JP2002105240A - Cellulose composition containing lignophenol derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition consisting of a lignophenol derivative obtained from a lignocellulose material and a cellulose derivative. SOLUTION: The cellulose composition consists of (1) a cellulose derivative and (2) at least one kind of lignocellulose derivatives selected from a lignophenol derivative prepared with a hydrocarbon by adding a phenol to a lignocellelose and subsequently adding an acid to the reaction mixture, an alkaline-treated derivative of the above lignophenol derivative, and a derivative having a protected hydroxyl group of either the lignophenol derivative or the alkaline- treated derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cellulosic composition. More specifically, the present invention provides a composition comprising a cellulose derivative and a lignophenol derivative, and a plasticizer and an ultraviolet absorber for the cellulose derivative containing the lignophenol derivative.

[0002]

2. Description of the Related Art In modern society, the use of fossil resources has become indispensable. However, reproduction of fossil resources is impossible, and there is a fear of exhaustion in the near future. Biomass resources are attracting attention as one of the alternatives to fossil resources. Among them, woody biomass is enormous on the earth, can be produced in a short period of time, and is continuously supplied through appropriate maintenance. It is attracting attention because it is a possible resource, and after it is used as a resource, it is degraded in nature and reborn as a new biomass resource. Currently, woody biomass is used in two ways: wood use and pulp use. However, a large amount of waste is discharged in the use as wood, and lignin is hardly used in the use as pulp because the purpose is to use carbohydrate (cellulose).

In order to use lignin effectively in woody (lignocellulosic) biomass,
First, it is necessary to separate the wood into its constituents.
The present inventors have found that, based on previous studies, the combination of swelling of carbohydrates by concentrated acid and the destruction of lignin by the combination of lignin solvation with phenol derivatives suppresses lignin inactivation and reduces A method has been developed for separating polyphenol-based substances and carbohydrates as constituents (JP-A-2-233701).
As a method of utilizing the polyphenol-based substance obtained by this method, for example, it has been reported that a molded article is produced by applying to a molding material such as a cellulose-based fiber (Japanese Patent Application Laid-Open No. 9-278904). However, in order to more fully utilize lignocellulosic resources, it has been desired to develop new uses of this polyphenol-based substance (lignophenol derivative).

[0004] On the other hand, cellulose is a natural polymer which is difficult to synthesize artificially, and its compound and the fine structure as a molecular assembly are extremely sophisticated. The molecule is a macromolecule in which glucose is linked in a long chain by β-1,4 bonds. Each glucose residue has three hydroxyl groups at the 2, 3, and 6 positions and has its own functionality. ing. However, most (70-90%) of natural cellulose molecular aggregates are crystallized and form hydrogen bonds within and between molecules, so that their accessibility to hydroxyl groups is small.
Therefore, development of various cellulose solvents and synthesis of derivatives are indispensable for contributing various functions and expanding the range of use.

[0005] Many cellulose derivatives have hydrophilic and hydrophobic moieties in the same molecule, and such derivatives have an activating effect. Hence emulsion stabilizers, dispersants,
It is used in many fields such as fibers, papermaking, food, cosmetics, paints, civil engineering, and pharmaceuticals as viscosity modifiers and adhesives. The most used ones are carboxymethylcellulose (CMC) hydroxyethylcellulose,
Examples include cellulose acetate, methyl cellulose, and hydroxy cellulose. Cellulose derivatives such as cellulose acetate may be used after being formed into a film. However, in a dry method other than the casting method (wet method), a film cannot be formed unless a plasticizer is added to the cellulose derivative. As a plasticizer, diethyl phthalate, glyceryl triacetate (triacetin), triphenyl phosphate, and the like are used. However, if a new plasticizer having both decay resistance and biodegradability is provided, use of a cellulose derivative will be promoted. Useful for

[0006]

SUMMARY OF THE INVENTION The present invention provides:
An object of the present invention is to provide a composition in which a ligphenol derivative separated from a lignocellulosic material and a cellulose derivative are combined. Another object of the present invention is to provide a plasticizer and an ultraviolet absorber for a cellulose derivative.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, first, an acid was added to a lignocellulosic substance to which a phenol derivative was added and mixed to form the lignocellulose. A lignophenol derivative obtained by separating a system material into a lignophenol derivative and a carbohydrate, an alkali-treated derivative thereof, and an acetylated derivative thereof were prepared. The present inventors have found that films obtained by complexing these various lignophenol derivatives with cellulose acetate exhibit excellent physical properties, and have completed the present invention.

That is, according to the present invention, an acid is added to (1) a cellulose derivative; and (2) a lignocellulosic material to which a phenol derivative is added, and the lignocellulosic material is mixed with a lignophenol derivative and a carbohydrate. At least one lignophenol derivative selected from the group consisting of a lignophenol derivative obtained by separating the lignophenol derivative, an alkali-treated derivative of the lignophenol derivative, and a hydroxy group-protected derivative of the lignophenol derivative or the alkali-treated derivative: There is provided a composition comprising:

Preferably, the addition amount of the lignophenol derivative is 1 to 50% by weight based on the total weight of the cellulose derivative and the lignophenol derivative. Preferably, the cellulose derivative is cellulose acetate, more preferably, cellulose diacetate or cellulose triacetate. Preferably, the phenol derivative added to the lignocellulosic material is a phenol that may have one or more substituents, more preferably,
It is p-cresol. Preferably, the acid added to the lignocellulosic material is 65% by weight or more concentrated sulfuric acid. Preferably, the lignophenol derivative is a hydroxyl-protected derivative.

According to another aspect of the present invention, there is provided a molded article comprising the composition of the present invention described above. Preferably,
The molding is in the form of a film.

According to still another aspect of the present invention, an acid is added to a lignocellulosic material to which a phenol derivative has been added and mixed to separate the lignocellulosic material into a lignophenol derivative and a carbohydrate. A plasticizer for a cellulose derivative, comprising at least one lignophenol derivative selected from the group consisting of a lignophenol derivative obtained, an alkali-treated derivative of the lignophenol derivative, and a hydroxy-protected derivative of the lignophenol derivative or the alkali-treated derivative. Is provided.

According to still another aspect of the present invention, the lignocellulosic material obtained by adding an acid to a lignocellulosic material to which a phenol derivative has been added and mixing the resulting mixture to separate the lignocellulosic material into a lignophenol derivative and a carbohydrate. Ultraviolet absorption for a cellulose derivative, comprising: a lignophenol derivative to be obtained, an alkali-treated derivative of the lignophenol derivative, and at least one lignophenol derivative selected from the group consisting of a protected hydroxyl group in the lignophenol derivative or the alkali-treated derivative. An agent is provided.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The cellulose derivative composition of the present invention is characterized by containing a cellulose derivative and a lignophenol derivative (or a further derivative thereof) obtained by treating a lignocellulosic substance with a phenol derivative and an acid.

The type of the cellulose derivative used in the present invention is not particularly limited. In the present invention, a biodegradable cellulose derivative can also be preferably used. A biodegradable cellulose derivative is a cellulose derivative that can be degraded in the environment. The cellulose derivative used in the present invention may be any of those obtained from nature, those obtained by chemical synthesis, and those produced by various microorganisms.

Examples of the cellulose derivative include (1) organic acid esters such as cellulose acetate, cellulose butyrate and cellulose propionate; (2) inorganic acid esters such as cellulose nitrate, cellulose sulfate and cellulose phosphate;
(3) Hybrid esters such as cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate acetate are exemplified. Among these, organic acid esters, particularly cellulose acetate, are preferred, and specifically, cellulose diacetate and cellulose triacetate are preferred. Hereinafter, these will be described.

(1) Cellulose diacetate (CDA) As the structural characteristics of cellulose diacetate (CDA), the ease of acetylation of the hydroxyl group of three glucose residues is as follows.
The order is 6th>2nd> 3rd, but since the degree of saponification is small, the distribution after saponification of some of the hydroxyl groups is random, and therefore the symmetry and order of the diacetate molecule Low in nature and amorphous. Since the bulky acetyl group replaces the hydrogen of the hydroxyl group, the density of cellulose is about 1.5, but the density decreases to 1.32.
It is more stable to ultraviolet rays than cotton, silk, rayon, nylon, etc., but more stable than acrylic or polyester fibers, and more hydrophobic to water than cellulose fibers in terms of the distribution density of hydroxyl groups. It dissolves in acetic acid, acetic anhydride, acetone, methyl ethyl ketone, methyl acetate, emulsified methyl, dioxane, phenol, cresol and the like, and swells with an organic solvent such as chloroform, methylene chloride and dichloroethylene. It is used as medical fiber, tobacco felter and general plastic.

(2) Cellulose triacetate (CA)
T) Since the substitution degree is 3 compared to cellulose diacetate, the molecular structure is symmetric and uniform, the crystallinity is high, and the density is 1.30, which is slightly lighter. Due to its crystallinity, it is almost the same for ultraviolet rays, but has a slightly higher resistance, and also has half the moisture absorption for water as compared with diacetate. Methylene chloride, chloroform, formic acid, hot acetic acid, metacresol,
Dissolves in phenol etc. As an application, it is used for photographic films in addition to fibers.

When a biodegradable cellulose derivative is used, the average degree of substitution of the cellulose ester is preferably 2.
15 or less, more preferably 1.0 to 2.15, particularly preferably 1.1 to 2.0, and ASTM 12520
After 4 weeks in a biodegradability test method according to 9-91, 60% by weight or more, preferably 65% by weight or more (for example,
(5 to 100% by weight) It is preferable to use a cellulose ester that decomposes. If the average degree of substitution is less than 1.0, the solubility in a solvent is poor, and if it exceeds 2.15, not only the compatibility with other components and the melt fluidity but also the biodegradability are significantly reduced. . The decomposition rate (%) of the cellulose ester is calculated by converting the amount of carbon dioxide gas generated by biodegradation into the number of decomposed carbon atoms and calculating the ratio to the total number of carbon atoms before decomposition.

The cellulose derivative can be produced by a conventional method, and the degree of substitution can be adjusted by adjusting the blending ratio of cellulose with an organic acid or acid anhydride.
In addition, after a cellulose ester having a high degree of substitution (for example, trisubstituted product) is produced, the cellulose ester can be hydrolyzed to lower the degree of substitution. The average degree of polymerization of the cellulose derivative is not particularly limited, but is preferably about 50 to 250, particularly preferably 100 to 200. This is because a cellulose derivative within this range is excellent in sufficient mechanical properties and biodegradability of a molded article, and excellent coating properties during production of the molded article.

In the cellulose derivative composition of the present invention, a lignophenol derivative is used as a plasticizer. A lignophenol derivative used in the present invention is a lignophenol derivative obtained by adding an acid to a lignocellulosic material to which a phenol derivative has been added, mixing and separating the lignocellulosic material into a lignophenol derivative and a carbohydrate, It is at least one selected from the group consisting of an alkali-treated derivative of the lignophenol derivative, and a derivative of the lignophenol derivative or the alkali-treated derivative in which a hydroxyl group is protected. Hereinafter, the lignophenol derivative used in the present invention will be described in detail.

As the phenol derivative to be added to the lignocellulosic substance, a monovalent phenol derivative, a divalent phenol derivative, a trivalent phenol derivative, or the like can be used. Specific examples of the monovalent phenol derivative include a phenol that may have one or more substituents, a naphthol that may have one or more substituents, and a phenol that may have one or more substituents. Good anthrol and anthroquinone ol which may have one or more substituents are exemplified. Specific examples of the divalent phenol derivative include catechol optionally having one or more substituents, resorcinol optionally having one or more substituents, and one or more substituents. Good hydroquinone and the like. Specific examples of the trivalent phenol derivative include pyrogallol which may have one or more substituents.

The type of the substituent that the phenol derivative may have is not particularly limited, and may have any substituent. Preferably, the phenol derivative has a substituent other than an electron-withdrawing group (such as a halogen atom). And an alkyl group (eg, a methyl group, an ethyl group, a propyl group), an alkoxy group (eg, a methoxy group, an ethoxy group, a propoxy group), and an aryl group (eg, a phenyl group). Further, at least one of the two ortho positions of the phenolic hydroxyl group on the phenol derivative is preferably unsubstituted.
A particularly preferred example of a phenol derivative is cresol, especially m-cresol or p-cresol.

The "lignocellulosic material" used in the present invention includes woody materials, various materials mainly wood, for example, wood flour, chips, waste materials, and offcuts. As the wood to be used, any kind of wood, such as conifers and hardwoods, can be used. further,
Various herbaceous plants and samples related thereto, such as agricultural wastes, can also be used.

As the acid to be added to the lignocellulosic substance, an acid having a swelling property with respect to cellulose is preferable. Specific examples of the acid include, for example, sulfuric acid having a concentration of 65% by weight or more (for example, 72% by weight of sulfuric acid), 85% by weight or more of phosphoric acid, 38% by weight or more of hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, Trichloroacetic acid, formic acid and the like can be mentioned.

Next, the method for producing the lignophenol derivative used in the present invention will be described in more detail. In the present invention, the term "lignophenol derivative" means a polymer containing a diphenylpropane unit in which a phenol derivative is introduced by a CC bond at the α-position of the side chain of the phenylpropane unit of lignin. . The amount and molecular weight of the introduced phenol derivative in this polymer vary depending on the lignocellulosic material as the raw material and the reaction conditions.

In order to obtain a lignophenol derivative from a lignocellulosic material, it is necessary to treat the lignin in the lignocellulosic material with a phenol derivative and extract it as a lignophenol derivative from the lignocellulosic material. Currently, there are two types of methods for extracting lignin in lignocellulosic materials as lignophenol derivatives.

The first method is a method described in JP-A-2-233701. In this method, for example, as shown in FIG. 1, a phenol derivative in a liquid state is added to a lignocellulose-based material such as wood flour (as described above,
For example, cresol or the like is infiltrated, lignin is solvated with a phenol derivative, and then the lignocellulosic material is added with a concentrated acid (as described above, for example, 72% sulfuric acid) and mixed to form a cellulose component. Dissolve. According to this method, a phenol derivative solvated with lignin and a concentrated acid in which a cellulose component is dissolved form a two-phase separation system. The lignin solvated by the phenol derivative is contacted with the acid only at the interface where the phenol derivative phase comes into contact with the concentrated acid phase, and the side chain α-position which is a high reaction site of the lignin basic structural unit generated by the contact with the acid. The cation at the (benzyl position) is attacked by the phenol derivative. As a result, a phenol derivative is CC at the α-position.
It is introduced by a bond, and the molecular weight is reduced by the cleavage of the benzyl aryl ether bond. As a result, lignin is reduced in molecular weight, and at the same time, a lignophenol derivative in which a phenol derivative is introduced at the benzyl position of the basic structural unit is formed in the phenol derivative phase (see FIG. 3). From this phenol derivative phase, a lignophenol derivative is extracted. The lignophenol derivative is obtained as a part of an aggregate of a low molecular weight lignin in which the benzyl aryl ether bond in the lignin is cleaved and reduced. It is known that some phenol derivatives are introduced at the benzyl position via the phenolic hydroxyl group.

The extraction of the lignophenol derivative from the phenol derivative phase can be performed, for example, by the following method. That is, the precipitate obtained by adding the phenol derivative phase to a large excess of ethyl ether is collected and dissolved in acetone. The acetone-insoluble portion is removed by centrifugation, and the acetone-soluble portion is concentrated. The acetone-soluble portion is added dropwise to a large excess of ethyl ether, and the precipitate is collected. After distilling off the solvent from this precipitation section, the precipitate is dried in a desiccator containing phosphorus pentoxide to obtain a lignophenol derivative as a dried product. The crude lignophenol derivative can be obtained by simply removing the phenol derivative phase by distillation under reduced pressure. The acetone-soluble part is directly converted into a lignophenol derivative solution and derivatized (alkali treatment).
Can also be used.

In the second method, as shown in FIG. 2, a solvent (for example, ethanol or acetone) in which a solid or liquid phenol derivative is dissolved is penetrated into a lignocellulosic material, and then the solvent is distilled off. (Phenol derivative sorption step). Next, a concentrated acid is added to the lignocellulosic material to dissolve the cellulose component. As a result, as in the first method, the lignin solvated with the phenol derivative causes the cation at the high reaction site (α side position of the side chain) of the lignin generated by contact with the concentrated acid to be attacked by the phenol derivative, and Derivatives are introduced.
Further, the benzyl aryl ether bond is cleaved to lower the molecular weight of lignin. The properties of the obtained lignophenol derivative are the same as those obtained by the first method. Then, similarly to the first method, the phenol-derivatized lignophenol derivative is extracted with the liquid phenol derivative. The extraction of the lignophenol derivative from the liquid phenol derivative phase can be performed in the same manner as in the first method. Alternatively, the entire reaction solution after the concentrated acid treatment is poured into excess water, the insoluble fraction is collected by centrifugation, and after deoxidation,
dry. Acetone or alcohol is added to the dried product to extract a lignophenol derivative. Further, similarly to the first method, the soluble fraction is dropped into excess ethyl ether or the like to obtain the lignophenol derivative as an insoluble fraction. In this method, similarly, the acetone-soluble portion can be used as a lignophenol derivative solution for derivatization treatment (alkali treatment).

Of these two methods, the second method is particularly the latter, that is, the method of extracting and separating a lignophenol derivative with acetone or alcohol requires a small amount of the phenol derivative. Is economical. Further, this method can treat many lignocellulosic materials with a small amount of a phenol derivative, and thus is suitable for mass synthesis of a lignophenol derivative. The lignophenol derivative obtained by the above method is also referred to herein as an original lignophenol derivative. In the present specification, when referred to as “lignophenol derivative”, unless otherwise specified, it includes, in addition to the above-mentioned original lignophenol derivative, those derivatives described below in the present specification (specifications). More specifically, all of an alkali-treated derivative or a derivative in which a hydroxyl group is protected are included.

The original lignophenol derivative obtained by the above method generally has the following characteristics. However, the characteristics of the lignophenol derivative used in the present invention are not limited to the following. (1) The weight average molecular weight is about 3,000 to 20,000. (2) It has almost no conjugated system in the molecule and its color tone is extremely light. (3) It has a melting point of about 170 ° C derived from softwood and about 130 ° C derived from hardwood. (4) As a result of selective grafting of the phenol derivative to the α-position of the side chain, the lignin derivative has an extremely large amount of phenolic hydroxyl groups and is imparted with high phenol properties. (5) The aromatic nucleus of the lignin structural unit and the aromatic nucleus of the phenol derivative grafted at the α-position of the side chain form a diphenylmethane type structure, and self-condensation is suppressed. (6) methanol, ethanol, acetone, dioxane, pyridine, THF (tetrahydrofuran), DMF
Easily soluble in various solvents such as (dimethylformamide).

The original lignophenol derivative obtained by the above method can be used as it is for the cellulose derivative of the present invention, but can also be used after further derivatization. As a treatment for obtaining such a derivative, alkali treatment of the original lignophenol derivative can be mentioned.

The original lignophenol derivative obtained by a phase separation process from natural lignin has its active Cα blocked by the phenol derivative.
Overall stable. However, under alkaline conditions, the phenolic hydroxyl group is easily dissociated and the resulting phenoxide ion attacks the adjacent Cβ position where sterically possible. As a result, the aryl ether bond at the Cβ position is cleaved, the lignophenol derivative is reduced in molecular weight, and the phenolic hydroxyl group in the introduced phenol nucleus is transferred to the lignin parent. Therefore, it is expected that the alkali-treated derivative will have higher hydrophobicity than the original derivative. At this time, the alkoxide ion or carbanion of the lignin aromatic nucleus existing at the Cγ position is
It is also expected to attack the β-position, but this requires much higher energy than the phenoxide ion.
Therefore, under mild alkaline conditions, the adjacent group effect of the phenolic hydroxyl group of the introduced phenol nucleus preferentially appears,
Under more severe conditions, a further reaction occurs, and the phenolic hydroxyl group of the once-etherified cresol nucleus is regenerated, whereby the lignophenol derivative is further reduced in molecular weight and the number of hydroxyl groups increases, and the hydrophilicity may increase. Be expected.

Furthermore, the original lignophenol derivative and the lignophenol derivative obtained by subjecting the lignophenol derivative to alkali treatment exhibit various characteristics due to the presence of phenolic and alcoholic hydroxyl groups. By protecting this hydroxyl group, derivatives having different different properties can be obtained. As a method for protecting the hydroxyl group, for example, an acyl group (for example, an acetyl group, a propionyl group, a benzyl group, etc., preferably an acyl group)
And protecting the hydroxyl group with a protecting group such as In the cellulose derivative composition of the present invention, a derivative whose hydroxyl group is protected as described above can be used.

The addition amount of the lignophenol derivative in the cellulose derivative composition of the present invention is preferably 1 to 50% by weight, more preferably 5 to 50% by weight, particularly preferably 5 to 50% by weight, based on the total weight of the cellulose derivative and the lignophenol derivative. Preferably it is 5 to 30% by weight, for example, 5
%, 10%, 20% or 30% by weight.

The cellulose derivative composition of the present invention is characterized by containing a cellulose derivative and a lignophenol derivative, but may contain other optional components. As an optional component, (A) a plasticizer other than the lignophenol derivative (for example,
Alkylphenol compounds, high-boiling esters of polybasic acids, polyhydric alcohols, aromatic sulfonamides, etc.), (B) stabilizers against thermal decomposition or oxidative decomposition, (C) inorganic fillers (eg, glass fiber, carbon fiber, plate-like) Or foil-like particles, silica, clay, magnesium silicate, etc.) (D) Organic fillers (eg, cellulose fibers or particles, protein fibers, synthetic polymer particles or fibers, wood flour) (E) Polymers other than cellulose derivatives (F ) Pigment (G) Nucleating agent (preferably 0.2 to 2.0 phr of boron nitride, talc, ammonium chloride or DZB / Zn
Stearates) (H) Volatile solvents for cellulose derivatives and lignophenol derivatives, and the like, but are not limited thereto.

The composition of the present invention can be processed into any form. For example, the composition of the present invention can be molded into a desired shape by using a mold, passing through a die, or the like to produce a molded article. In the case of a molded product, additives such as a heat stabilizer, an antioxidant, a plasticizer, an ultraviolet absorber, and a coloring agent are usually added to the cellulose derivative. In the present invention, a lignophenol derivative is used as a plasticizer or an ultraviolet absorber. An appropriate mixing ratio of the cellulose derivative and the lignophenol derivative can be selected in consideration of the physical properties of the molded product, the molding method, and the like.

The composition of the present invention can be used for compression molding, injection molding,
A molded product can be produced by various molding methods such as extrusion molding, blow molding, foam molding, casting molding, and spinning. In compression molding, for example, a lignophenol derivative and a solvent are added to a cellulose derivative, and the mixture is stirred with a kneader to form a soft syrup, and then the solvent is evaporated to form pellets. Then, the pellet is subjected to a compression molding machine to produce a sheet. In the case of injection molding,
For example, a lignophenol derivative and a solvent are added to a cellulose derivative, and the mixture is stirred with a kneader to form a soft syrup, and then the solvent is evaporated to form pellets. And
The pellet is processed by an injection molding machine to produce a curved molded product.

The cellulose derivative composition of the present invention can be processed into a film form. When processing into a film, there are a wet method for producing a film using a solvent and a dry method for producing a film using a plasticizer only with heat and pressure without using a solvent. The cellulose derivative composition of the present invention can be preferably processed into a film by a dry method.

Extrusion can be carried out by a dry method for forming a film. In this case, it is important to sufficiently dry the sample, and the molding temperature in extrusion molding is generally 140 to 240 ° C., and varies depending on the degree of substitution (degree of acetylation) and the type and amount of the plasticizer. . As a general film forming method, there is a hot press method, which is a method of forming a film by pressing a pellet or powder between two thick plates. In this case, when the spacer is inserted between the polymer and the hot plate, the adjustment of the thickness of the film, the releasability and the surface condition are improved.

Although the use of the composition of the present invention is not particularly limited, examples of molded articles include automobile parts, building material wallpaper, and the like.
It can be used for filter paper for metal adsorption, air washing filter, films and containers for agricultural and horticultural use (heat insulation curtains for agricultural lands, seed bags, etc.). Furthermore, medical wound healing promotion tape vans, medical drug bags, medical chart paper It can also be used for food packaging bags and the like. The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.

[0042]

EXAMPLES Example 1 Production of Lignophenol Derivatives (1) Sorption of Cresol The moisture content of defatted wood flour was measured in advance, and 1 kg of absolutely dry weight of 20 mesh pass wood flour (hinoki as a softwood material, hardwood material) Beech) was placed in a 25 L stainless steel tank. 3 mol times p per ₉ units of lignin C
Acetone solution containing cresol (about 6 L with cypress, about 4 L with beech) was added, fine bubbles were wiped off, covered and left overnight. After the adsorption, the acetone was distilled off in the fume hood until it reached the upper surface of the wood flour, and then transferred to a stainless steel vat, and the solvent was completely distilled off with constant stirring in the fume hood.

(2) Concentrated Acid Treatment The sorbed wood flour was divided into four equal portions in a 3 L beaker (250 g of wood flour per beaker). Hereinafter, one beaker will be described. 72% sulfuric acid (about 1.2
L, about 0.8 L with beech) was added in several portions with good stirring with a glass rod. The portion where the wood flour was not in contact with the sulfuric acid was eliminated and the mixture was vigorously stirred. Sulfuric acid was added and after about 10 minutes a stirrer was used. One hour after the addition of sulfuric acid, stirring was stopped, and the reaction was stopped by half-pouring into two 5 L Erlenmeyer flasks previously containing 2-3 L of deionized water. Thereafter, deionized water was added to a scale of 5 L, and the mixture was left for 2 days.

(3) Deoxidation treatment Two days later, the supernatants of eight 5 L Erlenmeyer flasks were decanted and collected in a 5 L Erlenmeyer flask. again,
Deionized water was added to the scale of 5 L, left to stir, allowed to settle naturally, decanted again, and the precipitate was placed in a dialysis membrane. Giant bat (length 72cm, width 37cm, depth 2
5 cm), the acid and excess p-cresol were removed by dialysis while stirring the precipitate in the dialysis membrane every day for about 2 weeks under running water with tap water. After confirming that the inside of the membrane was neutral, the tap water in the vat was replaced with deionized water and left for 2 days. The deionized water was replaced again, and the mixture was left for 2 days. After confirming that the inside of the membrane was neutral, the process was completed.

(4) Drying of the acid-treated precipitate The acid-treated precipitate was transferred to two 3 L beakers, left for 3 days, and the supernatant was decanted. The precipitate was spread on a stainless steel vat as it was, dried for about 5 days in a dryer set at 40 ° C, and further dried at 60 ° C for 2 days.
Then, it was completely dried over phosphorus pentoxide.

(5) Extraction with Acetone The dry solid obtained in (4) was divided into two 5 L Erlenmeyer flasks, 4 L of acetone was added, and the mixture was stirred for 3 days to extract lignocresol. Centrifuge the extraction mixture,
The supernatant was filtered with glass fiber filter paper (Whatman GF / A). Extraction and filtration were performed again in the same procedure to obtain an acetone extraction solution.

(6) Purification The acetone-extracted solution was concentrated by an evaporator to 20 times the weight of the lignin, and the remaining unreacted unreacted product was added dropwise to benzene: hexane = 2: 1 10 times the amount of the concentrated solution. The p-cresol and lignocresol low molecular weight fractions were removed and left overnight. Thereafter, the supernatant was decanted, and the precipitate was collected by centrifugation and washed five times with benzene: hexane = 2: 1. Thereafter, the solvent was replaced with diethyl ether, and the mixture was washed twice. The collected centrifugation tube was dried in a fume hood for 2 days, and then completely dried over diphosphorus pentoxide to obtain powdered lignocresol (hereinafter also referred to as original lignocresol).

Example 2 Preparation of Derivatives by Secondary Function Conversion of Lignocresol (Alkali Treatment) Lignocresol obtained in Example 1 in a 200 mL beaker (for each of the samples from cypress and beech) 0 g and 0.5N NaOH to 160 m
After adding L and confirming complete dissolution, the mixture was transferred to two 100 mL stainless steel autoclaves. Put the autoclave into the oil bath whose temperature has been set to 170 ° C in advance,
After the temperature reached the predetermined temperature again, the reaction was performed for 1 hour (20 minutes later, 4
(Stirred after 0 minutes). Then, it was cooled with water. After cooling sufficiently, the contents were transferred to a 500 mL beaker. 2
The mixture was acidified to pH 2 while measuring the pH with N HCl. The deposited precipitate is centrifuged (3000
rpm, 10 minutes, room temperature), washed three times with deionized water, lyophilized, dried over diphosphorus pentoxide,
A 170 ° C.-treated secondary derivative was obtained.

Example 3: Acetylation treatment of original lignocresol and derivative treated at 170 ° C. 7.5 g of lignin sample (original lignocresol obtained in Example 1, derivative treated at 170 ° C. obtained in Example 2)
Into a 200 mL Erlenmeyer flask and pyridine 75 mL
Was added to completely dissolve the lignin. Next, acetic anhydride 75
mL was added, sealed and left for 48 hours. 48 hours later,
The reaction was added dropwise to 3 L of cold water (about 5 ° C.). After dripping,
Centrifuge the reaction (3000 rpm, 10 minutes, 5 ° C)
Then, it was washed only once with cold water. After freeze-drying the precipitate, a wrapping paper was placed in a petri dish, the precipitate was spread thereon, and dried under reduced pressure over phosphorus pentoxide until it was odorless.
Hereinafter, a sample having a hydroxyl group is referred to as an original sample,
Add “Original” to the sample name. Further, a sample having an acetyl group is referred to as an acetylated sample, and acetate is added to the sample name.

Example 4 Analysis of Properties of Lignocresol Derivative (1) Gel Permeation Chromatography (GPC) About 1 mg of a sample of the lignocresol derivative was completely dissolved in about 1 ml of rectified tetrahydrofuran (THF), and p-type was used as an internal standard. Add a drop of cresol / THF solution and add CO
Filtered with SMONICE Filter "S". The measurement was performed under the following conditions. Column: Shodex KF801, KF802, KF803, KF804 Solvent: THF Flow rate: 1 ml / min Pressure: 50 kgf / cm ² Detector: UV 280 nm Sample: 25 μl The results showing the molecular weight distribution are shown in FIG. Table 1 below shows the weight average molecular weight, number average molecular weight, and dispersion ratio of each sample.

[0051]

[Table 1]

(2)¹H-NMR measurement Original sample of lignophenol derivative and acetyl
For each of the sample¹1 H-NMR was measured. Hino
Ki sample¹FIG. 5 shows the H-NMR of the beech sample. ¹H-N
FIG. 6 shows the MR.

(3) Measurement of UV and ionization differential spectra UV and ionization differential spectra were measured for each of the original sample and the acetylated sample of the lignophenol derivative. FIG. 7 shows the UV and ionization differential spectrum of the hinoki sample, and FIG. 8 shows the UV and ionization differential spectrum of the beech sample.

(4) Measurement of IR Spectrum The IR spectrum was measured for each of the original sample and the acetylated sample of the lignophenol derivative. FIG. 9 shows the IR spectrum of the hinoki sample, and FIG.
The R spectrum is shown in FIG.

Example 5: Preparation of composite film of lignophenol derivative and cellulose derivative Cellulose diacetate (CDA, Wako Pure Chemical Industries), cellulose acetate (CTA, Aldrich chemical compa)
ny Inc.) was dissolved in each solvent (acetone, chloroform), and the volume was increased to a 500 mL volumetric flask to prepare a 25 mg / ml solution, which was used as a cellulose solution. 250 mg of various lignin samples
A 10 mg / ml solution was prepared by taking the sample in a 5 mL volumetric flask and raising the volume, and this was used as a lignin solution. Take these into a 50 mL beaker with a female pipette so that the total weight of the film is 1 g and the added amount of the lignin sample is 0, 5, 10, and 20%, add the solvent up to the 40 mL line, and add it to a glass rod (diameter 3 mm). Then, the mixture was stirred until it was uniformly dispersed and cast on a stainless steel pad, and then the solvent was distilled off under cooling (2 ° C.) with acetone and at 20 ° C. with chloroform. The rectangular film was peeled off with a cutter and tweezers, sandwiched between plain papers, and weighed to completely evaporate the solvent and impart smoothness to the film.

Example 6: Thermal behavior of film (A) Method The same sample was used for all of TMA, TG and DSC measurements. After confirming complete drying, the lignin sample was pulverized with an agate bowl, and the control film and the composite film were pulverized with a vibrating mill for 20 minutes (hereinafter referred to as a film sample) as a measurement sample.

(A-1) TMA (Thermomechanical ana)
lysis) Measurement About 3 mg of the sample was placed in an aluminum pan having a diameter of 5 mm, and after giving the sample smoothness, the sample and the aluminum plate were blended so that the aluminum plate was fixed. At a heating rate of 2 ° C./min with a load of 5 g applied vertically downward on the center of the aluminum plate, the displacement amount from 25 ° C. to 250 ° C. for the lignin sample and 25 ° C. to 300 ° C. for the film sample was measured. Thermo Plus TMA 8310 (manufactured by Rigaku Denki Co., Ltd.) was used for the measurement. The phase transition point (Ts) was determined at the intersection of the tangents of two points (low and high temperatures) near the phase transition.

(A-2) TG-DSC (Thermogravimet)
ry-Differential scanning calorimetry) measurement Put about 3mg of alumina and sample in aluminum pan,
Alumina was placed on the reference side and the sample was placed on the sample side. Helium was flowed at a rate of 20 ml for 1 minute, and at a heating rate of 2 ° C./min, the weight displacement and calorie of the lignin sample from 25 ° C. to 250 ° C. and the film sample from 25 ° C. to 300 ° C. were measured. Thermoflex TA for measurement
S200 (manufactured by Rigaku Denki Co., Ltd.) was used. Decomposition starting temperatures are:
It was determined from the intersection of two tangent lines (low temperature and high temperature sides) near the weight loss point.

(B) Results (B-1) Thermal Behavior of Cellulose Derivative FIG. 11 shows TMA and DS of CDA and CTA controls.
C is indicated. In the CDA control, the phase transition starts at about 200 ° C., and although slight, a phase transition can be confirmed at about 225 ° C., and also at about 248 ° C., and all phase transitions occur at about 265 ° C. Regarding CTA control,
The behavior is quite different from that of the CDA, and a gradual phase transition with a small displacement for the first time around 175 ° C, 278 ° C
A phase transition with a large displacement amount was observed for the second time in the vicinity.

(B-2) Thermal Behavior of Lignocresol Derivative FIG. 12 shows the TMA curves of the lignin samples synthesized in Examples 1 to 3, and Table 2 shows the weight average molecular weight, phase transition point (Ts), The TG shows the weight loss start point (DST).

[0061]

[Table 2]

In the case of Hinoki lignocresol (original), a clear phase transition was observed at about 193 ° C., and one peak was present at about 250 ° C. Hinoki lignocresol (original) has relatively high molecular weight molecules in the molecular weight distribution by GPC, and has a high dispersion ratio of 4.88.
Wide range of molecular weight. Therefore, a molecule having a relatively low molecular weight (a molecule that is more linear and has a shorter molecular chain) is likely to move at a lower temperature and thus undergoes a faster phase transition, whereas a molecule having a higher molecular weight (a molecule with a large number of branches) does not move unless the temperature is higher.
Therefore, after a clear phase transition, when a molecule having a large molecular weight is dissolved, the air is trapped and foamed, as in CDA, so that the needle rises.
After that, when air escaped, such TM
It is considered that an A curve was drawn.

On the other hand, bunarignocresol (original) is around 170 ° C.
The phase transition has been completed by 0 ° C. This is due to the fact that the hardwood lignin is easily fragmented due to the difference in constituent units due to the phase separation process, and the dispersion ratio in the molecular weight distribution is smaller than that of hinoki.

The Hinoki secondary derivative II (original) showed a Two peak pattern in the molecular weight distribution, and it was found that a high molecular fraction and a low molecular fraction were present. This TM
The A measurement showed a two-stage phase transition point (around 90 ° C. and 142 ° C.), and similarly a beech secondary derivative II also observed a two-stage phase transition point (around 77 ° C. and 104 ° C.).
This indicates that the phase transition was performed in the order of the low molecular fraction and the high molecular fraction. The difference in the phase transition point between tree species is different from that of lignocresol (original), and correlates with the weight average molecular weight. Also in beech rather than cypress,
It was sharper and the polymer fraction underwent a phase transition at temperatures as low as about 40 ° C. It can be said that this caused the phase transition point of the high molecular fraction at lower temperature because beech has a larger amount of the low molecular fraction. As described in Hinoki lignocresol (original), the low-molecular-weight fraction was rich and the viscosity was low, and air from the dissolved sample was not trapped.

Next, these acetylated samples were measured. Acetylation of lignocresol (original) lowered the phase transition point by about 50 ° C, while that of the secondary derivative was reduced by about 15 ° C. In both cases, the phase transition is sharp. This is because, due to acetylation, no hydrogen bond exists in the molecule and the association of the molecules disappears. Further, by acylating not an acetyl group but an acyl group having a longer or larger carbon chain, a further decrease in the phase transition point can be expected.

Looking at the starting point of weight loss from TG,
As the weight average molecular weight increases, the weight decreases at lower temperatures, which can be said to be inversely related. this is,
This is presumably because the movement of molecules increases as the temperature rises, and the more branched and larger the molecules, the more destruction of the molecules occurs. When the original sample and its acetylated sample are compared, the acetylated sample is decomposed at a lower temperature. This is thought to be due to the absence of intermolecular hydrogen bonds.

(B-3) Thermal Behavior of Composite Film The TMA pattern of the composite film having a composite amount of 10% is shown in FIG.
3, FIG. 14 and FIG. CDA-hinoki sample (FIG. 13), CDA-beech sample (FIG. 14), and CTA, respectively.
-Corresponds to the acetylated sample (Fig. 15).

For the CDA-hinoki sample (FIG. 13)
Compared with the CDA control, there is almost no change in the hinoki lignocresol (original) composite film, and the hinoki secondary derivative
The same was true for II (original). The phase transition temperatures are decreased by about 5 ° C. and 12 ° C., respectively, and it is considered that the lower the phase transition temperature of the composite lignin sample, the lower the temperature becomes. In these DSCs, an endothermic peak indicating decrystallization as seen in the control film was not observed. On the other hand, when those acetates were combined, the cypress secondary derivative II (acetate) was almost the same as the control. However, with lignocresol (acetate), a sharp phase transition occurred at 187 ° C. in one step. Further, in this film, an endothermic peak due to dissolution was observed in the vicinity of the phase transition in DSC measurement, and no decrystallization peak was observed. From these results, lignocresol (acetate) was found to contain C
It is considered that the amorphous region of DA is plasticized and the crystal structure is not completely formed, and an integral structure is formed as a composite film. FIG. 16 shows the relationship between cellulose chains and lignin molecules in these composite films.

The factors can be considered as follows. 1) In the original sample having hydroxyl groups, hydrogen bonds between CDA molecules occur due to hydrogen bonds with hydroxyl groups of CDA.
The formation of a crystal structure was suppressed. The difference between lignocresol (original) and the secondary derivative II (original) was faster in the secondary derivative II (original) where the phase transition was performed at lower temperature. 2) In lignocresol (acetate), a large molecule having no hydroxyl group exists between CDA molecules.
A hydrogen bond between DAs was prevented, and a crystal structure was not completely formed, and an integrated structure was formed as a composite film. Therefore, one-step sharp phase transition occurred. 3) Despite the fact that the phase transition temperature of the secondary derivative II (acetate) was the lowest, there was not much plasticizing effect because the molecular bond was too small to form hydrogen bonds between CDAs as much as lignocresol (acetate). This is because it could not be suppressed.

The tendency of the beech sample (FIG. 14) was similar to that of the cypress sample. As in 1) above, it correlates with the phase transition temperature of the lignin sample, and 2) can be confirmed by the fact that the acetylated sample has a slightly higher phase transition point than the original sample. In 3), hinoki lignocresol (original) It is probable that because the molecule was smaller, the hydrogen bond could not be suppressed as much as Hinoki, and the phase transition point was high.

In the CTA-acetylated sample (FIG. 15),
It showed a tendency similar to CDA. Although there is no hydroxyl group in the CTA molecule, the crystal structure is high because the molecular structure is uniform. Therefore, it is important for plasticization that this crystal structure is not formed in the synthesized lignin sample. Lignocresol (acetate) did not show an endothermic peak for decrystallization by DSC. However, secondary derivative II
(Acetate) had a slight endothermic peak, though not as strong as the control. This remarkably appears in the TMA pattern, and it can be seen that when lignocresol (acetate) is compounded, the phase transition of the second crystal region is reduced by about 50 ° C. The difference between hinoki and beech clearly shows that the phase transition point of the sample to be complexed in the amorphous region is related to the molecular size in the crystalline region.
On the other hand, in the secondary derivative II, the crystal structure was highly maintained due to the small size of the molecule. Therefore, only a change in the phase transition in the amorphous region was observed, and no difference was observed at 200 ° C. or higher. However, this is due to the fact that, similarly to the above-mentioned CDA film, CT by dissolving the secondary derivative II (acetate) in a vibration mill
The possibility that A has recrystallized cannot be denied. TG is C
The tendency was the same as that of the DA-acetylated sample. In the case of lignocresol (acetate), a decrease was observed after the phase transition in the amorphous region, and in the case of the secondary derivative II (acetate), it was similar to the control. From the above results, it was found that lignocresol can give a plasticizing effect to a cellulose derivative.

Further, CDA and lignocresol (acetate) were blended at a ratio of 9: 1, and TMA measurement was performed (FIG. 17). As a result, a phase transition was observed at 197 ° C. Transition end temperature is 240 ° C
It was near. Therefore, it is considered that the phase transition completion temperature was high only by blending because the hydrogen bonds between the cellulose chains existed as described above. Further, it is considered that the completion temperature is lowered by increasing the amount of compounding.

(Difference depending on the amount of compounding)
(D) CDA-original sample composite film, FIG.
(A) to (d) show the CDA-acetylated sample, (a) to (d) in FIG. 20 show the TMA pattern due to the difference in the amount of composite in each sample of the CTA composite film, and Table 3 shows the phase transition point (Ts). ), The starting point of weight loss (DST) by TG is summarized.

[0074]

[Table 3]

From the results of the DSC measurement, it was found that the CDA composite film was 5% other than bunarignocresol (acetate).
% Film, an endothermic peak of decrystallization was observed.
Therefore, it can be understood that the amount of the composite is less than 5% in order to eliminate the crystal structure. As shown in FIG.
The hinoki lignocresol (acetate), which exhibited a sharp phase transition at 0%, had a small amount of conjugate when the conjugate amount was halved to 5%, and could not completely prevent the crystallization of CDA. However, in the case of bunarignocresol (acetate), the phase transition was as sharp as 10%.

Regarding CTA [FIG. 20], when the amount of conjugate in lignocresol (acetate) was set to 5%, an endothermic peak was observed, and the secondary derivative II (acetate) was observed.
, A peak was observed at 20%. Therefore, C
In the case of the TA secondary derivative II acetate composite film, a higher composite amount is required to reduce the crystal structure. Hinoki and beech lignocresol (acetate) 2
In the 0% composite film, three phases of 178, 220 and 268 ° C. were observed.

The shift width of the phase transition point to the lower temperature side due to the increase in the amount of composite to 5, 10, 20% basically increased as the phase transition point of the lignin sample was lower. However, the hydrogen bond between CDA chains could not be suppressed in the acetylated sample due to the factor 3-3-1 of the original sample and the acetate sample of the secondary derivative II in CDA, and the shift width was small.

Example 7: Influence of UV rays on composite film (A) Method (A-1) UV transmittance test The following equipment was used as an apparatus. UV irradiation device H
P-15L [Ato Scientific Instruments] was used. Wavelength region: UVA (320-380 nm) Peak: 365 nm Ultraviolet intensity: 1100 μW / cm ² Ultraviolet Blocking Eyewear UVC-503 (Goggle), UVC-
803 (Faceshield) [UVPInc.] Colorimeter CR-100 [MINOLTA] UV SENSOR [Swannet (Yes)]

This test was performed in a dark room to remove factors other than the wavelength irradiated from the ultraviolet irradiation device. The color before irradiation of UV SENSOR, whose color changes depending on the amount of ultraviolet rays, is measured in advance with a colorimeter and the color difference display L * a *
The value of a * for b * was recorded. (The value of a * is-
After confirming that it was in the range of 1.5 ± 0.2, it proceeded to the next. ) UV at a position 10 cm away from the UV irradiation device
SENSOR, on which various composite films selected in the range of 70 to 80 μm in thickness are placed. At this time, both ends of the film were fixed so that the film was surely brought into contact with the UV SENSOR. Irradiate for 3 minutes, measure the value of a * in the color difference display L * a * b * again with a colorimeter, and measure the difference in color intensity that changes with the amount of ultraviolet light transmitted after 20 seconds. Is the amount of transmitted ultraviolet light. When irradiating with ultraviolet rays, the eyes were protected with a UV Blocking Eyewear. The ultraviolet transmittance was determined by the following calculation method. Rs = As / An × 100 Rs = UV transmittance (%) of test piece An = UV transmittance when no film is installed As = UV transmittance of test piece

(A-2) Tensile test after irradiation of ultraviolet rays A test piece was placed on a stainless steel bat at a position 20 cm away from the ultraviolet irradiation apparatus, and a center mark portion (a narrow neck portion) of a 5% composite film test piece was placed. In order to be able to completely irradiate the test piece, the thick part of the end of the test piece was placed so as to overlap. At the time of ultraviolet irradiation, test pieces were taken out after irradiation for 1, 2, and 3 weeks, respectively. This test piece was subjected to a tensile test.

(B) Results (B-1) Ultraviolet transmittance test When the composite film was irradiated with ultraviolet rays, the composite film glowed, and the control film did not change. The glowing color differs depending on the type and amount of the composite lignin sample, and the lignin sample in the composite film absorbed ultraviolet rays. . However, a film [CDA] in which the color intensity and turbidity increase as the amount of composite increases.
Lignocresol (original) composite film] and a film that is transparent but increases in color depth [CDA secondary derivative II]
(Original) composite film], the luminous intensity at the time of irradiation with ultraviolet light increased as the amount of compounding increased in the former and decreased in the latter as the amount of compounding increased.
From these facts, it can be said that the color of the film due to the irradiation of ultraviolet rays is a color absorbing ultraviolet rays, and the luminous intensity is the degree of reflection.

FIG. 21, FIG. 22, and FIG. 23 show the ultraviolet transmittance of each composite film. The value of the ultraviolet transmittance is a ratio when the amount of ultraviolet light without the film is set to 100%, and it can be said that the smaller the numerical value, the less ultraviolet light is transmitted and the ultraviolet light is absorbed. For CDA and CTA control films (composite amount 0%), 95, respectively
97%, which was almost the same as the state without the film, and it was found that the film did not absorb ultraviolet rays. Compared with CDA and CTA, the transmittance of CTA was slightly higher.

FIG. 21 shows the ultraviolet transmittance of the composite film of CDA and hinoki sample, and FIG. 22 shows the ultraviolet transmittance of the composite film of CDA and beech sample. The tendency is that the more complex the lignin sample is, the more the original sample is from the acetylated sample.
The secondary derivative II had a lower ultraviolet transmittance than the primary derivative. When the amount of composite is increased, the transmittance is further decreased.
%, And it is clear that ultraviolet rays are completely absorbed. However, this tendency does not apply to the relationship between the original sample of the secondary derivative II of hinoki and the acetylated sample at a complexing amount of 20%. FIG. 23 shows a composite film of CTA and an acetylated sample. In the CTA composite film, the same tendency as described in the CDA composite film is used.
A much better correlation was obtained than with the CDA composite film.

From these results, a 20% CDA-beech secondary derivative II (original) composite film having a transparent film and the lowest ultraviolet transmittance was irradiated with ultraviolet rays for a long time. 5,10,20,30,6
The ultraviolet transmittance after irradiation for 0, 120 minutes and 24 hours was determined. As a result, the ultraviolet transmittance was 0% until 24 hours later.
From the above results, it was demonstrated that the composite of the lignin sample with the cellulose derivative actually imparted the ultraviolet absorbing ability.

(Summary) It was shown that the film containing only CDA and CTA did not absorb ultraviolet light and was almost equivalent to the film without the film. When the composite film was irradiated with ultraviolet light, the film glowed, The color and degree depended on the type of lignin sample and the amount of lignin. From the relationship between the transparency of the film and the amount of compounding, it was considered that the absorption of ultraviolet rays appeared in the color and the reflection of the films appeared in the luminosity. The complexed lignin sample was 2 times better than the original sample than the acetylated sample and more than the primary derivative.
The lower the derivative II, the lower the ultraviolet transmittance, and the transmittance was further decreased as the amount of the composite increased, and it became clear that the ultraviolet ray was not completely transmitted by the 20% composite film. The beech sample had a slightly lower transmittance as a whole, and it was considered that the difference in the ultraviolet transmittance was caused by the amount of the introduced cresol in lignocresol and the amount of the stilbene structure in the secondary derivative II.

In the CTA composite film, the factor of ultraviolet reflection due to turbidity was reduced by one factor, and it was thought that the results were more reliable in the concept of ultraviolet absorption instead of ultraviolet transmittance. For a 20% composite film of CDA-beech secondary derivative II (original), UV irradiation is performed for a long time, the UV transmittance is 0% even after 24 hours, and it is effective for the UV irradiation for a long time. It was shown that. As a result, it was demonstrated that the films in which the lignin samples having different ultraviolet absorption properties were combined with the cellulose derivative retained the respective properties.

In order to examine the effect of ultraviolet irradiation, discoloration due to ultraviolet irradiation for 0 to 3 weeks was observed, and the original sample was darkened with irradiation time. This was thought to be due to the fact that the hydroxyl groups in lignocresol were oxidized and the conjugated system in the molecule became longer. In the lignin sample composite film, the strength and elongation were maintained because the lignin sample absorbed ultraviolet rays to suppress degradation of the cellulose chain.

[0088]

According to the present invention, it has become possible to provide a novel cellulosic composition exhibiting excellent physical properties. Further, according to the present invention, a novel plasticizer and an ultraviolet absorber for a cellulose derivative have been provided. A new use of the lignophenol derivative separated from the lignocellulosic material according to the present invention will be provided,
Effective utilization of timber resources will be further promoted.

[Brief description of the drawings]

FIG. 1 is a diagram showing a first method for producing a lignophenol derivative.

FIG. 2 is a diagram showing a second method for producing a lignophenol derivative.

FIG. 3 is a diagram showing a reaction between lignin and a phenol derivative through contact with a concentrated acid at an interface of the phenol derivative phase in a two-phase separation system of a phenol derivative phase and a concentrated acid phase. .

FIG. 4 shows the results of gel permeation chromatography of a lignocresol derivative.

FIG. 5 shows ¹ H-NMR of a cypress-derived lignophenol derivative.

FIG. 6 shows the results of the analysis of a lignophenol derivative derived from beech.
¹ H-NMR is shown.

FIG. 7 shows the UV and ionization differential spectra of cypress-derived lignophenol derivatives.

FIG. 8 shows UV and ionization differential spectra of beech derived lignophenol derivatives.

FIG. 9 shows an IR spectrum of a cypress-derived lignophenol derivative.

FIG. 10 shows an IR spectrum of a lignophenol derivative derived from beech.

FIG. 11 shows TMA and DSC for CDA and CTA controls.

FIG. 12 shows TMA curves of various lignin samples.

FIG. 13 shows a TMA pattern of a composite film using a CDA-hinoki sample and having a composite amount of 10%.

FIG. 14 shows a TMA pattern of a composite film having a composite amount of 10% using a CDA-beech sample.

FIG. 15 shows a TMA pattern of a composite film having a composite amount of 10% using a CTA-acetylated sample.

FIG. 16 shows the relationship between cellulose chains and lignin molecules in a composite film.

FIG. 17 shows TMA curves of CDA, bunarignocresol (acetate), their blends and composite films.

FIG. 18 shows a TMA pattern of a CDA-original lignophenol derivative composite film.

FIG. 19 shows a TMA pattern of a CDA-acetylated lignophenol derivative composite film.

FIG. 20 shows a TMA pattern of a CTA-acetylated lignophenol derivative composite film.

FIG. 21 shows the ultraviolet transmittance of a composite film of CDA and a cypress sample.

FIG. 22 shows the ultraviolet transmittance of a composite film of CDA and a beech sample.

FIG. 23 shows the ultraviolet transmittance of a composite film of CTA and an acetylated sample.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C09K 3/00 104 C09K 3/00 104Z F term (reference) 4F071 AA09 AA73 AF29 AF53 AH01 AH03 AH04 BA01 BB03 BB05 BB06 BC01 BC03 BC04 BC06 4J002 AB02W AH00X GA01 GD02 GG01 GG02 GL00 GN00

Claims (12)

[Claims] (1) a cellulose derivative; and (2)
A lignophenol derivative obtained by adding and mixing an acid to a lignocellulosic material to which a phenol derivative has been added and separating the lignocellulosic material into a lignophenol derivative and a carbohydrate, an alkali-treated derivative of the lignophenol derivative, A composition comprising at least one lignophenol derivative selected from the group consisting of a hydroxy group-protected derivative of the above-mentioned lignophenol derivative or alkali-treated derivative. 2. The composition according to claim 1, wherein the amount of the lignophenol derivative is 1 to 50% by weight based on the total weight of the cellulose derivative and the lignophenol derivative. 3. The composition according to claim 1, wherein the cellulose derivative is cellulose acetate. 4. The method according to claim 3, wherein the cellulose derivative is cellulose diacetate or cellulose triacetate.
A composition according to claim 1. 5. The composition according to claim 1, wherein the phenol derivative to be added to the lignocellulosic substance is a phenol optionally having one or more substituents. 6. The composition according to claim 5, wherein the phenol derivative added to the lignocellulosic substance is p-cresol. 7. The composition according to claim 1, wherein the acid added to the lignocellulosic substance is 65% by weight or more of concentrated sulfuric acid. 8. The composition according to claim 1, wherein the lignophenol derivative is a derivative in which a hydroxyl group is protected. 9. A molded article comprising the composition according to any one of claims 1 to 8. 10. The molding according to claim 9, which is in the form of a film. 11. A lignophenol derivative obtained by adding an acid to a lignocellulosic material to which a phenol derivative is added, mixing the lignocellulosic material into a lignophenol derivative and a carbohydrate, and the lignophenol derivative A plasticizer for a cellulose derivative, comprising: an alkali-treated derivative of the above; and at least one lignophenol derivative selected from the group consisting of the above-mentioned lignophenol derivative or a derivative in which a hydroxyl group is protected in the alkali-treated derivative. 12. A lignophenol derivative obtained by adding an acid to a lignocellulosic material to which a phenol derivative is added, mixing and separating the lignocellulosic material into a lignophenol derivative and a carbohydrate, and the lignophenol derivative An ultraviolet absorber for cellulose derivatives, comprising an alkali-treated derivative of the above, and at least one lignophenol derivative selected from the group consisting of the above-mentioned lignophenol derivative or a derivative in which a hydroxyl group is protected in the alkali-treated derivative.