WO2014024978A1 - 導電性セルロース系樹脂組成物 - Google Patents
導電性セルロース系樹脂組成物 Download PDFInfo
- Publication number
- WO2014024978A1 WO2014024978A1 PCT/JP2013/071522 JP2013071522W WO2014024978A1 WO 2014024978 A1 WO2014024978 A1 WO 2014024978A1 JP 2013071522 W JP2013071522 W JP 2013071522W WO 2014024978 A1 WO2014024978 A1 WO 2014024978A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cellulose acetate
- degree
- resin composition
- conductive
- substitution
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/045—Fullerenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Definitions
- the present invention relates to a cellulose resin composition excellent in conductivity, a conductive molded body composed of the cellulose resin composition, and a method for producing the same.
- Non-Patent Documents 1 to 4 In recent years, in order to obtain even higher conductivity, methods have been attempted to reduce the surface resistivity or volume resistivity by using carbon nanotubes as an alternative to carbon black (Non-Patent Documents 1 to 4). However, in order to mix carbon nanotubes and resin and to exhibit high conductivity, it is necessary to use a special resin or to add a third component. Furthermore, when a resin composition containing carbon nanotubes is formed into a film or the like, it is necessary to form the resin composition by dissolving it in a solvent. In recent years, from the viewpoint of reducing the environmental load, there is a demand for a processing technique for a conductive molded body that does not use a solvent.
- An object of the present invention is to provide a conductive resin composition that exhibits high conductivity without adding a special resin or a third component, a conductive molded body composed of the resin composition, and a method for producing the same. There is. Another object of the present invention is to provide a conductive molded body having high conductivity and capable of being molded in an aqueous system, and a method for producing the same.
- the present inventors have mixed cellulose acetate having an acetyl group total substitution degree of 0.5 to 1.1 and a carbon material such as carbon nanotubes in an aqueous system and subjected to molding.
- the inventors have found that a conductive molded body having high conductivity can be easily and easily produced, and completed the present invention.
- the present invention comprises cellulose acetate (A) having a total substitution degree of acetyl group of 0.5 to 1.1, and single-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled graphene, multi-layered graphene, fullerene, and carbon black.
- A cellulose acetate
- B carbon material
- the volume resistivity of the conductive cellulose resin composition for example, 10 -3 ⁇ 20 ⁇ ⁇ cm, preferably from 10 -3 ⁇ 1 ⁇ ⁇ cm.
- the content of the carbon material (B) is, for example, 0.1 to 80% by weight of the entire conductive cellulose resin composition.
- composition distribution index (CDI) defined below of cellulose acetate is, for example, 1.0 to 2.0.
- CDI (actual value of composition distribution half width) / (theoretical value of composition distribution half width)
- Measured value of half width of composition distribution half width of composition distribution obtained by HPLC analysis of cellulose acetate propionate obtained by propionylating all remaining hydroxyl groups of cellulose acetate (sample)
- DS Degree of total acetyl substitution
- DPw Degree of weight average polymerization (value determined by GPC-light scattering method using cellulose acetate propionate obtained by propionylating all remaining hydroxyl groups of cellulose acetate (sample))
- the present invention also provides a conductive molded body composed of the conductive cellulose resin composition.
- the present invention further relates to a method for producing the conductive molded article, comprising cellulose acetate (A) having a total substitution degree of acetyl groups of 0.5 to 1.1, single-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled carbon nanotubes, Conductivity including a step of shaping an aqueous dispersion containing at least one carbon material (B) selected from the group consisting of layer graphene, multilayer graphene, fullerene and carbon black, and drying the shaped hydrous molding Provided is a method for producing a molded product.
- A cellulose acetate
- B aqueous dispersion containing at least one carbon material selected from the group consisting of layer graphene, multilayer graphene, fullerene and carbon black
- cellulose acetate (A) having a water-soluble acetyl group total substitution degree of 0.5 to 1.1 is used, so it is mixed with a carbon material such as carbon nanotubes in an aqueous system, shaped and dried.
- a conductive molded body having high conductivity can be produced.
- the conductive cellulose resin composition and the molded body thereof of the present invention exhibit high conductivity without using a special resin or a third component. Furthermore, even if incinerated, greenhouse gases (SOx, NOx) are not discharged or hardly discharged.
- the conductive cellulose resin composition of the present invention comprises cellulose acetate (A) having a total acetyl group substitution degree of 0.5 to 1.1, single-walled carbon nanotubes, multi-walled carbon nanotubes, single-layer graphene, multi-layer graphene, And at least one carbon material (B) selected from the group consisting of fullerene and carbon black.
- the cellulose acetate ester (A) in the present invention has an acetyl total substitution degree (average substitution degree) of 0.5 to 1.1. When the total degree of acetyl substitution is within this range, the solubility in water is excellent, and when it is outside this range, the solubility in water tends to decrease.
- a preferred range of the total degree of acetyl substitution is 0.55 to 1.0, and a more preferred range is 0.6 to 0.95.
- the total degree of acetyl substitution can be measured by a known titration method in which cellulose acetate is dissolved in water and the degree of substitution of cellulose acetate is determined. The total degree of acetyl substitution can also be measured by NMR after propionylating the hydroxyl group of cellulose acetate (see the method described later), dissolving in deuterated chloroform.
- the total degree of acetyl substitution can be obtained by converting the degree of acetylation determined according to the method for measuring the degree of acetylation in ASTM: D-817-91 (testing method for cellulose acetate, etc.) by the following formula. This is the most common method for determining the degree of substitution of cellulose acetate.
- DS 162 ⁇ AV ⁇ 0.01 / (60-42 ⁇ AV ⁇ 0.01)
- DS Degree of total acetyl substitution
- AV Degree of acetylation (%)
- 500 mg of dried cellulose acetate (sample) was precisely weighed and dissolved in 50 ml of a mixed solvent of ultrapure water and acetone (volume ratio 4: 1), 50 ml of 1N sodium hydroxide aqueous solution was added, and 25 ° C. Saponify for 2 hours.
- AV (degree of acetylation) (%) is calculated according to the following formula.
- AV (%) (A ⁇ B) ⁇ F ⁇ 1.21 / sample weight (g)
- composition distribution index (CDI) composition distribution index (intermolecular substitution degree distribution) of the cellulose acetate ester (A) is not particularly limited, and the composition distribution index (CDI) is, for example, 1.0 to 3.0.
- the composition distribution index (CDI) is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, still more preferably 1.0 to 1.6, particularly preferably 1.0 to 1.5. It is.
- the composition distribution index (CDI) of the cellulose acetate ester (A) is smaller (closer to 1.0), and the composition distribution (intermolecular substitution degree distribution) becomes more uniform. The strength of time is very high.
- composition distribution index is the ratio of the measured value to the theoretical value of the half value width of the composition distribution [(actual value of the half value width of the composition distribution) / (theoretical value of the half value width of the composition distribution)]. Defined.
- the composition distribution half-width is also referred to as “intermolecular substitution degree half-width” or simply “substitution degree distribution half-width”.
- the maximum peak half-value width (also referred to as “half-value width”) of the intermolecular substitution degree distribution curve of cellulose acetate can be used as an index.
- the half width is the width of the chart at half the height of the peak of the chart, where the acetyl substitution degree is on the horizontal axis (x axis) and the abundance at this substitution degree is on the vertical axis (y axis). It is an index representing the standard of variation in distribution.
- the half value width of the substitution degree distribution can be determined by high performance liquid chromatography (HPLC) analysis.
- the theoretical distribution of the half value width of composition distribution (substitution degree distribution half width) can be calculated stochastically. That is, the theoretical value of the composition distribution half width is obtained by the following equation (1).
- m Total number of hydroxyl groups and acetyl groups in one molecule of cellulose acetate
- DPw Weight average polymerization degree (by GPC-light scattering method) A method for measuring the weight average degree of polymerization (DPw) will be described later.
- the theoretical value of the composition distribution half width is represented by the substitution degree and the polymerization degree, it is expressed as follows.
- the following formula (2) is a defining formula for obtaining the theoretical value of the composition distribution half width.
- DS Degree of total acetyl substitution
- DPw Degree of weight average polymerization (by GPC-light scattering method) A method for measuring the weight average degree of polymerization (DPw) will be described later.
- the actual value of the composition distribution half width is the composition distribution half width obtained by HPLC analysis of cellulose acetate propionate obtained by propionylating all remaining hydroxyl groups (unsubstituted hydroxyl groups) of cellulose acetate (sample). It is.
- cellulose acetate having a total degree of acetyl substitution of 2 to 3 can be subjected to high performance liquid chromatography (HPLC) analysis without pretreatment, whereby the half width of the composition distribution can be determined.
- HPLC high performance liquid chromatography
- JP 2011-158664 A describes a composition distribution analysis method for cellulose acetate having a substitution degree of 2.27 to 2.56.
- the actual value of the composition distribution half-width is obtained by derivatizing the residual hydroxyl group in cellulose acetate as a pretreatment before HPLC analysis, and then performing HPLC analysis.
- Ask. The purpose of this pretreatment is to convert the low-substituted cellulose acetate into a derivative that can be easily dissolved in an organic solvent to enable HPLC analysis. That is, the residual hydroxyl group in the molecule is completely propionylated, and the fully derivatized cellulose acetate propionate (CAP) is subjected to HPLC analysis to determine the composition distribution half width (actual value).
- CAP fully derivatized cellulose acetate propionate
- CAP fully derivatized cellulose acetate propionate
- Mw / Mn polydispersity
- DPw weight average polymerization degree
- HPLC analysis a plurality of cellulose acetate propionates having different degrees of acetyl substitution are used as standard samples, HPLC analysis is performed with a predetermined measuring apparatus and measurement conditions, and a calibration created using the analysis values of these standard samples. Obtain the half-value width (measured value) of cellulose acetate (sample) from the curve [Curve showing the relationship between the elution time of cellulose acetate propionate and the degree of acetyl substitution (0 to 3), usually a cubic curve]. Can do. What is required by HPLC analysis is the relationship between the elution time and the distribution of acetyl substitution degree of cellulose acetate propionate.
- Substitution degree distribution curve obtained from the calibration curve [Substitution degree distribution curve of cellulose acetate propionate with the abundance of cellulose acetate propionate as the vertical axis and the acetyl substitution degree as the horizontal axis] ("Intermolecular substitution degree distribution curve )),
- the half value width of the substitution degree distribution is obtained as follows for the maximum peak (E) corresponding to the average substitution degree.
- the base (A) on the low substitution degree side of the peak (E) and the base line (AB) in contact with the high substitution side base (B) are drawn, and from this peak, the maximum peak (E) Take a vertical line on the horizontal axis.
- An intersection (C) between the perpendicular and the base line (AB) is determined, and an intermediate point (D) between the maximum peak (E) and the intersection (C) is obtained.
- a straight line parallel to the base line (AB) is drawn through the intermediate point (D) to obtain two intersection points (A ′, B ′) with the intermolecular substitution degree distribution curve.
- a perpendicular line is drawn from the two intersections (A ′, B ′) to the horizontal axis, and the width between the two intersections on the horizontal axis is defined as the half-value width of the maximum peak (that is, the substitution value distribution half-value width).
- the half-value width of the substitution degree distribution depends on the degree of acetylation of the hydroxyl chain of each glucose chain constituting the molecular chain of cellulose acetate propionate in the sample. (Retention time) is different. Therefore, ideally, the holding time width indicates the width of the composition distribution (in units of substitution degree).
- tubes such as a guide column for protecting the column
- the width of the holding time that is not caused by the width of the composition distribution is often included as an error. As described above, this error is affected by the length and inner diameter of the column, the length from the column to the detector, the handling, and the like, and varies depending on the apparatus configuration.
- the half value width of the substitution degree distribution of cellulose acetate propionate can be usually obtained as the correction value Z based on the correction formula represented by the following formula.
- Z (X2-Y2) 1/2
- X is the half-value width (uncorrected value) of the substitution degree distribution obtained with a predetermined measuring apparatus and measurement conditions.
- Y ax + b (0 ⁇ x ⁇ 3).
- a is the half-value width of the substitution degree distribution of cellulose acetate having a total degree of substitution of 3 determined using the same measuring apparatus and measurement conditions as X
- b is the total degree of substitution of 3 obtained using the same measuring apparatus and measuring conditions as X. It is a half value width of substitution degree distribution of cellulose propionate.
- x is the total acetyl substitution degree of the measurement sample (0 ⁇ x ⁇ 3)]
- the cellulose acetate (or cellulose propionate) having a total substitution degree of 3 is a cellulose ester in which all of the hydroxyl groups of cellulose are esterified, and (ideally) the half-width of the substitution degree distribution. (Ie, the substitution degree distribution half-width 0) cellulose ester.
- the measured value of the composition distribution half width (substitution degree distribution half width) of the cellulose acetate ester (A) is preferably 0.12 to 0.34, more preferably 0.13 to 0.00. 25.
- substitution degree distribution theoretical formula described above is a probabilistic calculation value that assumes that all acetylation and deacetylation proceed independently and equally. That is, the calculated value according to the binomial distribution. Such an ideal situation is not realistic. Unless special measures are taken for the hydrolysis reaction of cellulose acetate or the post-treatment after the reaction, the substitution degree distribution of the cellulose ester is much wider than that stochastically determined by the binomial distribution.
- Precipitation of cellulose acetate having a substitution degree of 2.3 involves fractionation depending on the molecular weight and a fractional fraction associated with the substitution degree (chemical composition). There is no report that significant fractionation can be achieved with the degree of substitution (chemical composition) as found by the present inventors. Furthermore, it has not been verified that the substitution degree distribution (chemical composition) can be controlled by dissolution fractionation or precipitation fractionation for low-substituted cellulose acetate.
- Another device for narrowing the substitution degree distribution found by the present inventors is a hydrolysis reaction (aging reaction) of cellulose acetate at a high temperature of 90 ° C. or higher (or higher than 90 ° C.).
- aging reaction aging reaction
- decomposition of cellulose is preferred in a high-temperature reaction at 90 ° C. or higher.
- This idea can be said to be a belief (stereotype) based solely on the consideration of viscosity.
- the present inventors hydrolyze cellulose acetate to obtain low-substituted cellulose acetate, it is in a large amount of acetic acid at a high temperature of 90 ° C. or higher (or higher than 90 ° C.), preferably in the presence of a strong acid such as sulfuric acid. It was found that when the reaction was carried out with the above, the degree of polymerization was not lowered, but the viscosity was lowered with a decrease in CDI. That is, it has been clarified that the viscosity decrease due to the high temperature reaction is not due to a decrease in the degree of polymerization but is based on a decrease in structural viscosity due to a narrow substitution degree distribution.
- the degree of acetyl substitution at the 2, 3 and 6 positions of the glucose ring of the cellulose acetate ester (A) is measured by the NMR method according to the method of Tezuka (Carbondr. Res. 273, 83 (1995)). It can. That is, a free hydroxyl group of a cellulose acetate sample is propionylated with propionic anhydride in pyridine. The obtained sample is dissolved in deuterated chloroform and the 13 C-NMR spectrum is measured.
- the carbon signal of the acetyl group appears in the order of 2, 3, 6 from the high magnetic field in the region of 169 ppm to 171 ppm, and the signal of the carbonyl carbon of the propionyl group appears in the same order in the region of 172 ppm to 174 ppm. From the abundance ratio of acetyl groups and propionyl groups at the corresponding positions, the degree of acetyl substitution at the 2, 3, and 6 positions of the glucose ring in the original cellulose diacetate can be determined. The degree of acetyl substitution can be analyzed by 1 H-NMR in addition to 13 C-NMR.
- the standard deviation ⁇ of the substitution degree at the 2nd, 3rd and 6th positions is defined by the following equation.
- the standard deviation of the acetyl substitution degree at the 2, 3 and 6 positions of the glucose ring of the cellulose acetate ester (A) is preferably 0.08 or less (0 to 0.08).
- Cellulose acetate having a standard deviation of 0.08 or less is evenly substituted at the 2, 3, and 6 positions of the glucose ring, and has excellent solubility in water.
- the high elongation when it is used as a film is high.
- polydispersity (Mw / Mn)
- polydispersity (dispersion degree; Mw / Mn) is a value obtained by GPC-light scattering method using cellulose acetate propionate obtained by propionylating all remaining hydroxyl groups of cellulose acetate (sample). is there.
- the polydispersity (dispersity: Mw / Mn) of the cellulose acetate ester (A) in the present invention is preferably in the range of 1.2 to 2.5.
- Cellulose acetate having a polydispersity Mw / Mn in the above range has a uniform molecular size, is excellent in water solubility, and has a high elongation when used as a film.
- the number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw / Mn) of cellulose acetate can be determined by a known method using HPLC.
- the polydispersity (Mw / Mn) of cellulose acetate is determined by dissolving cellulose acetate (sample) in the same manner as in the case of obtaining the measured value of the half-value width of the composition distribution in order to make the measurement sample soluble in an organic solvent.
- Is completely derivatized cellulose acetate propionate (CAP) Is completely derivatized cellulose acetate propionate (CAP), and then size exclusion chromatography analysis is performed under the following conditions (GPC-light scattering method).
- the weight average degree of polymerization (DPw) is a value determined by GPC-light scattering method using cellulose acetate propionate obtained by propionylating all remaining hydroxyl groups of cellulose acetate (sample).
- the weight average polymerization degree (DPw) of the cellulose acetate ester (A) in the present invention is preferably in the range of 50 to 800. If the weight average degree of polymerization (DPw) is too low, the strong elongation tends to be low. On the other hand, if the weight average degree of polymerization (DPw) is too high, filterability tends to deteriorate.
- the weight average degree of polymerization (DPw) is preferably 55 to 700, more preferably 60 to 600.
- the weight average degree of polymerization is obtained by completely derivatizing cellulose acetate (sample) with a method similar to that for obtaining the measured half-value width of the composition distribution. After obtaining propionate (CAP), it is determined by size exclusion chromatography analysis (GPC-light scattering method).
- the molecular weight (polymerization degree) and polydispersity (Mw / Mn) of water-soluble cellulose acetate are measured by a GPC-light scattering method (GPC-MALLS, GPC-LALLS, etc.).
- GPC-MALLS GPC-light scattering method
- detection of light scattering is generally difficult with an aqueous solvent. This is because aqueous solvents generally have a large amount of foreign matter and are easily contaminated by secondary contamination once purified.
- the spread of molecular chains may not be stable due to the influence of ionic dissociation groups present in a trace amount, and if water-soluble inorganic salt (for example, sodium chloride) is added to suppress this, it will dissolve.
- water-soluble inorganic salt for example, sodium chloride
- the state may become unstable, and an aggregate may be formed in an aqueous solution.
- One effective method for avoiding this problem is to derivatize water-soluble cellulose acetate so that it is dissolved in an organic solvent that is less contaminated and less susceptible to secondary contamination, and GPC-light scattering measurement is performed in the organic solvent. That is.
- Propionylation is effective for derivatization of water-soluble cellulose acetate for this purpose, and specific reaction conditions and post-treatment are as described in the explanation of the measured value of the half width of the composition distribution.
- the 6% viscosity of the cellulose acetate ester (A) in the present invention is, for example, 5 to 500 mPa ⁇ s, preferably 6 to 300 mPa ⁇ s. If the 6% viscosity is too high, filterability may deteriorate. On the other hand, if the 6% viscosity is too low, the strength at the time of forming a film tends to decrease.
- the 6% viscosity of cellulose acetate can be measured by the following method. Add 3.00 g of dry sample to a 50 ml volumetric flask and add distilled water to dissolve. The obtained 6 wt / vol% solution is transferred to a predetermined Ostwald viscometer mark and temperature-controlled at 25 ⁇ 1 ° C. for about 15 minutes. Measure the flow-down time between the time marks and calculate the 6% viscosity by the following formula.
- the cellulose acetate ester (A) (low-substituted cellulose acetate) in the present invention includes, for example, (A) a medium to high-substituted cellulose acetate hydrolysis step (aging step), (B) a precipitation step, and as necessary. According to (C) washing
- (A) Hydrolysis step (aging step)
- medium to high-substituted cellulose acetate (hereinafter sometimes referred to as “raw cellulose acetate”) is hydrolyzed.
- the total acetyl substitution degree of the medium to high substitution cellulose acetate used as a raw material is, for example, 1.5 to 3, preferably 2 to 3.
- As the raw material cellulose acetate commercially available cellulose diacetate (acetyl total substitution degree: 2.27 to 2.56) and cellulose triacetate (acetyl total substitution degree: more than 2.56 to 3) can be used.
- the hydrolysis reaction can be performed by reacting raw material cellulose acetate with water in the presence of a catalyst (aging catalyst) in an organic solvent.
- a catalyst aging catalyst
- the organic solvent include acetic acid, acetone, alcohol (such as methanol), and mixed solvents thereof. Among these, a solvent containing at least acetic acid is preferable.
- a catalyst generally used as a deacetylation catalyst can be used.
- sulfuric acid is particularly preferable.
- the amount of the organic solvent (for example, acetic acid) used is, for example, 0.5 to 50 parts by weight, preferably 1 to 20 parts by weight, and more preferably 3 to 10 parts by weight with respect to 1 part by weight of the raw material cellulose acetate. .
- the amount of the catalyst (for example, sulfuric acid) used is, for example, 0.005 to 1 part by weight, preferably 0.01 to 0.5 part by weight, more preferably 0.02 to 1 part by weight based on 1 part by weight of the raw material cellulose acetate. 0.3 parts by weight. If the amount of the catalyst is too small, the hydrolysis time becomes too long, which may cause a decrease in the molecular weight of cellulose acetate. On the other hand, if the amount of the catalyst is too large, the degree of change in the depolymerization rate with respect to the hydrolysis temperature increases, and even if the hydrolysis temperature is low to some extent, the depolymerization rate increases and it is difficult to obtain cellulose acetate having a somewhat high molecular weight. Become.
- the amount of water in the hydrolysis step is, for example, 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, and more preferably 2 to 7 parts by weight with respect to 1 part by weight of the raw material cellulose acetate.
- the amount of the water is, for example, 0.1 to 5 parts by weight, preferably 0.3 to 2 parts by weight, more preferably 0.5 to 1 part per 1 part by weight of the organic solvent (for example, acetic acid). .5 parts by weight.
- all amounts of water may be present in the system at the start of the reaction, in order to prevent precipitation of cellulose acetate, a part of the water to be used is present in the system at the start of the reaction, and the remaining water is removed. It may be added to the system in 1 to several times.
- the reaction temperature in the hydrolysis step is, for example, 40 to 130 ° C., preferably 50 to 120 ° C., more preferably 60 to 110 ° C.
- a positive reaction preferably when a strong acid such as sulfuric acid is used as a catalyst and acetic acid is used excessively as a reaction solvent, a positive reaction (hydrolysis reaction).
- a reverse reaction acetylation reaction
- the substitution degree distribution becomes narrow, and it is possible to obtain a low substituted cellulose acetate having a very small composition distribution index CDI without any particular ingenuity in the post-treatment conditions. .
- precipitation is performed using a mixed solvent containing two or more solvents as the precipitation solvent, precipitation fractionation and / or dissolution.
- a low-substituted cellulose acetate having a very small composition distribution index CDI can be obtained.
- Step 2 After completion of the hydrolysis reaction, the temperature of the reaction system is cooled to room temperature, and a precipitation solvent is added to precipitate low-substituted cellulose acetate.
- a precipitation solvent an organic solvent miscible with water or an organic solvent having high solubility in water can be used. Examples thereof include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and isopropyl alcohol; esters such as ethyl acetate; nitrogen-containing compounds such as acetonitrile; ethers such as tetrahydrofuran; and mixed solvents thereof.
- the mixed solvent include a mixed solvent of acetone and methanol, a mixed solvent of isopropyl alcohol and methanol, and the like.
- composition distribution (intermolecular substitution degree distribution) is narrow, A low-substituted cellulose acetate having a very small composition distribution index CDI can be obtained.
- low-substituted cellulose acetate (solid matter) obtained by precipitation is dissolved in water to obtain an aqueous solution having an appropriate concentration (for example, 2 to 10% by weight, preferably 3 to 8% by weight).
- a poor solvent is added to this aqueous solution (or the aqueous solution is added to the poor solvent), and maintained at an appropriate temperature (for example, 30 ° C. or less, preferably 20 ° C. or less) to precipitate low-substituted cellulose acetate, This can be done by collecting the precipitate.
- the poor solvent include alcohols such as methanol and ketones such as acetone.
- the amount of the poor solvent used is, for example, 1 to 10 parts by weight, preferably 2 to 7 parts by weight with respect to 1 part by weight of the aqueous solution.
- the low-substituted cellulose acetate (solid matter) obtained by the precipitation or the low-substituted cellulose acetate (solid matter) obtained by the precipitation fractionation is mixed with water and an organic solvent (for example, acetone or the like).
- an organic solvent for example, acetone or the like.
- a mixed solvent of an alcohol such as ketone and ethanol, and the like and after stirring at an appropriate temperature (for example, 20 to 80 ° C., preferably 25 to 60 ° C.), it is separated into a concentrated phase and a diluted phase by centrifugation, A precipitation solvent (for example, a ketone such as acetone or an alcohol such as methanol) is added to the dilute phase, and the precipitate (solid matter) is recovered.
- the concentration of the organic solvent in the mixed solvent of water and organic solvent is, for example, 5 to 50% by weight, preferably 10 to 40% by weight.
- the precipitate (solid matter) obtained in the precipitation step (B) is preferably washed with an organic solvent (poor solvent) such as alcohol such as methanol and ketone such as acetone. Moreover, it is also preferable to wash and neutralize with an organic solvent containing a basic substance (for example, alcohol such as methanol, ketone such as acetone).
- alkali metal compounds for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal carbonates such as sodium hydrogen carbonate) Hydrogen salts; alkali metal carboxylates such as sodium acetate and potassium acetate; sodium alkoxides such as sodium methoxide and sodium ethoxide), alkaline earth metal compounds (for example, alkaline earth such as magnesium hydroxide and calcium hydroxide) Alkaline earth metal carbonates such as metal hydroxide, magnesium carbonate and calcium carbonate; alkaline earth metal carboxylates such as magnesium acetate and calcium acetate; alkaline earth metal alkoxides such as magnesium ethoxide, etc.) can be used. .
- alkali metal compounds such as potassium acetate are particularly preferable.
- the conductive filler is at least one selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, single-layer graphene, multi-layer graphene, fullerene, and carbon black.
- the carbon material (B) is used.
- Single-walled and multi-walled carbon nanotubes, single-walled and multi-layer graphene, fullerene, and carbon black are common in that they are composed of carbon atoms, and can be imparted with high conductivity to the resin composition by being blended with a cellulose-based resin.
- Carbon nanotubes, graphene, and fullerene are carbon allotropes.
- Carbon nanotubes include single-walled carbon nanotubes having a single graphite film (graphene sheet) forming a tube and multi-walled carbon nanotubes having multiple layers.
- the number of multi-walled carbon nanotubes is, for example, 2 to 50, preferably 3 to 30.
- Carbon nanotubes are not limited to raw materials and production methods.
- the diameter (outer diameter) of the carbon nanotube is usually 0.5 to 180 nm as an average diameter, preferably 0.7 to 100 nm, and more preferably 1 to 50 nm.
- the average length of the carbon nanotubes is usually 0.2 ⁇ m to 2000 ⁇ m, preferably 0.3 ⁇ m to 1000 ⁇ m, more preferably 0.5 ⁇ m to 100 ⁇ m, and particularly preferably 1 ⁇ m to 50 ⁇ m.
- the aspect ratio of the carbon nanotube is preferably 5 or more, and more preferably 50 or more.
- Graphene is a sheet of sp 2 bonded carbon atoms with a thickness of 1 atom, and there are single layer graphene and multilayer graphene.
- the number of layers of the multilayer graphene is, for example, about 2 to 200, preferably 3 to 50.
- the maximum dimension in the plane direction of graphene is, for example, about 1 to 100 ⁇ m.
- Fullerenes are clusters composed of tens or more carbon atoms. Exemplary fullerenes are C 60 fullerenes.
- Carbon black is a fine particle of carbon having a diameter of about 3 to 500 nm. Carbon black is not limited to raw materials and production methods.
- the content of the carbon material (B) in the conductive cellulose resin composition can be selected within a wide range, for example, 0.1 to 80% by weight, preferably 1 to 70% by weight, and more preferably 3%. ⁇ 60% by weight.
- high conductivity is exhibited even if the content of the carbon material (B) is small. Further, even if a large amount of the carbon material (B) is contained, the moldability is excellent.
- a mixer In preparing the dispersion, a mixer is usually used.
- the mixer include a container with a stirrer, a Henschel mixer, a bead mill, a plast mill, a Banbury mixer, and an extruder.
- the amount of water used in preparing the dispersion can be appropriately selected according to the type and amount of the cellulose acetate ester (A) and the type and amount of the carbon material (B).
- the amount is usually 10 to 3000 parts by weight, preferably 20 to 2000 parts by weight, and usually 200 to 300000 parts by weight, preferably 300 to 20000 parts by weight with respect to 100 parts by weight of the carbon material (B). It is.
- a filler [a carbon material (B) is excluded]
- light stability Agents colorants, flow modifiers, antistatic agents, antibacterial agents, ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, flame retardants and the like.
- the amount of these additives used is preferably 30% by weight or less, more preferably 15% by weight or less, and still more preferably 5% by weight or less, as the content in the conductive cellulose resin composition.
- the total amount of these additives is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less as the content in the conductive cellulose resin composition.
- Cellulose acetate prepared by (1) preparing an aqueous dispersion of carbon material (B) Step of adding to aqueous solution of ester (A), mixing and stirring (3) Step of shaping the dispersion obtained in step (2) (4) Drying the shaped hydrous molded product and solidifying ( Solidification process
- cellulose acetate (A) and carbon material This is considered to be due to the formation of a dispersed state in which B) has an appropriate affinity and is easy to develop conductivity.
- the volume resistivity of the conductive cellulose resin composition thus obtained is usually 10 ⁇ 3 to 20 ⁇ ⁇ cm, preferably 10 ⁇ 3 to 1 ⁇ ⁇ cm.
- the conductive cellulose resin composition of the present invention and the conductive molded body of the present invention exhibit extremely high conductivity without using a special resin or a third component such as an iron or cobalt component.
- the conductive molded body (film, sheet, etc.) of the present invention is, for example, a conductive material used for wiring of electric / electronic devices, etc .; a conductive material such as a shielding material that shields or absorbs electromagnetic waves, or an ESD (electrostatic discharge) prevention material. It can be used as a sex material.
- the total hydrolysis time is 6 hours.
- the first aging from the start of the reaction to the first water addition, the second aging from the first water addition to the second water addition, the reaction from the second water addition to the end of the reaction (ripening completed) This is called the third aging.
- the temperature of the system is cooled to room temperature (about 25 ° C.), and 15 parts by weight of acetone / methanol 1: 1 (weight ratio) mixed solvent (precipitating agent) is added to the reaction mixture to precipitate. Generated.
- the precipitate was recovered as a wet cake having a solid content of 15% by weight, and washed by adding 8 parts by weight of methanol and draining to a solid content of 15% by weight. This was repeated three times. The washed precipitate was further washed twice with 8 parts by weight of methanol containing 0.04% by weight of potassium acetate, neutralized and dried to obtain low-substituted cellulose acetate.
- the total acetyl substitution degree (DS), weight average polymerization degree (DPw), polydispersity (dispersion degree) (Mw / Mn), and composition distribution index (CDI) of the low substituted cellulose acetate obtained in each synthesis example are as follows. It measured by the method of. Table 1 shows the production conditions and the measurement results of the physical properties of the resulting low-substituted cellulose acetate. The “sample number” in Table 1 means the sample number of the obtained low-substituted cellulose acetate.
- CDI composition distribution index
- CDI Z / Z 0
- Z 0 is the composition distribution generated when acetylation and partial deacetylation in the preparation of all partially substituted cellulose acetates occur with equal probability for all hydroxyl groups (or acetyl groups) of all molecules.
- DPw weight average polymerization degree
- p (acetyl DS of unknown sample) / 3 q: 1-P
- Examples 1 to 10, Comparative Examples 1 and 2 The low-substituted cellulose acetate obtained in Synthesis Examples 1 to 12, a 4% by weight carbon nanotube dispersion (multilayer, outer diameter of about 13 nm; manufactured by Wako Pure Chemical Industries), and water are mixed at a ratio shown in Table 2 to reduce the amount. An aqueous dispersion containing cellulose acetate with substitution degree and carbon nanotubes was prepared. In the column of “Polymer” in Table 2, the sample number of the low-substituted cellulose acetate used is shown.
- a predetermined amount of low-substituted cellulose acetate and a predetermined amount of water were placed in a glass container equipped with a stirring blade, and mixed and stirred at 25 ⁇ 5 ° C. for 16 hours to prepare an aqueous solution of low-substituted cellulose acetate.
- a predetermined amount of the 4 wt% carbon nanotube dispersion is added to the aqueous solution of low-substituted cellulose acetate, and the mixture is further stirred for 4 hours, so that the carbon nanotube (CNT) has a predetermined content (1 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%) low-substituted cellulose acetate aqueous dispersion was obtained.
- the obtained aqueous dispersion was allowed to stand for 7 days. Adjust the amount of the aqueous dispersion applied so that the solid content after drying is 45 ⁇ m, cast it on a glass plate with a bar coater, and dry at 70 ° C.
- PVA 117 degree of saponification 98.7%, aqueous solution viscosity (4 wt%, 20 ° C.) 28.2 mPa ⁇ s
- PVA HC degree of saponification 99.9%, aqueous solution viscosity (4% by weight, 20 ° C.) 24.8 mPa ⁇ s
- PVA 217 degree of saponification 88.1%, aqueous solution viscosity (4% by weight, 20 ° C.) 22.6 mPa ⁇ s That is, a predetermined amount of polyvinyl alcohol and a predetermined amount of water were put into a glass container equipped with stirring blades, and mixed and stirred at 70 ⁇ 5 ° C.
- an aqueous solution of polyvinyl alcohol This aqueous solution of polyvinyl alcohol is cooled to 25 ⁇ 5 ° C., a predetermined amount of 4 wt% carbon nanotube dispersion liquid (multilayer, outer diameter of about 13 nm; manufactured by Wako Pure Chemical Industries, Ltd.) is added, and further stirred for 4 hours.
- a polyvinyl alcohol aqueous dispersion containing a predetermined content (% by weight) was obtained. Adjust the amount of the aqueous dispersion applied so that the solid content after drying is 45 ⁇ m, cast it on a glass plate with a bar coater, and dry at 70 ° C. for 90 minutes. It was.
- the formed film was peeled off from the glass plate and further dried at 70 ° C. for 30 minutes.
- the volume resistivity (volume resistivity) ( ⁇ ⁇ cm) of the obtained film was measured according to JIS K7194.
- the trade name “Loresta” (MCP-T610 type) (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used as the measuring apparatus. The results are shown in Table 3.
- the films of the examples are excellent in conductivity even when the content of the carbon material is small, and can maintain the film shape even when the content of the carbon material is increased. Can be demonstrated.
- the conductive cellulose resin composition and the molded body thereof of the present invention exhibit high conductivity without using a special resin or a third component. Further, it can be easily molded in an aqueous system. For this reason, for example, it can be used as a conductive material such as a conductive material used for wiring of electric / electronic devices, a shielding material that blocks or absorbs electromagnetic waves, and an ESD (electrostatic discharge) prevention material.
- a conductive material such as a conductive material used for wiring of electric / electronic devices, a shielding material that blocks or absorbs electromagnetic waves, and an ESD (electrostatic discharge) prevention material.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Nanotechnology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Conductive Materials (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
本発明の他の目的は、高い導電性を有するとともに、水系で成形できる導電性成形体、及びその製造方法を提供することにある。
CDI=(組成分布半値幅の実測値)/(組成分布半値幅の理論値)
組成分布半値幅の実測値:酢酸セルロース(試料)の残存水酸基をすべてプロピオニル化して得られるセルロースアセテートプロピオネートをHPLC分析して求めた組成分布半値幅
DPw:重量平均重合度(酢酸セルロース(試料)の残存水酸基をすべてプロピオニル化して得られるセルロースアセテートプロピオネートを用いてGPC-光散乱法により求めた値)
(アセチル総置換度)
本発明における酢酸セルロースエステル(A)は、アセチル総置換度(平均置換度)が0.5~1.1である。アセチル総置換度がこの範囲であると水に対する溶解性に優れ、この範囲を外れると水に対する溶解性が低下する傾向となる。前記アセチル総置換度の好ましい範囲は0.55~1.0であり、さらに好ましい範囲は0.6~0.95である。アセチル総置換度は、酢酸セルロースを水に溶解し、酢酸セルロースの置換度を求める公知の滴定法により測定できる。また、該アセチル総置換度は、酢酸セルロースの水酸基をプロピオニル化した上で(後述の方法参照)、重クロロホルムに溶解し、NMRにより測定することもできる。
DS=162×AV×0.01/(60-42×AV×0.01)
DS:アセチル総置換度
AV:酢化度(%)
まず、乾燥した酢酸セルロース(試料)500mgを精秤し、超純水とアセトンとの混合溶媒(容量比4:1)50mlに溶解した後、1N-水酸化ナトリウム水溶液50mlを添加し、25℃で2時間ケン化する。次に、1N-塩酸50mlを添加し、フェノールフタレインを指示薬として、1N-水酸化ナトリウム水溶液(1N-水酸化ナトリウム規定液)で、脱離した酢酸量を滴定する。また、同様の方法によりブランク試験(試料を用いない試験)を行う。そして、下記式にしたがってAV(酢化度)(%)を算出する。
AV(%)=(A-B)×F×1.21/試料重量(g)
A:1N-水酸化ナトリウム規定液の滴定量(ml)
B:ブランクテストにおける1N-水酸化ナトリウム規定液の滴定量(ml)
F:1N-水酸化ナトリウム規定液のファクター
本発明において、前記酢酸セルロースエステル(A)の組成分布(分子間置換度分布)は特に限定されず、組成分布指数(CDI)は、例えば1.0~3.0である。組成分布指数(CDI)は、好ましくは1.0~2.0、より好ましくは1.0~1.8、さらに好ましくは1.0~1.6、特に好ましくは1.0~1.5である。前記酢酸セルロースエステル(A)の組成分布指数(CDI)が小さいほど(1.0に近づくほど)、組成分布(分子間置換度分布)が均一となり、低置換度であっても、フィルムとした時の強伸度が非常に高い。また、炭素材料(B)の含有量が多くても、クラックの発生を防止でき、自立フィルムとして使用に供することができる。これは、組成分布が均一であることにより、フィルム構造の欠陥が減少するためである。また、組成分布が均一であると、総置換度が通常よりも広い範囲で水溶性を確保できる。
組成分布半値幅(置換度分布半値幅)は確率論的に理論値を算出できる。すなわち、組成分布半値幅の理論値は以下の式(1)で求められる。
p:酢酸セルロース1分子中の水酸基がアセチル置換されている確率
q=1-p
DPw:重量平均重合度(GPC-光散乱法による)
重量平均重合度(DPw)の測定法は後述する。
DPw:重量平均重合度(GPC-光散乱法による)
重量平均重合度(DPw)の測定法は後述する。
本発明において、組成分布半値幅の実測値とは、酢酸セルロース(試料)の残存水酸基(未置換水酸基)をすべてプロピオニル化して得られるセルロースアセテートプロピオネートをHPLC分析して求めた組成分布半値幅である。
装置: Agilent 1100 Series
カラム: Waters Nova-Pak phenyl 60Å 4μm(150mm×3.9mmΦ)+ガードカラム
カラム温度: 30℃
検出: Varian 380-LC
注入量: 5.0μL(試料濃度:0.1%(wt/vol))
溶離液: A液:MeOH/H2O=8/1(v/v),B液:CHCl3/MeOH=8/1(v/v)
グラジェント:A/B=80/20→0/100(28min);流量:0.7mL/min
Z=(X2-Y2)1/2
[式中、Xは所定の測定装置および測定条件で求めた置換度分布半値幅(未補正値)である。Y=ax+b(0≦x≦3)である。ここで、aは前記Xと同じ測定装置および測定条件で求めた総置換度3のセルロースアセテートの置換度分布半値幅、bは前記Xと同じ測定装置および測定条件で求めた総置換度3のセルロースプロピオネートの置換度分布半値幅である。xは測定試料のアセチル総置換度(0≦x≦3)である]
2693-2696.)によれば、置換度2.3の酢酸セルロースの沈澱分別では、分子量に依存した分画と置換度(化学組成)に伴う微々たる分画が起こるとされており、本発明者らが見出したような置換度(化学組成)で顕著な分画ができるとの報告はない。さらに、低置換度酢酸セルロースについて、溶解分別や沈澱分別で置換度分布(化学組成)を制御できることは検証されていなかった。
本発明において、前記酢酸セルロースエステル(A)のグルコース環の2,3,6位の各アセチル置換度は、手塚(Tezuka,Carbonydr.Res.273,83(1995))の方法に従いNMR法で測定できる。すなわち、酢酸セルロース試料の遊離水酸基をピリジン中で無水プロピオン酸によりプロピオニル化する。得られた試料を重クロロホルムに溶解し、13C-NMRスペクトルを測定する。アセチル基の炭素シグナルは169ppmから171ppmの領域に高磁場から2位、3位、6位の順序で、そして、プロピオニル基のカルボニル炭素のシグナルは、172ppmから174ppmの領域に同じ順序で現れる。それぞれ対応する位置でのアセチル基とプロピオニル基の存在比から、元のセルロースジアセテートにおけるグルコース環の2,3,6位の各アセチル置換度を求めることができる。アセチル置換度は、13C-NMRのほか、1H-NMRで分析することもできる。
本発明において、多分散性(分散度;Mw/Mn)は、酢酸セルロース(試料)の残存水酸基をすべてプロピオニル化して得られるセルロースアセテートプロピオネートを用いてGPC-光散乱法により求めた値である。
装置:Shodex製 GPC 「SYSTEM-21H」
溶媒:アセトン
カラム:GMHxl(東ソー)2本、同ガードカラム
流速:0.8ml/min
温度:29℃
試料濃度:0.25%(wt/vol)
注入量:100μl
検出:MALLS(多角度光散乱検出器)(Wyatt製、「DAWN-EOS」)
MALLS補正用標準物質:PMMA(分子量27600)
本発明において、重量平均重合度(DPw)は、酢酸セルロース(試料)の残存水酸基をすべてプロピオニル化して得られるセルロースアセテートプロピオネートを用いてGPC-光散乱法により求めた値である。
本発明における前記酢酸セルロースエステル(A)の6%粘度は、例えば5~500mPa・s、好ましくは6~300mPa・sである。6%粘度が高すぎると濾過性が悪くなる場合がある。また、6%粘度が低すぎると、フィルムとした時の強伸度が低下しやすくなる。
50mlのメスフラスコに乾燥試料3.00gを入れ、蒸留水を加え溶解させる。得られた6wt/vol%の溶液を所定のオストワルド粘度計の標線まで移し、25±1℃で約15分間整温する。計時標線間の流下時間を測定し、次式により6%粘度を算出する。
6%粘度(mPa・s)=C×P×t
C:試料溶液恒数
P:試料溶液密度(0.997g/cm3)
t:試料溶液の流下秒数
試料溶液恒数は、粘度計校正用標準液[昭和石油社製、商品名「JS-200」(JIS Z 8809に準拠)]を用いて上記と同様の操作で流下時間を測定し、次式より求める。
試料溶液恒数={標準液絶対粘度(mPa・s)}/{標準液の密度(g/cm3)×標準液の流下秒数}
本発明における前記酢酸セルロースエステル(A)(低置換度酢酸セルロース)は、例えば、(A)中乃至高置換度酢酸セルロースの加水分解工程(熟成工程)、(B)沈殿工程、及び、必要に応じて行う(C)洗浄、中和工程により製造できる。
この工程では、中乃至高置換度酢酸セルロース(以下、「原料酢酸セルロース」と称する場合がある)を加水分解する。原料として用いる中乃至高置換度酢酸セルロースのアセチル総置換度は、例えば、1.5~3、好ましくは2~3である。原料酢酸セルロースとしては、市販のセルロースジアセテート(アセチル総置換度2.27~2.56)やセルローストリアセテート(アセチル総置換度2.56超~3)を用いることができる。
この工程では、加水分解反応終了後、反応系の温度を室温まで冷却し、沈殿溶媒を加えて低置換度酢酸セルロースを沈殿させる。沈殿溶媒としては、水と混和する有機溶剤若しくは水に対する溶解度の大きい有機溶剤を使用できる。例えば、アセトン、メチルエチルケトン等のケトン;メタノール、エタノール、イソプロピルアルコール等のアルコール;酢酸エチル等のエステル;アセトニトリル等の含窒素化合物;テトラヒドロフラン等のエーテル;これらの混合溶媒などが挙げられる。
沈殿工程(B)で得られた沈殿物(固形物)は、メタノール等のアルコール、アセトン等のケトンなどの有機溶媒(貧溶媒)で洗浄するのが好ましい。また、塩基性物質を含む有機溶媒(例えば、メタノール等のアルコール、アセトン等のケトンなど)で洗浄、中和することも好ましい。
本発明では、樹脂組成物に導電性を付与するため、導電性フィラーとして、単層カーボンナノチューブ、多層カーボンナノチューブ、単層グラフェン、多層グラフェン、フラーレン及びカーボンブラックからなる群より選択された少なくとも1種の炭素材料(B)を用いる。単層及び多層カーボンナノチューブ、単層及び多層グラフェン、フラーレン、カーボンブラックは、炭素原子からなる点で共通し、セルロース系樹脂に配合することで該樹脂組成物に高い導電性を付与できる。カーボンナノチューブ、グラフェン、フラーレンは炭素同素体である。
本発明の導電性セルロース系樹脂組成物の製造には、任意の方法が採用される。例えば、前記アセチル総置換度0.5~1.1の酢酸セルロースエステル(A)と、前記炭素材料(B)と、水と、必要に応じて分散剤や界面活性剤、その他の添加剤とを含む分散液を調製し、該分散液を賦形し(例えば、フィルム状又はシート状に流延し)、賦形された含水成形物を乾燥し、固化(固体化)することにより、本発明の導電性セルロース系樹脂組成物、及び本発明の導電性成形体を得ることができる。なお、本発明の導電性セルロース系樹脂組成物は溶媒を乾燥除去した後の樹脂組成物を意味する。
(1)アセチル総置換度が0.5~1.1の酢酸セルロースエステル(A)を水に溶解する工程
(2)炭素材料(B)の水分散液を上記(1)で調製した酢酸セルロースエステル(A)の水溶液に添加し、混合撹拌する工程
(3)上記(2)の工程で得られた分散液を賦形する工程
(4)賦形された含水成形物を乾燥し、固化(固体化)する工程
酢酸セルロース(ダイセル社製、商品名「L-50」、アセチル総置換度2.43、6%粘度:110mPa・s)1重量部に対して、5.1重量部の酢酸および2.0重量部の水を加え、40℃で5時間撹拌して外観均一な溶液を得た。この溶液に0.13重量部の硫酸を加え、得られた溶液を70℃に保持し、加水分解(部分脱アセチル化反応;熟成)を行った。なお、この熟成過程においては、途中で2回、水を系に添加した。すなわち、反応を開始して1時間後に0.67重量部の水を加え、さらに2時間後、1.67重量部の水を加え、さらに3時間反応させた。合計の加水分解時間は6時間である。なお、反応開始時から1回目の水の添加までを第1熟成、1回目の水の添加から2回目の水の添加までを第2熟成、2回目の水の添加から反応終了(熟成完了)までを第3熟成という。
加水分解を実施した後、系の温度を室温(約25℃)まで冷却し、反応混合物に15重量部のアセトン/メタノール1:1(重量比)混合溶媒(沈殿化剤)を加えて沈殿を生成させた。
固形分15重量%のウェットケーキとして沈殿を回収し、8重量部のメタノールを加え、固形分15重量%まで脱液することにより洗浄した。これを3回繰り返した。洗浄した沈殿物を、酢酸カリウムを0.04重量%含有するメタノール8重量部でさらに2回洗浄して中和し、乾燥して、低置換度酢酸セルロースを得た。
反応温度、第1熟成時間、第2熟成時間、第3熟成時間、沈殿化剤を表1に示す条件とした以外は、合成例1と同様にして低置換度酢酸セルロースを得た。
手塚の方法(Carbohydr. Res. 273, 83(1995))に準じて低置換度酢酸セルロース試料の未置換水酸基をプロピオニル化した。プロピオニル化低置換度酢酸セルロースのアセチル置換度は、手塚の方法(同)に準じて13C-NMRにおける169~171ppmのアセチルカルボニルのシグナルおよび172~174ppmのプロピオニルカルボニルのシグナルから決定した。
低置換度酢酸セルロースの重量平均重合度および分散度は、プロピオニル化低置換度酢酸セルロースに導いた後に次の条件でGPC-光散乱測定を行うことで決定した。
装置:Shodex製 GPC 「SYSTEM-21H」
溶媒:アセトン
カラム:GMHxl(東ソー)2本、同ガードカラム
流速:0.8ml/min
温度:29℃
試料濃度:0.25%(wt/vol)
注入量:100μl
検出:MALLS(多角度光散乱検出器)(Wyatt製、「DAWN-EOS」)
MALLS補正用標準物質:PMMA(分子量27600)
低置換度酢酸セルロースのCDIは、プロピオニル化低置換度酢酸セルロースに導いた後に次の条件でHPLC分析を行うことで決定した。
装置: Agilent 1100 Series
カラム: Waters Nova-Pak phenyl 60Å 4μm(150mm×3.9mmΦ)+ガードカラム
カラム温度: 30℃
検出: Varian 380-LC
注入量: 5.0μL(試料濃度:0.1%(wt/vol))
溶離液: A液:MeOH/H2O=8/1(v/v),B液:CHCl3/MeOH=8/1(v/v)
グラジェント:A/B=80/20→0/100(28min);流量:0.7mL/min
まず、アセチルDS(アセチル基総置換度)が0~3の範囲でDS既知の標品をHPLC分析することで、溶出時間対DSの較正曲線を作成した。較正曲線に基づき、未知試料の溶出曲線(時間対検出強度曲線)をDS対検出強度曲線(組成分布曲線)に変換し、この組成分布曲線の未補正半値幅Xを決定し、次式により組成分布の補正半値幅Zを決定した。
Z=(X2-Y2)1/2
なお、Yは次式で定義される装置定数である。
Y=ax+b
a: アセチルDS=3の標品のX値
b: アセチルDS=0の標品のX値
x: 未知試料のアセチルDS
補正半値幅Zから、次式により組成分布指数(CDI)を決定した。
CDI=Z/Z0
ここに、Z0は全ての部分置換酢酸セルロースの調製におけるアセチル化および部分脱アセチル化が全ての分子の全ての水酸基(またはアセチル基)に対して等しい確率で生じた場合に生成する組成分布であり、次式で定義される。
p:(未知試料のアセチルDS)/3
q:1-P
合成例1~12で得られた低置換度酢酸セルロースと4重量%カーボンナノチューブ分散液(多層、外径約13nm;和光純薬製)と水とを表2に示す割合で混合して、低置換度酢酸セルロース及びカーボンナノチューブを含む水分散液を調製した。表2の「ポリマー」の欄に、用いた低置換度酢酸セルロースのサンプル番号を記した。
すなわち、所定量の低置換度酢酸セルロースと所定量の水を撹拌羽根を備えたガラス容器に入れ、16時間、25±5℃で混合撹拌して、低置換度酢酸セルロースの水溶液を調製した。この低置換度酢酸セルロースの水溶液に、前記4重量%カーボンナノチューブ分散液を所定量添加して、さらに4時間撹拌し、カーボンナノチューブ(CNT)を所定の含有率(1重量%、10重量%、20重量%、30重量%、40重量%、50重量%)で含む低置換度酢酸セルロース水分散液を得た。得られた水分散液を7日間静置した。
上記水分散液を、乾燥後の固形分の厚みで45μmとなるように、水分散液塗布量を調整して、ガラス板上にバーコーターで流延し、70℃で90分間乾燥し、フィルムとした。形成されたフィルムをガラス板から剥離し、70℃でさらに30分間乾燥した。
得られたフィルムの体積固有抵抗(体積抵抗率)(Ω・cm)を、JIS K7194に従い測定した。測定装置として、商品名「ロレスタ」(MCP-T610型)(三菱化学アナリテック社製)を用いた。結果を表3に示す。表3中の「-」は、フィルムにクラックが生じたか、又はフィルムが脆く、ガラス板から剥離して自立フィルムとすることができなかったことを示す。
ポリビニルアルコールと4重量%カーボンナノチューブ分散液(多層、外径約13nm;和光純薬製)と水とを表2に示した割合で混合して、ポリビニルアルコール及びカーボンナノチューブを含む水分散液を調製した。表2の「ポリマー」の欄に、用いたポリビニルアルコール(「クラレポバール」;クラレ社製)の品番を記した。各ポリビニルアルコールの物性を以下に示す。
「PVA 117」:ケン化度98.7%、水溶液粘度(4重量%、20℃)28.2mPa・s
「PVA HC」:ケン化度99.9%、水溶液粘度(4重量%、20℃)24.8mPa・s
「PVA 217」:ケン化度88.1%、水溶液粘度(4重量%、20℃)22.6mPa・s
すなわち、所定量のポリビニルアルコールと所定量の水を撹拌羽根を備えたガラス容器に入れ、7時間、70±5℃で混合撹拌して、ポリビニルアルコールの水溶液を調製した。このポリビニルアルコールの水溶液を25±5℃まで冷却し、4重量%カーボンナノチューブ分散液(多層、外径約13nm;和光純薬製)を所定量添加して、さらに4時間撹拌し、カーボンナノチューブを所定の含有率(重量%)で含むポリビニルアルコール水分散液を得た。
上記水分散液を、乾燥後の固形分の厚みで45μmとなるように、水分散液塗布量を調整して、ガラス板上にバーコーターで流延し、70℃で90分間乾燥し、フィルムとした。形成されたフィルムをガラス板から剥離し、70℃でさらに30分間乾燥した。
得られたフィルムの体積固有抵抗(体積抵抗率)(Ω・cm)を、JIS K7194に従い測定した。測定装置として、商品名「ロレスタ」(MCP-T610型)(三菱化学アナリテック社製)を用いた。結果を表3に示す。
Claims (7)
- アセチル基総置換度が0.5~1.1の酢酸セルロースエステル(A)と、単層カーボンナノチューブ、多層カーボンナノチューブ、単層グラフェン、多層グラフェン、フラーレン及びカーボンブラックからなる群より選択された少なくとも1種の炭素材料(B)とを含む導電性セルロース系樹脂組成物。
- 体積抵抗率が10-3~20Ω・cmである請求項1記載の導電性セルロース系樹脂組成物。
- 体積抵抗率が10-3~1Ω・cmである請求項1記載の導電性セルロース系樹脂組成物。
- 前記炭素材料(B)の含有量が、導電性セルロース系樹脂組成物全体の0.1~80重量%である請求項1~3の何れか1項に記載の導電性セルロース系樹脂組成物。
- 請求項1~5の何れか1項に記載の導電性セルロース系樹脂組成物で構成された導電性成形体。
- 請求項6に記載の導電性成形体の製造方法であって、アセチル基総置換度が0.5~1.1の酢酸セルロースエステル(A)と、単層カーボンナノチューブ、多層カーボンナノチューブ、単層グラフェン、多層グラフェン、フラーレン及びカーボンブラックからなる群より選択された少なくとも1種の炭素材料(B)を含む水分散液を賦形し、賦形された含水成形物を乾燥する工程を含む導電性成形体の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014529560A JP6157472B2 (ja) | 2012-08-08 | 2013-08-08 | 導電性セルロース系樹脂組成物 |
EP13828277.7A EP2883907B1 (en) | 2012-08-08 | 2013-08-08 | Conductive cellulose-based resin composition |
US14/419,946 US9543057B2 (en) | 2012-08-08 | 2013-08-08 | Conductive cellulose-based resin composition |
CN201380042175.2A CN104520370B (zh) | 2012-08-08 | 2013-08-08 | 导电性纤维素类树脂组合物 |
KR1020157004591A KR102047236B1 (ko) | 2012-08-08 | 2013-08-08 | 도전성 셀룰로오스계 수지 조성물 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-175786 | 2012-08-08 | ||
JP2012175786 | 2012-08-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014024978A1 true WO2014024978A1 (ja) | 2014-02-13 |
Family
ID=50068198
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/071520 WO2014024977A1 (ja) | 2012-08-08 | 2013-08-08 | 導電性セルロース系樹脂組成物 |
PCT/JP2013/071522 WO2014024978A1 (ja) | 2012-08-08 | 2013-08-08 | 導電性セルロース系樹脂組成物 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/071520 WO2014024977A1 (ja) | 2012-08-08 | 2013-08-08 | 導電性セルロース系樹脂組成物 |
Country Status (6)
Country | Link |
---|---|
US (2) | US9595366B2 (ja) |
EP (2) | EP2883906B1 (ja) |
JP (2) | JP6157472B2 (ja) |
KR (2) | KR102047236B1 (ja) |
CN (2) | CN104520371B (ja) |
WO (2) | WO2014024977A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014125634A (ja) * | 2012-12-26 | 2014-07-07 | Akihiko Ito | 導電性フィルム |
JP2016172823A (ja) * | 2015-03-17 | 2016-09-29 | 大阪瓦斯株式会社 | 炭素材料含有複合体、分散液及びそれらの製造方法並びにその複合体を含む樹脂組成物 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016203657A1 (ja) * | 2015-06-19 | 2016-12-22 | 株式会社ダイセル | 水溶性酢酸セルロース系樹脂組成物、被覆製剤、水溶性酢酸セルロース複合体成形品及びその製造方法 |
US10090078B2 (en) | 2015-10-07 | 2018-10-02 | King Fahd University Of Petroleum And Minerals | Nanocomposite films and methods of preparation thereof |
JP6839166B2 (ja) * | 2016-02-15 | 2021-03-03 | ダイセルポリマー株式会社 | セルロースアセテート組成物 |
WO2017217503A1 (ja) * | 2016-06-17 | 2017-12-21 | 日本電気株式会社 | セルロース系樹脂組成物、成形体及びこれを用いた製品 |
JP6940162B2 (ja) * | 2016-06-17 | 2021-09-22 | 日本電気株式会社 | セルロース系樹脂組成物、成形体及びこれを用いた製品 |
IT201600075854A1 (it) | 2016-07-21 | 2018-01-21 | Fondazione St Italiano Tecnologia | Process for the preparation of graphene dispersions |
CN106519307B (zh) * | 2016-10-20 | 2019-05-14 | 华南理工大学 | 一种细菌纤维素/富勒烯复合材料及其制备方法 |
CN108948529A (zh) * | 2018-07-06 | 2018-12-07 | 佛山市高明区爪和新材料科技有限公司 | 一种复合型导电塑料的制备方法 |
WO2020218271A1 (ja) * | 2019-04-22 | 2020-10-29 | ダイセルポリマー株式会社 | セルロースエステル組成物 |
RU2731635C9 (ru) * | 2019-11-05 | 2020-11-12 | МСД Текнолоджис С.а.р.л. | Электропроводящая резиновая композиция для сплошных шин и не оставляющая следов сплошная шина |
EP3862388B1 (en) * | 2019-12-09 | 2023-07-26 | Daicel Corporation | Cellulose acetate and cellulose acetate composition |
CN111073059B (zh) * | 2019-12-30 | 2022-06-24 | 广西大学 | 一种纳米纤维素电热膜及其制备方法 |
US11932539B2 (en) | 2020-04-01 | 2024-03-19 | Graphul Industries LLC | Columnar-carbon and graphene-plate lattice composite |
JP6965411B1 (ja) * | 2020-07-14 | 2021-11-10 | 株式会社ダイセル | エアロゾル冷却部材 |
EP4194497A4 (en) * | 2020-08-07 | 2023-10-11 | Daicel Corporation | CELLULOSE ACETATE RESIN COMPOSITION |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4860934A (ja) * | 1971-11-29 | 1973-08-27 | ||
JPS5918734A (ja) * | 1982-07-23 | 1984-01-31 | Ricoh Co Ltd | 導電性フイルム組成物 |
JP2003201301A (ja) | 2001-11-05 | 2003-07-18 | Daicel Chem Ind Ltd | セルロースアセテートのアセチル置換度の調整方法 |
JP2011132466A (ja) * | 2009-12-25 | 2011-07-07 | Fujifilm Corp | 成形材料、成形体、及びその製造方法、並びに電気電子機器用筐体 |
JP2011132457A (ja) * | 2009-12-25 | 2011-07-07 | Fujifilm Corp | 成形材料、成形体、及びその製造方法、並びに電気電子機器用筐体 |
JP2011158664A (ja) | 2010-01-29 | 2011-08-18 | Daicel Chemical Industries Ltd | 位相差フィルム用セルロースジアセテート |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3376149A (en) * | 1966-03-25 | 1968-04-02 | Eastman Kodak Co | Preparation of carbon black dispersion for producing a high optical density of cellulose acetate film base |
JP3749746B2 (ja) | 1995-09-14 | 2006-03-01 | ダイセル化学工業株式会社 | 均質な酢酸セルロース |
US6864351B2 (en) * | 2000-09-14 | 2005-03-08 | Daicel Chemical Industries, Inc. | Aliphatic copolyester resin, a preparation method, an aliphatic polyester resin composition, uses thereof, a coating composition, a particle-state composition for agriculture and gardening coated by degradable layer |
DE60327380D1 (de) * | 2002-01-30 | 2009-06-04 | Idemitsu Kosan Co | Thermoplastische Harzzusammensetzung, Polycarbonat-Harzzusammensetzung und daraus geformter Artikel |
FR2907442B1 (fr) * | 2006-10-19 | 2008-12-05 | Arkema France | Materiau composite conducteur a base de polymere thermoplastique et de nanotube de carbone |
JP5266907B2 (ja) * | 2007-06-29 | 2013-08-21 | 東レ株式会社 | カーボンナノチューブ集合体、分散体および導電性フィルム |
JP2009057407A (ja) * | 2007-08-30 | 2009-03-19 | Hodogaya Chem Co Ltd | 積層加熱加圧によるカーボンナノチューブ含有樹脂成形体の導電性改善方法 |
FR2937324B1 (fr) | 2008-10-22 | 2012-03-16 | Arkema France | Procede de preparation d'un materiau composite a base de nanotubes, notamment de carbone |
DE112011103114T5 (de) * | 2010-09-17 | 2013-06-27 | Lg Hausys, Ltd. | Leitfähige Polymerzusammensetzung für ein PTC-Element mit verringerten NTC-Eigenschaften unter Verwendung von Kohlenstoff-Nanoröhren |
US20130150501A1 (en) * | 2011-12-07 | 2013-06-13 | Eastman Chemical Company | Cellulose esters in highly-filled elastomaric systems |
-
2013
- 2013-08-08 JP JP2014529560A patent/JP6157472B2/ja active Active
- 2013-08-08 CN CN201380042224.2A patent/CN104520371B/zh active Active
- 2013-08-08 WO PCT/JP2013/071520 patent/WO2014024977A1/ja active Application Filing
- 2013-08-08 EP EP13827218.2A patent/EP2883906B1/en active Active
- 2013-08-08 KR KR1020157004591A patent/KR102047236B1/ko active IP Right Grant
- 2013-08-08 WO PCT/JP2013/071522 patent/WO2014024978A1/ja active Application Filing
- 2013-08-08 JP JP2014529559A patent/JP6189844B2/ja active Active
- 2013-08-08 US US14/420,288 patent/US9595366B2/en active Active
- 2013-08-08 KR KR1020157004267A patent/KR102113466B1/ko active IP Right Grant
- 2013-08-08 US US14/419,946 patent/US9543057B2/en active Active
- 2013-08-08 CN CN201380042175.2A patent/CN104520370B/zh active Active
- 2013-08-08 EP EP13828277.7A patent/EP2883907B1/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4860934A (ja) * | 1971-11-29 | 1973-08-27 | ||
JPS5918734A (ja) * | 1982-07-23 | 1984-01-31 | Ricoh Co Ltd | 導電性フイルム組成物 |
JP2003201301A (ja) | 2001-11-05 | 2003-07-18 | Daicel Chem Ind Ltd | セルロースアセテートのアセチル置換度の調整方法 |
JP2011132466A (ja) * | 2009-12-25 | 2011-07-07 | Fujifilm Corp | 成形材料、成形体、及びその製造方法、並びに電気電子機器用筐体 |
JP2011132457A (ja) * | 2009-12-25 | 2011-07-07 | Fujifilm Corp | 成形材料、成形体、及びその製造方法、並びに電気電子機器用筐体 |
JP2011158664A (ja) | 2010-01-29 | 2011-08-18 | Daicel Chemical Industries Ltd | 位相差フィルム用セルロースジアセテート |
Non-Patent Citations (13)
Title |
---|
A. J. ROSENTHAL; B. B. WHITE, IND. ENG. CHEM., vol. 44, no. 11, 1952, pages 2693 - 2696 |
APPL. PHYS. LETT., vol. 82, 2003, pages 1290 |
C.BASAVARAJA ET AL.: "Electromagnetic Interference Shielding of Cellulose Triacetate/Multiwalled Carbon Nanotube Composite Films", POLYMER COMPOSITES, vol. 32, no. 3, 2011, pages 438 - 444, XP055192728 * |
CHEMPHYSCHEM, vol. 5, 2004, pages 998 |
CIBMENT, L.; RIVIBRE, C., BULL. SOC. CHIM., vol. 1, no. 5, 1934, pages 1075 |
CURR. APPL. PHYS, vol. 4, 2004, pages 577 |
GIL WOO JEON ET AL.: "High performance cellulose acetate propionate composites reinforced with exfoliated graphene", COMPOSITES: PART B, vol. 43, no. 8, 9 January 2012 (2012-01-09), pages 3412 - 3418, XP028941858 * |
J. POLYM. SCI. PART A POLYM. CHEM., vol. 44, 2006, pages 5283 |
JOURNAL OF THE SOCIETY OF FIBER SCIENCE AND TECHNOLOGY, JAPAN, vol. 42, 1986, pages 25 |
MEILU LI ET AL.: "Cellulose Acetate/Multiwalled Carbon Nanotube Nanocomposites with Improved Mechanical, Thermal, and Electrical Properties", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 118, no. 4, 2010, pages 2475 - 2481, XP055192733 * |
SOOKNE, A. M.; RUTHERFORD, H. A.; MARK, H.; HARRIS, M. J., RESEARCH NATL. BUR. STANDARDS, vol. 29, 1942, pages 123 |
TEZUKA, CARBOHYDR. RES., vol. 273, 1995, pages 83 |
TEZUKA, CARBONYDR. RES., vol. 273, 1995, pages 83 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014125634A (ja) * | 2012-12-26 | 2014-07-07 | Akihiko Ito | 導電性フィルム |
JP2016172823A (ja) * | 2015-03-17 | 2016-09-29 | 大阪瓦斯株式会社 | 炭素材料含有複合体、分散液及びそれらの製造方法並びにその複合体を含む樹脂組成物 |
Also Published As
Publication number | Publication date |
---|---|
EP2883907A4 (en) | 2016-04-27 |
JPWO2014024978A1 (ja) | 2016-07-25 |
EP2883907A1 (en) | 2015-06-17 |
US9543057B2 (en) | 2017-01-10 |
US20150221411A1 (en) | 2015-08-06 |
JP6157472B2 (ja) | 2017-07-05 |
CN104520370B (zh) | 2017-07-28 |
JP6189844B2 (ja) | 2017-08-30 |
US20150221410A1 (en) | 2015-08-06 |
KR102047236B1 (ko) | 2019-11-21 |
JPWO2014024977A1 (ja) | 2016-07-25 |
US9595366B2 (en) | 2017-03-14 |
EP2883906B1 (en) | 2019-08-07 |
CN104520371B (zh) | 2017-03-08 |
KR102113466B1 (ko) | 2020-05-21 |
CN104520371A (zh) | 2015-04-15 |
WO2014024977A1 (ja) | 2014-02-13 |
CN104520370A (zh) | 2015-04-15 |
KR20150040304A (ko) | 2015-04-14 |
EP2883906A1 (en) | 2015-06-17 |
EP2883907B1 (en) | 2019-05-08 |
KR20150040935A (ko) | 2015-04-15 |
EP2883906A4 (en) | 2016-04-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6157472B2 (ja) | 導電性セルロース系樹脂組成物 | |
JP6851342B2 (ja) | 低置換度酢酸セルロース | |
Sriupayo et al. | Preparation and characterization of α-chitin whisker-reinforced poly (vinyl alcohol) nanocomposite films with or without heat treatment | |
JP5514597B2 (ja) | 熱可塑性セルロース組成物の製造方法及びその成形体の製造方法 | |
JP6283523B2 (ja) | 水溶性酢酸セルロース系樹脂組成物、水溶性酢酸セルロース複合体成形品及びその製造方法 | |
JP2014152320A (ja) | 透明導電性パターン形成用の導電性高分子含有塗料、透明導電性パターン形成物およびその製造方法 | |
Feng et al. | Interaction of water soluble chitosan with multiwalled carbon nanotubes | |
JP2019044102A (ja) | 熱成形用セルロースアセテート組成物及び成形体 | |
Fan et al. | Enhancing multiwalled carbon nanotubes/poly (amide-imide) interfacial strength through grafting polar conjugated polymer on multiwalled carbon nanotubes | |
Li et al. | Preparation and plasticizing mechanism of deep eutectic solvent/lignin plasticized chitosan films | |
Sun et al. | Nanocomposite film prepared by depositing xylan on cellulose nanowhiskers matrix | |
WO2015114679A1 (ja) | 量子ドット複合体、当該複合体を有する波長変換素子、光電変換装置および太陽電池 | |
Tahir et al. | Alkynyl Ethers of Glucans: Substituent Distribution in Propargyl‐, Pentynyl‐and Hexynyldextrans and‐amyloses and Support for Silver Nanoparticle Formation | |
JP2014082061A (ja) | 導電性積層フィルム | |
JPH1171464A (ja) | セルロース混合エステル溶液及びその調製法 | |
JP2015140296A (ja) | シート状酸化グラフェンとその製造方法、及び電解質膜 | |
JP2014092668A (ja) | セルロースアシレート用光学特性調節剤、それを用いたセルロースアシレート樹脂組成物及びセルロースアシレート光学フィルム | |
JP6369610B1 (ja) | 樹脂組成物及び樹脂成形体 | |
Kassab et al. | Process-structure-property relationships of cellulose nanocrystals derived from Juncus effusus stems on ҡ-carrageenan-based bio-nanocomposite films | |
Kim et al. | Study on the influence of pretreatment and chain length of substituents on cellulose mixed esters |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13828277 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014529560 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14419946 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20157004591 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013828277 Country of ref document: EP |