because a gas component is not included in the polysaccharide solid.
Moreover, since the polysaccharide solid of this invention does not enclose a gas component in this polysaccharide solid, the physical property is favorable.

[Polysaccharide solids]
First, the preferable manufacturing method of the polysaccharide solid substance used for this invention is demonstrated.

  In the method for producing a polysaccharide solid according to the present invention, a polysaccharide solution obtained by dissolving a polysaccharide raw material in a liquid containing an ionic liquid is brought into contact with the solidified liquid to solidify the polysaccharide. This is a production method in which the polysaccharide solution is degassed under normal pressure or under pressure and then contacted with the solidified liquid.

Examples of polysaccharides in polysaccharide raw materials (raw materials containing polysaccharides) used in the present invention include cellulose and cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, nitrocellulose, and cationized cellulose; gum arabic Carrageenan such as κ-carrageenan, ι-carrageenan, and λ-carrageenan; guar gum; locust bean gum; pectin; tragacanth; corn starch; phosphorylated starch; Used.
The polysaccharide solid material of the present invention is obtained by bringing a polysaccharide solution obtained by dissolving a polysaccharide raw material including a cellulose raw material into a liquid containing an ionic liquid into contact with the solidifying liquid to solidify the polysaccharide. It will be. When manufacturing a fiber using the said polysaccharide solid substance, it is preferable that this solidification method is what carried out wet spinning or dry-wet spinning.
The spinning method of the wet spinning or the dry wet spinning is not particularly limited, and the fiber can be spun by a known spinning method.

In the present invention, the cellulose raw material is not particularly limited as long as it contains cellulose, and may be a plant-derived cellulose raw material, an animal-derived cellulose raw material, or a microorganism-derived cellulose raw material. Or a regenerated cellulose raw material.
Plant-derived cellulose raw materials include cellulose raw materials derived from unprocessed natural plants such as wood, cotton, hemp and other herbs, and plants derived from plants that have been processed in advance, such as pulp, wood flour, and paper products. Examples include processed cellulose raw materials.
Examples of animal-derived cellulose raw materials include squirt-derived cellulose raw materials.
Examples of the cellulose raw material derived from microorganisms include those produced by the raw materials of microorganisms belonging to the genus Aerobacter, Acetobacter, Achromobacter, Agrobacterium, Alacaligenes, Azotobacter, Pseudomonas, Rhizobium, Sarcina, etc.
Examples of the regenerated cellulose raw material include a cellulose raw material obtained by regenerating a cellulose raw material derived from plants, animals, or microorganisms as described above by a known method such as a viscose method.
Especially, as a cellulose raw material used in this invention, the pulp which melt | dissolves favorably in an ionic liquid is preferable.

  In the present invention, before the polysaccharide raw material containing cellulose or the like is dissolved in the liquid containing the ionic liquid, the polysaccharide raw material can be pretreated for the purpose of improving the solubility in the ionic liquid. Specifically, the pretreatment may include a drying treatment, a physical pulverization treatment such as pulverization and grinding, a chemical modification treatment using an acid or an alkali, and the like. Any of these can be performed by a conventional method.

  In the present invention, the ionic liquid refers to a solvent that is liquid at 100 ° C. or lower and is composed only of ions, and the cation part or the anion part or both are composed of organic ions.

The ionic liquid is preferably composed of a cation portion and an anion portion. The cation portion of the ionic liquid is not particularly limited, and may be generally used for the cation portion of the ionic liquid.
Especially, as a preferable thing of the cation part of the ionic liquid used for this invention, a nitrogen-containing aromatic cation, an ammonium ion, and a phosphonium ion are mentioned.

Specific examples of the nitrogen-containing aromatic cation include pyridinium ion, pyridazinium ion, pyrimidinium ion, pyrazinium ion, imidazolium ion, pyrazonium ion, oxazolium ion, 1,2,3-triazoli. Umum ion, 1,2,4-triazolium ion, thiazolium ion, piperidinium ion, pyrrolidinium ion and the like.
Especially, as a nitrogen-containing aromatic cation, an imidazolium ion and a pyrimidinium ion are preferable, and an imidazolium ion represented by the following general formula (C3) is more preferable.

［式中、Ｒ^５及びＲ^６は、それぞれ独立に、炭素数１〜１０のアルキル基、又は炭素数２〜１０のアルケニル基であり、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、又は炭素数１〜１０のアルキル基である。］

[Wherein R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and R ⁷ , R ⁸ and R ⁹ are each independently A hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

In formula (C3), R ^{5 to} R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. .
Specific examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
Specific examples of the branched alkyl group include 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2, Examples thereof include 2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.
The cyclic alkyl group may be a monocyclic group or a polycyclic group. Specific examples include monocyclic groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, and polycyclic groups such as norbornyl group, adamantyl group, and isobornyl group.
The number of carbon atoms in the alkyl group in R ⁵ to R ⁶ is preferably 1-8.
Examples of the alkenyl group having 2 to 10 carbon atoms include an alkyl group having 2 to 10 carbon atoms in which one carbon-carbon single bond is substituted with a double bond. Preferred examples include a vinyl group, Examples include allyl group. The position of the double bond is not particularly limited.
The number of carbon atoms of the alkenyl group for R ⁵ to R ⁶ is preferably 2-8.
R ^{5 to} R ⁶ may be the same or different from each other.

In formula (C3), R ^{7 to} R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. . Here, examples of the linear, branched, and cyclic alkyl groups include the same alkyl groups as those described above for R ^{5 to} R ⁶ .
The number of carbon atoms of the alkyl group in R ^{7 to} R ⁹ is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1.
R ^{7 to} R ⁹ may be the same or different from each other.

  A preferred specific example of the imidazolium ion represented by the formula (C3) is shown as the following formula (1).

［式中、Ｒ^１は、炭素数１〜４のアルキル基、又は炭素数２〜４のアルケニル基を示し、Ｒ^２は、水素原子又はメチル基を示し、Ｒ^３は、炭素数１〜８のアルキル基、又は炭素数２〜８のアルケニル基を示す。］

[Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents 1 to 8 carbon atoms. Or an alkenyl group having 2 to 8 carbon atoms. ]

  Moreover, the preferable specific example of an imidazolium ion represented by Formula (1) is shown as following formula (1-1)-(1-3).

The phosphonium ion is not particularly limited as long as it has “P ⁺ ”. Specifically, the phosphonium ion is preferably a general formula “R ₄ P ⁺ (a plurality of R are independently hydrogen atoms). It is an atom or a hydrocarbon group having 1 to 30 carbon atoms.) ”.
The hydrocarbon group having 1 to 30 carbon atoms may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group is preferably a saturated hydrocarbon group (alkyl group), and the alkyl group may be linear, branched, or cyclic.
The linear alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 16 carbon atoms. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, A hexadecyl group etc. are mentioned.
The branched alkyl group has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 16 carbon atoms. Specifically, 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylbutyl Group, 2-methylbutyl group, 3-methylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.
The cyclic alkyl group has 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 16 carbon atoms, and even a monocyclic group, It may be a polycyclic group. Specific examples include monocyclic groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, and polycyclic groups such as norbornyl group, adamantyl group, and isobornyl group.
The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms. Specifically, an aryl group such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl group, a tolyl group, or a benzyl group And arylalkyl groups such as a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.
Here, the plurality of R in the general formula “R ₄ P ⁺ ” may be the same or different.

  Especially, as a phosphonium ion, the cation part represented by a following formula (C1) is preferable.

［式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立に、炭素数１〜１６のアルキル基である。］

[Wherein, R ^{31 to} R ³⁴ each independently represents an alkyl group having 1 to 16 carbon atoms. ]

In formula (C1), R ^{31 to} R ³⁴ are each independently an alkyl group having 1 to 16 carbon atoms. The alkyl group having 1 to 16 carbon atoms may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. . Here, examples of the linear, branched, and cyclic alkyl groups include those described above.
R ^{31 to} R ³⁴ may be the same or different from each other, but it is preferable that three or more of R ^{31 to} R ³⁴ are the same from the viewpoint of availability.

Among them, in the present invention, the alkyl group of R ³¹ to R ^34, preferably a linear or branched alkyl group having 1 to 14 carbon atoms, straight-chain or branched-chain having 1 to 10 carbon atoms Are more preferable, linear or branched alkyl groups having 1 to 8 carbon atoms are more preferable, and linear or branched alkyl groups having 1 to 4 carbon atoms are particularly preferable.
A preferred specific example of the cation moiety represented by the formula (C1) is shown as the following formula (C2).

  In the present invention, the cation moiety is more preferably at least one selected from the group consisting of imidazolium ions, pyridinium ions, ammonium ions, and phosphonium ions.

In the present invention, examples of the anion moiety include halogen ions, carboxylate ions, phosphate ions, phosphonate ions, and phosphinate ions.
Examples of the halogen ion include ions such as chloride, bromide, and iodide, and chloride ion is preferable.
Examples of the carboxylate ion include formate, acetate, propionate, butyrate, hexanoate, maleate, fumarate, oxalate, lectate, pyruvate, and the like. Formate ion, acetate ion, and propionate ion are preferable.
As a phosphate ion, what is represented by the following general formula (A1) is mentioned.

［式中、Ｒ^２５及びＲ^２６はそれぞれ独立に水素原子、又はアルキル基である。］

[Wherein, R ²⁵ and R ²⁶ each independently represent a hydrogen atom or an alkyl group. ]

In formula (A1), R ²⁵ and R ²⁶ are each independently a hydrogen atom or an alkyl group, and the alkyl group may be any of linear, branched, and cyclic, It is preferably a linear or branched alkyl group. The carbon number of the alkyl group of R ²⁵ and R ²⁶ is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and carbon number 1 for industrial reasons. Or an alkyl group of 2 is particularly preferred.
R ²⁵ and R ²⁶ may be the same or different.

  Of these phosphate ions, diethyl phosphate ions are preferred.

  Examples of the phosphonate ion include those represented by the following general formula (A2).

［式中、Ｒ^２５は上記と同様である。］

[Wherein R ²⁵ is the same as defined above. ]

Wherein ^{(A2), R 25} is the same as ^{R 25} in the formula (A1).

  Of these phosphonate ions, methyl phosphonate ions are preferred.

  The phosphinate ion is represented by the following general formula (A3).

  In addition, pseudohalogen ions may be mentioned as other anion moieties. Pseudohalogen ions have properties similar to those of halogen ions. Pseudohalogen ions include ions such as cyanate, oxocyanate, thiocyanate, and selenocyanate.

  In the present invention, the anion moiety is more preferably one or more ions selected from the group consisting of chloride, formate, acetate, propionate, diethyl phosphate ion, methyl phosphonate, and phosphinate.

The ionic liquid in the present invention is composed of a cation portion and an anion portion as described above. The combination of a cation part and an anion part is not specifically limited, The thing which can melt | dissolve a polysaccharide raw material suitably can be suitably selected 1 or more types.
Preferred ionic liquids include 1-allyl-3-methylimidazolium chloride (AmimCl), 1-ethyl-3-methylimidazolium acetate (C2mimAc), 1-ethyl-3-methylimidazolium diethylphosphate (C2mim (EtO)) ₂ PO _2), 1-ethyl-3-methylimidazolium methyl phosphonate Nate (C2mim MeOHPO _2), or 1-ethyl-3-methylimidazolium phosphinothricin Nate (C2mim H ₂ PO _2), and the like.

  In the present invention, the use amount of the ionic liquid is not particularly limited, but the concentration of the polysaccharide raw material in the polysaccharide solution is preferably 3 to 30% by mass, and 5 to 25% by mass. It is more preferable. When the concentration of the polysaccharide raw material is too low, there are many ionic liquids that are removed during the solidification process, and when fibers are produced as polysaccharide solids, it is difficult to form dense fibers and it is difficult to produce strength. On the other hand, when the concentration of the polysaccharide raw material is too high, the polysaccharide raw material cannot be completely dissolved.

  In the present invention, the liquid that dissolves the polysaccharide raw material containing cellulose or the like contains the ionic liquid. The liquid may or may not contain liquid components other than the ionic liquid. Specific examples of liquid components other than the ionic liquid include organic solvents.

The organic solvent is not particularly limited as long as it is other than the ionic liquid, and can be appropriately selected in consideration of compatibility with the ionic liquid, viscosity, and the like.
Among these, the organic solvent is preferably at least one selected from the group consisting of amide solvents, sulfoxide solvents, nitrile solvents, cyclic ether solvents, and aromatic amine solvents.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone and the like.
Examples of the sulfoxide solvent include dimethyl sulfoxide and hexamethylene sulfoxide.
Examples of nitrile solvents include acetonitrile, propionitrile, benzonitrile and the like.
Examples of the cyclic ether solvent include 1,3-dioxolane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1,3,5-trioxane and the like.
Examples of the aromatic amine solvent include pyridine.

When these organic solvents are used, the blending mass ratio between the ionic liquid and the organic solvent is preferably 6: 1 to 0.1: 1, and more preferably 5: 1 to 0.2: 1. More preferably, it is 4: 1 to 0.5: 1. By setting it as the said range, it can be set as the solvent which is easy to swell a polysaccharide raw material.
Moreover, the usage-amount of an organic solvent is although it does not specifically limit, It is preferable that it is 1-30 mass parts with respect to 1 mass part of polysaccharide raw materials, and it is preferable that it is 1-25 mass parts. More preferably, it is -20 mass parts. By setting it as the said range, it can be set as the polysaccharide solution of moderate viscosity.
The organic solvent as described above is preferable because the solubility of the polysaccharide raw material is further improved by using it together with the ionic liquid.

In the present invention, the method for dissolving the polysaccharide raw material containing cellulose or the like in the liquid containing the ionic liquid is not particularly limited. For example, the liquid containing the ionic liquid and the polysaccharide raw material are brought into contact with each other. A polysaccharide solution can be obtained by performing heating and stirring according to the conditions.
The method for bringing the liquid containing the ionic liquid into contact with the polysaccharide raw material is not particularly limited. For example, the polysaccharide raw material may be added to the liquid containing the ionic liquid, or the ionic liquid may be added to the polysaccharide raw material. A liquid containing may be added.
When heating is performed during dissolution, the heating temperature is preferably 30 to 200 ° C, more preferably 70 to 180 ° C. By heating, the solubility of the polysaccharide raw material containing cellulose and the like is further improved, which is preferable.
The stirring method is not particularly limited, and the liquid containing the ionic liquid and the polysaccharide raw material may be mechanically stirred using a stirrer, a stirring blade, a stirring rod, etc., and the liquid containing the ionic liquid And the polysaccharide raw material may be sealed in a sealed container and stirred by shaking the container. The stirring time is not particularly limited, and it is preferable to carry out the stirring until the polysaccharide raw material is suitably dissolved.

In addition, when the liquid containing the ionic liquid contains an organic solvent in addition to the ionic liquid, the organic solvent and the ionic liquid may be mixed in advance, and after mixing the ionic liquid and the polysaccharide raw material, A solvent may be added and dissolved, or after mixing an organic solvent and a polysaccharide raw material, an ionic liquid may be added and dissolved.
Especially, it is preferable to mix an organic solvent and an ionic liquid beforehand, and to manufacture a liquid mixture. At this time, it is preferable to stir while heating at 70 to 180 ° C. for about 5 to 30 minutes so that the organic solvent and the ionic liquid are uniformly mixed, and to mix until the liquid containing the ionic liquid becomes uniform. .
The polysaccharide solution obtained from the ionic liquid thus obtained may contain additives such as fillers such as carbon nanotubes, clay and silica, surfactants and anti-aging agents, if necessary.

The polysaccharide solution thus obtained may have a high viscosity, in which case gas components such as air are likely to be included. Conventionally, the polysaccharide raw material is dissolved under vacuum or under reduced pressure to prevent the gas component from being included in the polysaccharide dissolving solution. A step of defoaming the solution under normal pressure or under pressure. By having such a step, it is possible to suppress a decrease in the elongation fluidity of the polysaccharide solution generated by dissolving the polysaccharide raw material under vacuum or under reduced pressure.
The pressure under pressure is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, and particularly preferably 1.0 MPa or more. The upper limit is preferably 200 MPa or less.
Examples of the defoaming method include a method of separating a gas component from a polysaccharide solution, or a method of dissolving a gas component in a polysaccharide solution. More specifically, centrifugal defoaming, continuous defoaming, ultrasonic defoaming, or defoaming using a single-screw extruder or a multi-screw extruder may be mentioned.
In the case of using a single screw extruder or a twin screw extruder, for example, defoaming is performed via a vent portion.

The polysaccharide solution obtained as described above is brought into contact with a solidifying liquid to solidify the polysaccharide to produce a polysaccharide solid. When the fiber is produced as the polysaccharide solid, it can be spun by a known spinning method such as dry-wet spinning or wet spinning.
Dry-wet spinning is a method of spinning a polysaccharide by introducing a polysaccharide solution once discharged into a gas from a spinneret into a solidification tank that holds the solidification liquid.
Wet spinning is a method of spinning a polysaccharide by discharging a polysaccharide solution from a spinneret disposed in the solidification tank.
Moreover, when manufacturing a film as the said polysaccharide solid substance, the polysaccharide solution discharged in the sheet form from die | dye is made to contact the said solidification liquid, and a polysaccharide is solidified. There is no limitation in the manufacturing method which produces a film.
A solidification tank means the bathtub by which the solidification liquid for solidifying a polysaccharide was hold | maintained. As said solidification liquid, 1 or more types chosen from the group which consists of water, a polar solvent, and the ionic liquid mentioned above are mentioned preferably.
Examples of the polar solvent include tetrahydrofuran, acetone, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, acetic acid, 1-butanol, 2-propanol, 1-propanol, ethanol, methanol, formic acid and the like.

[Fiber-Rubber Composite]
A high-performance tire can be obtained by using the fiber-rubber composite of the present invention using the fiber thus obtained for a carcass ply or a band ply. Especially, it is preferable to use the fiber-rubber composite of the present invention for the carcass ply, and a tire excellent in pressure resistance and side cut resistance can be obtained.
Moreover, although a fiber-rubber composite may be used for at least one of the carcass ply and the band ply, it can also be used for both the carcass ply and the band ply.

  As the cords produced from the fibers, a single twist structure composed of one twisted filament bundle, and a multiple twist structure in which two or more filament bundles that have been twisted are combined in an upper twist are employed. The fineness per cord is preferably 1000 to 10000 dtex, more preferably 1500 to 6000 dtex. If a cord of less than 1000 dtex is used, it is necessary to increase the number of carcass in order to maintain the tire strength, leading to an increase in tire manufacturing costs. If a cord exceeding 10,000 dtex is used, the thickness of the carcass layer will increase more than necessary, leading to an increase in tire weight.

Ｄ：総デシテック数
Ｐ：コード比重
Ｔ：撚り数（回／ｃｍ） The twist coefficient of the cord is preferably 0.20 to 0.80, and more preferably 0.40 to 0.70.
The twist coefficient tanθ is obtained by the following equation.

D: Total decitec number P: Cord specific gravity T: Number of twists (times / cm)

  The cord or the fiber is dipped in a general adhesive such as RFL (resolvin-formalin-latex), dipped, and subjected to heat treatment including a drying step and a baking step. The dip cord produced in this manner is topped with a coating rubber to produce a fiber-rubber composite.

[Film-Rubber Composite]
Moreover, a high performance tire can be obtained by using the film-rubber composite of the present invention using the film obtained as described above for the inner liner layer. Such an inner liner layer can prevent air leakage of the tire and keep the tire air pressure constant. There is no limitation on the number of films of the inner liner layer, and it may be a single single layer or a plurality of multiple layers.
The following method is mentioned as a manufacturing method of a film-rubber composite.
As with the fiber-rubber composite, the film is immersed in a general adhesive such as RFL (resolvin-formalin-latex), dipped, and subjected to a heat treatment consisting of a drying step and a baking step. Topping to produce a film-rubber composite

The fiber-rubber composite of the present invention and the film-rubber composite of the present invention include, for example, natural rubber (NR), synthetic rubber having a carbon-carbon double bond, or a blend of two or more of these. Is used as a rubber composition.
Examples of the synthetic rubber include polyisoprene rubber (IR), polybutadiene rubber (BR), polychloroprene rubber which are homopolymers of conjugated diene compounds such as isoprene, butadiene and chloroprene; the conjugated diene compound and styrene and acrylonitrile. Styrene butadiene copolymer rubber (SBR), vinyl pyridine butadiene styrene copolymer rubber, acrylonitrile butadiene copolymer rubber, which are copolymers with vinyl compounds such as vinyl pyridine, acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, etc. , Acrylic butadiene copolymer rubber, methacrylic acid butadiene copolymer rubber, methyl acrylate butadiene copolymer rubber, methyl methacrylate butadiene copolymer rubber, etc .; ethylene, propylene, isobutylene Copolymers of olefins and diene compounds such as isobutylene isoprene copolymer rubber (IIR); Copolymers of olefins and non-conjugated dienes (EPDM) [eg ethylene-propylene-cyclopentadiene terpolymer Polymer, ethylene-propylene-5-ethylidene-2-norbornene terpolymer, ethylene-propylene-1,4-hexadiene terpolymer]; and further, halides of these various rubbers such as chlorinated isobutylene isoprene copolymer Polymerized rubber (Cl-IIR), brominated isobutylene isoprene copolymer rubber (Br-IIR) and the like; and norbornene ring-opening polymers.
Polyalkenamers obtained by ring-opening polymerization of cycloolefins to the above synthetic rubbers (for example, polypentenamers), rubbers obtained by ring-opening polymerization of oxirane rings (for example, polyepichlorohydrin rubbers capable of sulfur vulcanization), polypropylene oxide rubbers, etc. The saturated elastic body can be blended.

In the rubber composition used in the present invention, sulfur, an organic sulfur compound, and other crosslinking agents are added to 100 parts by mass of the rubber composition, preferably 0.01 to 10 parts by mass, more preferably 1 to 5 parts by mass. The vulcanization accelerator may be added to 100 parts by mass of the rubber composition, preferably 0.01 to 10 parts by mass, and more preferably 0.5 to 5 parts. In this case, although the kind of vulcanization accelerator is not limited, the vulcanization time can be shortened by using dibenzothiazyl sulfide (DM), diphenylguanidine (D) or the like.
The rubber composition used in the present invention includes, for example, paraffinic, naphthenic, or aromatic process oil, ethylene-α-olefin co-oligomer, paraffin wax, liquid paraffin, and other mineral oils; castor oil, cottonseed oil, Oils such as linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, and other vegetable oils may be blended.
Further, according to the conventional method, the rubber composition used in the present invention includes fillers such as carbon black, silica, calcium carbonate, calcium sulfate, clay, mica, etc .; zinc white, stearic acid, etc. Additives usually used in the rubber industry such as vulcanization accelerating aids; anti-aging agents may be added.

  The tire of the present invention can be produced by using the fiber-rubber composite of the present invention or the film-rubber composite of the present invention and undergoing normal molding and vulcanization processes.

  EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to a following example.

[Production of cellulose fiber]
Pulp was treated with 1-allyl-3-methylimidazolium chloride (AmimCl), 1-ethyl-3-methylimidazolium acetate (C2mimAc), 1-ethyl-3-methylimidazolium diethylphosphate (C2mim (EtO) ₂ PO ₂ ) , 1-ethyl-3-methylimidazolium methylphosphonate (C2mim MeOHPO ₂ ) or 1-ethyl-3-methylimidazolium phosphinate (C2mim H ₂ PO ₂ ), respectively. After heating this to the spinning temperature, it was extruded into a solidification tank with an extruder under the conditions shown in Table 1, and the cellulose fibers of Examples 1 to 7 and Comparative Examples 1 and 2 were subjected to washing and drying processes. Obtained.

The properties of the cellulose solution and the cellulose fiber in each Example and Comparative Example were measured by the following test methods, and the results are shown in Tables 1 and 2.
(1) Spinnability About 0.06 ml of the cellulose solution in each Example and Comparative Example is dropped onto a measurement dish, and a measuring element having a diameter of 3 mm is pressed against the measurement dish and evaluated at a height when pulled up at a speed of 10 mm / s. did.

(2) Encapsulation state of gas component in solution The encapsulation state of the gas component of the cellulose solution in each Example and Comparative Example was visually confirmed.
Visual inspection was performed by putting the cellulose solution in a container having an inner diameter of about 55 mm and a height of 80 mm.
The judgment criteria are shown below.
×: There are countless large bubbles and small bubbles, and it is difficult to count the number of bubbles. ○: There are some fine bubbles, but there are only enough bubbles to be counted. ◎: There are almost no bubbles.

(3) Fiber productivity The productivity of the cellulose fiber in each Example and Comparative Example was evaluated.
The judgment criteria are shown below.
X: Cannot be wound around the bobbin or fiber can be wound around the bobbin, but the amount of winding cannot be taken up.
◎: There is almost no thread breakage and a sufficient winding amount can be secured.

As shown in Tables 1 and 2, in Examples 1 to 7 in which the cellulose solution was degassed at normal pressure or under pressure, the fiber component was not included in the fiber, and the fiber spinnability was also improved. Maintained good productivity.
On the other hand, in Comparative Example 1 in which defoaming was not performed, a gas component was encapsulated in the fiber, and in Comparative Example 2 in which defoaming was performed under reduced pressure, the spinnability of the fiber was reduced, resulting in a fiber. The productivity of was decreasing.

Claims (12)

A method for producing a polysaccharide solid, wherein a polysaccharide solution obtained by dissolving a polysaccharide raw material in a liquid containing an ionic liquid is brought into contact with a solidifying liquid to solidify the polysaccharide. method for producing a polysaccharide solids comprising contacting the solidified liquid from the degassing under pressure.   2. The polysaccharide according to claim 1, wherein the ionic liquid includes a cation portion and an anion portion, and the cation portion is at least one selected from the group consisting of an imidazolium ion, a pyridinium ion, an ammonium ion, and a phosphonium ion. A method for producing a solid material.   The method for producing a polysaccharide solid according to claim 1 or 2, wherein the solidified liquid is at least one selected from the group consisting of water, a polar solvent, and the ionic liquid. The method for producing a polysaccharide solid according to claim 2 or 3, wherein the cation moiety is an imidazolium ion represented by the following general formula (1).

[Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents 1 to 8 carbon atoms. Or an alkenyl group having 2 to 8 carbon atoms. ]   The manufacturing method of the polysaccharide solid substance as described in any one of Claim 1 to 4 which discharges the said polysaccharide solution in the said solidification liquid, and obtains a fiber as said polysaccharide solid substance.   The manufacturing method of the polysaccharide solid substance as described in any one of Claim 1 to 4 which discharges the said polysaccharide solution in the said solidification liquid in a sheet form, and obtains a film as the said polysaccharide solid substance. It manufactured using the manufacturing method of the polysaccharide solid substance as described in any one of Claim 1 to 6. The polysaccharide solid substance characterized by the above-mentioned. The polysaccharide solid material according to claim 7 , wherein the polysaccharide solid material has a fiber shape, and the fiber of the polysaccharide solid material is twisted. A fiber-rubber composite comprising the polysaccharide solid according to claim 7 in a fiber shape and using the fiber of the polysaccharide solid or the cord according to claim 8.   A tire using the fiber-rubber composite according to claim 9. The film-rubber composite , wherein the polysaccharide solid according to claim 7 is in a film shape, and the film of the polysaccharide solid is used.   A tire comprising the film-rubber composite according to claim 11.