WO2011125801A1 - 微細セルロース繊維分散液の製造方法 - Google Patents
微細セルロース繊維分散液の製造方法 Download PDFInfo
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- WO2011125801A1 WO2011125801A1 PCT/JP2011/058140 JP2011058140W WO2011125801A1 WO 2011125801 A1 WO2011125801 A1 WO 2011125801A1 JP 2011058140 W JP2011058140 W JP 2011058140W WO 2011125801 A1 WO2011125801 A1 WO 2011125801A1
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
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- 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
- C08L1/02—Cellulose; Modified cellulose
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- 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
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- 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
- C08L1/12—Cellulose acetate
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- 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
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
Definitions
- the present invention relates to a method for producing a fine cellulose fiber dispersion. More specifically, the present invention relates to a method for producing a fine cellulose fiber dispersion, in which cellulose fibers are defibrated in the presence of at least one of a resin and a resin precursor and an organic solvent.
- Patent Documents 1 to 3 cellulose fiber and resin are impregnated by impregnating a non-woven fabric or gel of cellulose fiber with a liquid resin precursor. It is disclosed that a complex with can be produced.
- an aqueous dispersion in which cellulose fibers are dispersed is made with a Teflon (registered trademark) filter membrane to produce a nonwoven fabric of cellulose fibers, and an epoxy resin is applied under high temperature conditions.
- the nonwoven fabric is impregnated to produce a composite.
- Patent Document 4 To 6).
- Patent Document 4 discloses that a fiber-reinforced composite resin composition containing cellulose fibers and a liquid precursor of a matrix resin is used as an adhesive and a sealant.
- Patent Document 5 discloses a cellulose dispersion in which cellulose is dispersed in a water-insoluble medium containing a surfactant, and states that a composite material can be obtained by compounding with a resin. Yes.
- Patent Document 6 discloses a method of obtaining a composite material using an epoxy resin composition in which microfibril cellulose is dispersed.
- Japanese Unexamined Patent Publication No. 2006-316253 Japanese Unexamined Patent Publication No. 2007-165357 Japanese Unexamined Patent Publication No. 2008-127510 Japanese Unexamined Patent Publication No. 2007-146143 Japanese Unexamined Patent Publication No. 2010-13604 Japanese Unexamined Patent Publication No. 2010-24413
- Patent Documents 4 to 6 have the following problems.
- cellulose fiber is defibrated in water to produce an aqueous solution in which cellulose fibers are dispersed, and then the aqueous solution and a liquid epoxy resin are mixed and subjected to reduced pressure conditions.
- the fiber reinforced composite resin composition is manufactured by evaporating water.
- a surfactant is contained in the dispersion. Therefore, when cellulose and resin are combined using the dispersion, surfactant or water is contained in the composite. There is a concern that it will be mixed and a heterogeneous structure will be formed in the composite, affecting various properties such as linear expansion. In addition, the surfactant may bleed out on the surface of the composite, and the properties of the composite may be impaired.
- Patent Document 6 a sheet-like microfibril cellulose obtained by replacing an aqueous solution containing cellulose fibers fibrillated in water with alcohol is redispersed with ultrasonic waves again in alcohol, and then the epoxy resin is converted from the alcohol. A method of performing a substitution is used.
- fine cellulose fibers having a fine average fiber diameter of nanometer level are uniformly dispersed in an organic solvent other than water, and further contain a resin or a precursor thereof to obtain a dispersion having excellent film forming properties. If it is possible, a composite in which fine cellulose fibers are uniformly dispersed can be easily produced, and it can be said that its industrial value is great.
- the present invention is that fine cellulose fibers are uniformly dispersed in an organic solvent, contain at least one of a resin and a resin precursor, and have excellent liquid stability and film-forming properties. It aims at providing the manufacturing method of the fine cellulose fiber dispersion liquid which can manufacture this composite_body
- Another object of the present invention is to provide a cellulose fiber composite and a production method thereof using the fine cellulose fiber dispersion obtained by the production method.
- the present inventors have found that the above problems can be solved by carrying out a fibrillation treatment of cellulose fibers in the presence of at least one of a resin and a resin precursor, and an organic solvent. I found it.
- a method for producing a fine cellulose fiber dispersion containing fine cellulose fibers, at least one of a resin and a resin precursor, and an organic solvent A fine cellulose fiber dispersion liquid comprising a fibrillation step in which cellulose fibers are defibrated to obtain fine cellulose fibers in a raw material dispersion liquid containing cellulose fibers, at least one of a resin and a resin precursor, and an organic solvent.
- Manufacturing method 2.
- a cellulose fiber composite comprising the fine cellulose fiber dispersion according to any one of 5 to 7 above, wherein the fine cellulose fiber dispersion is subjected to at least one of heat treatment and exposure treatment, the organic solvent is removed, and the fine cellulose fiber and the resin are contained.
- the manufacturing method of a cellulose fiber composite including the compounding process which obtains. 10. 10.
- a method for producing a cellulose fiber composite containing fine cellulose fibers and a resin In a raw material dispersion containing cellulose fibers, at least one of a resin and a resin precursor, and a solvent, a cellulose fiber is defibrated to obtain fine cellulose fibers, and The dispersion containing the fine cellulose fibers is subjected to at least one of heat treatment and exposure treatment, The manufacturing method of a cellulose fiber composite including the compounding process of removing the said solvent and obtaining the cellulose fiber composite containing a fine cellulose fiber and resin.
- a laminate comprising the substrate and the cellulose fiber composite according to 8 or 12 above.
- the laminated body of preceding clause 13 containing a protective film.
- a wiring board comprising the laminate according to item 13 or 14.
- the method for producing a fine cellulose fiber dispersion of the present invention obtains fine cellulose fibers by defibrating cellulose fibers in a raw material dispersion containing at least one of cellulose fibers, a resin and a resin precursor, and an organic solvent. Includes defibration process. By passing through the defibrating step, re-aggregation of the fine cellulose fibers can be suppressed, the stability of the dispersion can be improved, the problem of aggregation and sedimentation of the fine cellulose fibers can be solved, and the fine cellulose fibers can be made uniform. A finely dispersed fine cellulose dispersion can be obtained.
- fine cellulose fibers are uniformly dispersed in an organic solvent, contain a resin or a resin precursor, have excellent liquid stability and film forming properties, and are a composite of fine cellulose fibers and a resin.
- the manufacturing method of the fine cellulose fiber dispersion liquid which can manufacture a body with sufficient productivity can be provided.
- the cellulose fiber composite using the dispersion liquid obtained by this manufacturing method and its manufacturing method can also be provided.
- FIG. 1 is a photographed image with a microscope of the cellulose fiber composite film obtained in Example 2. The photographing magnification is 26.5 times.
- FIG. 2 is a photographed image with a microscope of the cellulose fiber composite film obtained in Example 8. The photographing magnification is 26.5 times.
- wt% is synonymous with “mass%”.
- the method for producing a fine cellulose fiber dispersion of the present invention obtains fine cellulose fibers by defibrating cellulose fibers in a raw material dispersion containing at least one of cellulose fibers, a resin and a resin precursor, and an organic solvent. Includes defibration process. By passing through the defibrating step, the problem of aggregation or sedimentation of fine cellulose fibers, which was unavoidable by conventional techniques, is solved, and a dispersion in which fine cellulose fibers are uniformly and stably dispersed can be obtained.
- the dispersion of the present invention is excellent in film forming properties and moldability.
- materials used in the present invention cellulose fiber, solvent, and at least one of resin and resin precursor, etc.
- the cellulose fiber used by this invention is a material (cellulose fiber raw material) used as the raw material of a fine cellulose fiber, The kind will not be specifically limited if it is a substance (cellulose containing material) containing a cellulose.
- impurities are removed from the substances listed below through purification, and cellulose obtained from plant-derived materials is particularly preferable.
- cellulose may be used as the cellulose fiber, or cellulose (cellulose raw material) partially containing impurities may be used.
- materials (substances) containing cellulose fibers include woods such as conifers and hardwoods, cotton such as cotton linter and cotton lint, pomace such as sugar cane and sugar radish, basts such as flax, ramie, jute and kenaf Fibers, leaf vein fibers such as sisal and pineapple, petiole fibers such as abaca and banana, fruit fibers such as coconut palm, stem trunk fibers such as bamboo, seaweeds such as bacterial cellulose produced by bacteria, seaweed such as valonia and clover, etc. Is mentioned. These natural celluloses are preferable because of their high crystallinity and low linear expansion and high elastic modulus.
- Bacterial cellulose is preferred because it can be easily obtained with a fine fiber diameter.
- Cotton is also preferable in that it is easy to obtain a fine fiber diameter, and more preferable in terms of easy acquisition of raw materials.
- wood of conifers and hardwoods with fine fiber diameters can be obtained, and it is the largest amount of biological resources on the planet, and is a sustainable resource that produces about 70 billion tons per year. Therefore, it contributes greatly to the reduction of carbon dioxide that affects global warming, which is advantageous from an economic point of view.
- the fiber diameter of the cellulose fiber used in the present invention is not particularly limited, and the number average fiber diameter may be 10 ⁇ m to 100 mm from the viewpoint of defibration efficiency and handleability during the defibrating process described later. Preferably, it is 50 ⁇ m to 0.5 mm. Those that have undergone general purification are about several hundred ⁇ m (preferably 50 to 500 ⁇ m), and those that have been fibrillated by a general method are several nm to 1 ⁇ m.
- a mechanical treatment with a disintegrator such as a refiner or a beater to make it about several mm.
- the number average fiber diameter measurement method is not particularly limited. Observe with SEM or TEM, draw a line on the diagonal line of the photograph, and randomly extract 12 fibers in the vicinity. It can be obtained by averaging 10 measured values from which fine fibers have been removed.
- the raw material may be cut or crushed at any time before, during, or after the treatment of the raw material, which will be described later.
- an impact pulverizer and a shear pulverizer can be used before the purification treatment, and a refiner can be used during the purification treatment and after the treatment.
- the cellulose fiber to be used is subjected to a purification treatment (purification step) to remove substances other than cellulose in the raw material, such as lignin, hemicellulose, or resin (resin). That is, it is preferable to use a cellulose fiber that has been subjected to a purification treatment.
- a purification treatment purification step
- the purification method is not particularly limited, and examples thereof include a method in which the raw material is degreased with benzene-ethanol, then subjected to delignification treatment by the Wise method, and dehemicellulose treatment with alkali.
- the manufacturing method of a general chemical pulp for example, manufacturing methods, such as a kraft pulp, a sulphid pulp, and an alkali pulp, are mentioned.
- water As a dispersion medium used for the purification treatment, water is generally used, but an aqueous solution of an acid or base or other treatment agent may be used, and in this case, it may be finally washed with water. .
- the raw material may be crushed into a state of wood chips or wood powder, and the crushing may be performed at any timing before, during or after the purification treatment as described above.
- the acid or base used for the purification treatment of cellulose fiber and other treatment agents are not particularly limited.
- Magnesium calcium oxide, acetic acid, oxalic acid, sodium hypochlorite, calcium hypochlorite, sodium chlorite, sodium chlorate, chlorine dioxide, chlorine, sodium perchlorate, sodium thiosulfate, hydrogen peroxide, ozone Hydrosulfite, anthraquinone, dihydrodihydroxyanthracene, tetrahydroanthraquinone, anthrahydroquinone, alcohols such as ethanol, methanol, 2-propanol, and
- bleaching treatment may be performed with chlorine, ozone, sodium hypochlorite, hydrogen peroxide, chlorine dioxide, or the like.
- two or more purification treatments can be performed using two or more kinds of treatment agents. In that case, it is preferable to wash with water between the purification treatments using different treatment agents.
- the temperature and pressure during the purification treatment are not particularly limited, and the temperature is selected in the range of 0 ° C. or more and 100 ° C. or less. In the case of treatment under pressure exceeding 1 atm, the temperature should be 100 ° C. or more and 200 ° C. or less. Is preferred.
- the cellulose fibers used may be those derived by chemical modification (chemically modified cellulose fibers).
- the chemical modification is a chemical modification in which a hydroxyl group in cellulose reacts with a chemical modifier.
- the chemical modification may be performed before or after the purification treatment for removing lignin or hemicellulose, etc., but from the viewpoint of efficient reaction of the chemical modifier, Modification is preferred. In addition, you may perform this chemical modification, after defibrating to a cellulose fiber by the defibrating process mentioned later.
- Substituents introduced into the hydroxyl group of cellulose by chemical modification are not particularly limited.
- X 1 , X 2 or X 3 represented by the following formula (1) is preferably a substituent listed above.
- an aromatic ring-containing substituent can be mentioned.
- the aromatic ring-containing substituent is a substituent derived from a hydrocarbon aromatic compound, a heterocyclic aromatic compound, or a non-benzenoid aromatic compound.
- the hydrocarbon aromatic compound is a benzene ring monocyclic compound such as benzene, naphthalene and anthracene, or a compound in which 2 to 12 of them are condensed.
- the upper limit of the number of condensation is preferably 6 or less.
- the heterocyclic aromatic compound is a 5- to 10-membered heterocyclic monocyclic compound such as furan, thiophene, pyrrole and imidazole, or a compound obtained by condensing 2 to 12 thereof.
- the upper limit of the number of condensation is preferably 6 or less.
- non-benzenoid aromatic compound examples include annulene, cyclopentadienyl anion, cycloheptatrienyl cation, tropone, metallocene, and acebreazilene.
- the substituent derived from a hydrocarbon aromatic compound and a heterocyclic aromatic compound is preferable, and the substituent derived from a hydrocarbon aromatic compound is more preferable.
- a substituent derived from benzene, naphthalene or anthracene is preferable from the viewpoint of easy availability of raw materials.
- a hydrogen atom in the substituent may be substituted with an alkyl group having 1 to 12 carbon atoms.
- the aromatic ring-containing substituent is a single bond or an alkylene group having 1 to 3 carbon atoms, wherein two or more selected from the group consisting of the hydrocarbon aromatic compounds, heterocyclic aromatic compounds, and non-benzenoid aromatic compounds. You may be connected by.
- the linking group that bonds the aromatic ring and cellulose is not particularly limited as long as it is obtained as a result of the reaction with the hydroxyl group of cellulose.
- O (oxygen atom) in the above formula and an aromatic ring may be directly bonded, or may be bonded to O (oxygen atom) of cellulose via —CO— or —CONH— as a linking group.
- -CO- is particularly preferred.
- a benzoyl group, a naphthoyl group, and an anthroyl group are preferable, and a benzoyl group is particularly preferable.
- Examples of the chemical modifier include an acid, an acid anhydride, and a halogenating reagent when an ester group is formed.
- examples thereof include cyclic ether compounds such as alcohols, phenolic compounds, alkoxysilanes, phenoxysilanes, and oxiranes (epoxies).
- cyclic ether compounds such as alcohols, phenolic compounds, alkoxysilanes, phenoxysilanes, and oxiranes (epoxies).
- an isocyanate compound etc. are mentioned, for example.
- These chemical modifiers may be used alone or in combination of two or more.
- halogenating reagent examples include acetyl halide, acryloyl halide, methacryloyl halide, propanoyl halide, butanoyl halide, 2-butanoyl halide, pentanoyl halide, benzoyl halide and naphthoyl halide.
- Examples of alcohols that are chemical modifiers that form ether groups include methanol, ethanol, propanol, and 2-propanol.
- Examples of phenolic compounds include phenol and naphthol.
- Examples of the alkoxysilane include methoxysilane, ethoxysilane, phenoxysilane, and the like.
- cyclic ether compound examples include ethyl oxirane, ethyl oxetane, oxirane (epoxy), and phenyl oxirane (epoxy).
- Examples of the isocyanate compound that is a chemical modifier that forms a carbamate group include methyl isocyanate, ethyl isocyanate, propyl isocyanate, and phenyl isocyanate.
- acetic anhydride acrylic acid, methacrylic anhydride, benzoyl halide and naphthoyl halide are particularly preferable.
- the chemical modification of the cellulose fiber can be performed by a known method. That is, chemical modification can be carried out by reacting cellulose with a chemical modifier according to a conventional method. At this time, a solvent or a catalyst may be used as necessary, and heating and decompression may be performed.
- this raw material is a water-containing state, it is preferable to replace this water with the reaction solvent and to suppress reaction with a chemical modifier and water as much as possible.
- the raw material is dried to remove water, it is difficult for the raw material to be refined in the defibration process described later, and therefore it is not preferable to include a drying process.
- the amount of the chemical modifier is not particularly limited, and varies depending on the type of the chemical modifier, but is preferably 0.01 times or more, more preferably 0.05 times or more, more preferably 100 times the number of moles of the hydroxyl group of cellulose. The following is preferable, and 50 times or less is more preferable.
- the solvent it is preferable to use a water-soluble organic solvent that does not inhibit esterification.
- the water-soluble organic solvent include organic solvents such as acetone and pyridine, and organic acids such as formic acid, acetic acid, and succinic acid, and organic acids such as acetic acid are particularly preferable.
- organic acid such as acetic acid
- the chemical modification progresses uniformly to the cellulose, so that it will be easy to fibrillate as described later, and the resulting composite is considered to exhibit high heat resistance and high productivity.
- the amount of the solvent to be used is not particularly limited, but it is usually preferably 0.5 times or more, more preferably 1 time or more, preferably 200 times or less, more preferably 100 times or less with respect to the weight of cellulose.
- the catalyst it is preferable to use a basic catalyst such as pyridine, triethylamine, sodium hydroxide and sodium acetate, or an acidic catalyst such as acetic acid, sulfuric acid and perchloric acid.
- the amount of the catalyst is not particularly limited and varies depending on the type, but is usually preferably 0.01 times or more, more preferably 0.05 times or more, and preferably 100 times or less, based on the number of moles of hydroxyl groups of cellulose. 50 times or less is more preferable.
- the temperature condition is not particularly limited, but if it is too high, there is concern about yellowing of the cellulose or a decrease in the degree of polymerization, and if it is too low, the reaction rate decreases, so 10 to 130 ° C. is preferable.
- the reaction time is not particularly limited, and is preferably from several minutes to several tens hours although it depends on the chemical modifier or the chemical modification rate.
- the chemical modification rate refers to the proportion of all hydroxyl groups in cellulose that have been chemically modified, and the chemical modification rate can be measured by the following titration method.
- Titration method 0.05 g of dried modified cellulose is precisely weighed, and 6 ml of methanol and 2 ml of distilled water are added thereto. The mixture is stirred at 60 to 70 ° C. for 30 minutes, and 10 ml of 0.05N aqueous sodium hydroxide solution is added. This is stirred at 60 to 70 ° C. for 15 minutes, and further stirred at room temperature for one day. Titrate with 0.02N aqueous hydrochloric acid using phenolphthalein.
- the number of moles Q of the substituent introduced by chemical modification can be obtained by the following formula.
- T is a value obtained by adding the oxygen atom weight (16) to the molecular weight of the substituent.
- the chemical modification rate is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and particularly preferably 10 mol% or more with respect to the total hydroxyl groups of cellulose. Moreover, 65 mol% or less is preferable, 50 mol% or less is more preferable, and 40 mol% or less is more preferable. Within this range, the dispersion stability of the fine cellulose fibers in the dispersion is further improved, and a composite exhibiting a low linear expansion coefficient when composited with a resin is obtained.
- the solvent used in the present invention is not particularly limited as long as the resin or resin precursor used is dissolved or dispersed, and may be an aqueous medium such as water or an organic solvent, but an organic solvent is preferable.
- organic solvent examples include organic solvents such as aromatic hydrocarbons, aprotic polar solvents, alcohol solvents, ketone solvents, glycol ether solvents, and halogen solvents.
- organic solvents such as aromatic hydrocarbons, aprotic polar solvents, alcohol solvents, ketone solvents, glycol ether solvents, and halogen solvents.
- aprotic polar solvents particularly amide solvents
- alcohol solvents particularly amide solvents
- ketone solvents and halogen solvents are preferred. These solvents may be used alone or in combination of two or more.
- the organic solvent used in the present invention preferably has a boiling point that is not too high since there is a step of removing the organic solvent in a later step.
- the boiling point of the organic solvent is preferably 300 ° C. or less, preferably 200 ° C. or less, and more preferably 180 ° C. or less.
- 0 degreeC or more is preferable from points, such as a handleability.
- the aromatic hydrocarbon is preferably an aromatic hydrocarbon having 6 to 12 carbon atoms, and specific examples include benzene, toluene and xylene.
- aprotic polar solvent examples include sulfoxide solvents such as dimethyl sulfoxide (DMSO), formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethyl.
- sulfoxide solvents such as dimethyl sulfoxide (DMSO)
- formamide such as dimethyl sulfoxide (DMSO)
- N-methylformamide such as dimethyl sulfoxide (DMSO)
- acetamide such as 2-pyrrolidone and N-methylpyrrolidone.
- the alcohol solvent is preferably an alcohol solvent having 1 to 7 carbon atoms, and specific examples include methanol, ethanol, propanol and butanol.
- the ketone solvent (referring to a liquid having a ketone group) is preferably a ketone solvent having 3 to 9 carbon atoms.
- a ketone solvent having 3 to 9 carbon atoms for example, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisopropyl ketone, di-tert-butyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, cyclohexylmethyl
- ketones acetophenone, acetylacetone and dioxane.
- methyl ethyl ketone MEK
- MIBK methyl isobutyl ketone
- cyclopentanone cyclohexanone
- methyl ethyl ketone MEK
- cyclohexanone cyclohexanone
- the glycol ether solvent is preferably a glycol ether solvent having 3 to 9 carbon atoms.
- halogen-based solvent examples include chloroform, methyl chloride, dichloromethane, carbon tetrachloride, trichloroacetic acid, methyl bromide, methyl iodide, tri (tetra) chloroethylene, chlorobenzene, and benzyl chloride.
- the resin or resin precursor used in the present invention is not particularly limited as long as it is a resin or resin precursor that can be combined with fine cellulose fibers described later.
- the resin or resin precursor include a thermoplastic resin, a thermosetting resin, a light (active energy ray) curable resin, or a precursor thereof.
- the resin or resin precursor include alcohol resins, amide resins, ether resins, amine resins, aromatic resins, and precursors thereof.
- a resin or a resin precursor a cellulose derivative is mentioned, for example.
- thermoplastic resins thermosetting resins, photocurable resins, and precursors thereof are preferable from the viewpoints of various performances of the obtained composite and productivity (handleability).
- resins or resin precursors may be used alone or in combination of two or more.
- thermoplastic resin and its precursor examples include styrene resin, acrylic resin, aromatic polycarbonate resin, aliphatic polycarbonate resin, aromatic polyester resin, aliphatic polyester resin, aliphatic polyolefin resin, and cyclic olefin resin. And polyamide resins, polyphenylene ether resins, thermoplastic polyimide resins, polyacetal resins, polysulfone resins, and amorphous fluorine resins. These thermoplastic resins may be used individually by 1 type, and may use 2 or more types together.
- the precursor of a thermoplastic resin means a precursor for producing the above resin.
- thermosetting resin and the light (active energy ray) curable resin mean a resin that is cured by heat or light.
- the precursor of the curable resin generally means a substance that is liquid, semi-solid or solid at room temperature and exhibits fluidity at room temperature or under heating. These can be insoluble and infusible resins formed by forming a network-like three-dimensional structure while increasing the molecular weight by causing a polymerization reaction or a crosslinking reaction by the action of a curing agent, a catalyst, heat or light.
- thermosetting resin and its precursor The thermosetting resin or precursor thereof in the present invention is not particularly limited.
- epoxy resin acrylic resin, oxetane resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, silicon resin, polyurethane resin, diallyl phthalate
- resins such as resins and thermosetting polyimide resins or precursors thereof.
- photocurable resin and its precursor Although the photocurable resin or its precursor in this invention is not specifically limited, for example, resin, such as an epoxy resin, an acrylic resin, and an oxetane resin illustrated in the description of the above-mentioned thermosetting resin, or its precursor is mentioned.
- epoxy resins or precursors thereof acrylic resins or precursors thereof are preferable, and epoxy resins or precursors thereof are particularly preferable in that they are soluble in a liquid or organic solvent at around room temperature.
- the epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, bisphenol AD type epoxy resin, bisphenol acetophenone type epoxy resin, and bisphenol fluorenone type epoxy resin.
- Type epoxy resin diglycidyl ether type epoxy resin of monocyclic dihydric phenol such as catechol, resorcin and hydroquinone, dihydroxy naphthalene type epoxy resin, dihydroxy dihydroanthracene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and bisphenol A glycidyl ether type epoxy resin such as novolak type epoxy resin, glycy Glycol ester type epoxy resin, glycidyl amine type epoxy resins, linear aliphatic epoxy resins, various epoxy resins such as alicyclic epoxy resins, and heterocyclic epoxy resins.
- epoxy resins may be substituted with substituents having no adverse effect such as alkyl groups, aryl groups, ether groups and ester groups.
- epoxy resins particularly preferable ones are bisphenol A type epoxy resins, bisphenol F type epoxy resins, crystalline resins which are easy to handle, and 4,4′-biphenol type epoxy resins which have a low viscosity above the melting point. 3,3 ', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin, phenol novolac type epoxy resin which is multifunctional and has a high crosslink density upon curing to give a heat-resistant cured product, cresol novolak Type epoxy resin and bisphenol A novolac type epoxy resin.
- Mw weight average molecular weight
- the weight average molecular weight of the epoxy resin is preferably 200 to 80,000, and more preferably 300 to 60,000.
- epoxy resin precursor examples include dihydric phenols, and any epoxy resin precursor may be used as long as a hydroxyl group is bonded to an aromatic ring.
- bisphenols such as bisphenol A, bisphenol F, bisphenol B, bisphenol AD, 4-4′-biphenyl and 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, biphenol, catechol, resorcin , Hydroquinone and dihydroxynaphthalene.
- epoxy resin precursors include those in which these dihydric phenols are substituted with non-interfering substituents such as alkyl groups, aryl groups, ether groups and ester groups.
- dihydric phenols bisphenol A, bisphenol F, 4,4'-biphenol and 3,3 ', 5,5'-tetramethyl-4,4'-biphenol are preferred. These dihydric phenols can be used in combination.
- polyfunctional phenol resin is mentioned as things other than a bihydric phenol.
- polyfunctional phenol resins include phenol novolac resins, bisphenol novolac resins, dicyclopentadiene phenol resins, Xylok phenol resins, terpene modified phenol resins, melamine modified phenol novolac resins, and triazine structure-containing novolac resins. It is done.
- acrylic resin examples include polymers and copolymers such as (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylic acid ester and (meth) acrylamide. Of these, polymers and copolymers of (meth) acrylic acid and (meth) acrylic acid esters are preferred.
- acrylic resin precursor examples include (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylic acid ester, (meth) acrylamide, and the like. Of these, (meth) acrylic acid and (meth) acrylic acid esters are preferred.
- the weight average molecular weight of the acrylic resin is not particularly limited, but is preferably 300 to 3,000,000, and more preferably 400 to 2,500,000 from the viewpoint of handleability.
- Alcohol-based resin examples include polyethylene glycol, polyether polyol, polyester polyol, polyvinyl alcohol, amylose, amylopectin, sorbitol, polycaprolactone, polyvalerolactone, polybutyrolactone, polyglycol, and polylactic acid.
- amide resin examples include polyacrylamide, chitin, chitosan, polyvinyl pyrrolidone, and polycaprolactam.
- ether resin examples include crown ether, polyethylene glycol, and polypropylene glycol.
- amine resin examples include polyallylamine, polylysine, and various amine-modified acrylic copolymers.
- Aromatic resin examples of the aromatic resin include polyphenylene oxide, catechin, tannin, and terpene. Of these, alcohol resins and amide resins are preferable, and polyvinyl alcohol and polyvinyl pyrrolidone are particularly preferable.
- Cellulose derivative examples include cellulose organic acid ester, cellulose ether, alkyl cellulose, hydroxyalkyl cellulose, and cellulose ether having an ionic substituent.
- examples of the cellulose organic acid ester include cellulose diacetate and cellulose triacetate.
- examples of the cellulose organic acid ester include acetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate with an appropriately adjusted degree of acetylation.
- cellulose ether examples include alkyl cellulose, hydroxyalkyl cellulose, and cellulose ether having an ionic substituent.
- alkyl cellulose examples include methyl cellulose and ethyl cellulose.
- hydroxyalkyl cellulose examples include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose.
- Examples of the cellulose ether having an ionic substituent include carboxymethyl cellulose.
- compounds such as a chain transfer agent, an ultraviolet absorber, a filler, a silane coupling agent, a photo / thermal polymerization initiator, a curing agent, and a curing accelerator are used as necessary. May be.
- the compound may be allowed to coexist during the defibrating process described later, or may be used by adding to the dispersion after the defibrating process.
- curing agent when using an epoxy resin or its precursor as resin or a resin precursor, an epoxy resin hardening
- curing agent is added to a dispersion liquid after the defibration process mentioned later.
- the epoxy resin curing agent to be used is not particularly limited.
- polyhydric phenol compounds, amine compounds and acid anhydrides and the following can be used.
- bisphenol A bisphenol F, bisphenol AD, hydroquinone, resorcin, methyl resorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, terpene phenol resin
- polyphenols such as dicyclopentadiene phenol resin, bisphenol A type novolak resin, naphthol novolak resin, biphenylphenol resin, brominated bisphenol A and brominated phenol novolak resin, various phenols and benzaldehyde, hydroxybenzaldehyde, Various aldehydes such as crotonaldehyde and glyoxal Polyphenolic resins obtained by condensation reaction with polyphenols, various phenolic resins such as heavy oils or co-condensation resins of pitches with phenols and formaldehyde,
- Cationic polymerization initiators can also be used as curing agents for epoxy resins or their precursors.
- the cationic polymerization initiator include an active energy ray cationic polymerization initiator that generates a cationic species or a Lewis acid by active energy rays, or a thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heat. Can be used.
- phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium tetraphenylborate, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl Imidazoles such as imidazole, 1-cyanoethyl-2-methylimidazole and 2,4-dicyano-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine, 1-cyanoethyl- 2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetraphenylborate and 2-ethyl-1,4-dimethylimidazolium tetraphenylborate -Imidazolium salts such as Toto, 2,4-6-Tris Acetylaminomethyl)
- tetraphenylborate, phenol salt, phenol novolak salt and 2-ethylhexanoate of these diazabicyclo compounds triflic acid salt, boron trifluoride ether complex compound, metal fluoroboron complex, bis (perfluoroalkyl sulfonyl) methane metal salts, aryl diazonium compounds, aromatic onium salts, periodic table dicarbonyl chelate of the IIIa ⁇ Va group elements, thiopyrylium salts, MF 6 - anion (where M is phosphorus Periodic group VIb elements, arylsulfonium complex salts, aromatic iodonium complex salts, aromatic sulfonium complex salts, bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluoro (selected from antimony and arsenic) Metal salts (eg, Salt, arsenate and anti
- mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
- Some of these salts are FX-512 (3M), UVR-6990 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (General Electric). ], KI-85 [Degussa], SP-150 and SP-170 (Asahi Denka), and Sun Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical Co., Ltd.) Available.
- a preferred thermal cationic polymerization initiator is triflate, for example, diethylammonium triflate, triethylammonium triflate, diisopropylammonium triflate, ethyl diisopropyl triflate available from 3M as FC-520. Ammonium and the like [many of these are R.I. R. Described in Modern Coatings published by Alm in October 1980].
- aromatic onium salts that are also used as active energy ray cationic polymerization initiators, there are those that generate cationic species by heat, and these can also be used as thermal cationic polymerization initiators.
- curing accelerator examples include amines such as benzyldimethylamine and various imidazole compounds, and phosphines such as triphenylphosphine.
- the cellulose fibers are defibrated in a raw material dispersion containing cellulose fibers, at least one of a resin and a resin precursor, and a solvent to obtain fine cellulose fibers. It is a process.
- the method for producing the raw material dispersion is not particularly limited, and can be prepared by mixing each component used.
- the raw material dispersion is preferably prepared through the following two steps (solvent replacement step and mixing step). That is, it is preferable that the following steps are performed before the defibrating step.
- the cellulose fiber is used for the defibrating treatment in a state of an aqueous dispersion or containing water by being subjected to a purification treatment or the like. Therefore, by preparing the raw material dispersion through the following two steps, water contained in the cellulose can be excluded, and the stability of the resulting fine cellulose fiber dispersion can be further improved. it can.
- the following solvent substitution processes are usually unnecessary.
- solvent replacement step Step of replacing water in an aqueous dispersion containing cellulose fibers with an organic solvent
- mixing step Step of mixing the dispersion obtained in the solvent replacement step with at least one of a resin and a resin precursor
- the method of replacing the solvent in the solvent replacement step is not particularly limited, but water is removed from the aqueous dispersion containing cellulose fibers (preferably cellulose fibers after purification or chemical modification) by filtration, etc.
- a method of adding an organic solvent used at the time, mixing by stirring, and removing the organic solvent by filtration again can be mentioned.
- the medium in the dispersion can be replaced with water from the organic solvent.
- organic solvent used for the defibration process described later when the organic solvent used for the defibration process described later is water-insoluble, it may be replaced with a water-soluble organic solvent and then replaced with a water-insoluble organic solvent.
- the main medium of the aqueous dispersion used is usually water, but it may contain some other solvent.
- the content of cellulose fiber in the aqueous dispersion is not particularly limited, but is preferably 0.1 to 60% by weight with respect to the total amount of the aqueous dispersion.
- the cellulose fiber content in the dispersion after solvent replacement is preferably 0.1 to 60% by weight based on the total amount of the dispersion.
- the mixing step is a step of mixing the dispersion containing the cellulose fiber and the organic solvent obtained in the solvent replacement step, and at least one of a resin and a resin precursor.
- At the time of mixing at least one of resin and resin precursor may be directly added to the dispersion and mixed, or after at least one of resin and resin precursor is dissolved in an organic solvent to prepare a solution, the solution is added. May be mixed.
- the organic solvent used may be the same as the organic solvent used in the solvent replacement step, or may be different as long as it is compatible.
- the mixing step when an organic solvent containing at least one of a resin and a resin precursor is used, the mixing step may not be performed.
- the content of cellulose fibers in the raw material dispersion is not particularly limited, but from the viewpoint of handleability such that the viscosity or liquid stability of the resulting fine cellulose fiber dispersion is suitable, the total amount of raw material dispersion, 0.5 wt% or more is preferable, 1 wt% or more is more preferable, 50 wt% or less is preferable, and 40 wt% or less is more preferable.
- the content of at least one of the resin and the resin precursor in the raw material dispersion is not particularly limited, but from the viewpoint of handleability such that the viscosity or liquid stability of the obtained fine cellulose fiber dispersion becomes suitable, the raw material dispersion 2 wt% or more is preferable, 2.5 wt% or more is more preferable, 95 wt% or less is preferable, and 80 wt% or less is more preferable.
- the content of the organic solvent in the raw material dispersion is not particularly limited, but from the viewpoint of handleability such that the viscosity or liquid stability of the resulting fine cellulose fiber dispersion becomes suitable, the total amount of the raw material dispersion is 1 wt% or more is preferable, 5 wt% or more is more preferable, 97.5 wt% or less is preferable, and 95 wt% or less is more preferable.
- the weight ratio of at least one of the resin and the resin precursor and the organic solvent in the raw material dispersion is not particularly limited, but the handleability such that the viscosity or liquid stability of the obtained fine cellulose fiber dispersion becomes suitable.
- the content of the organic solvent is preferably 5 to 2000 parts by weight and more preferably 25 to 1000 parts by weight with respect to 100 parts by weight of at least one of the resin and the resin precursor.
- the weight ratio between the cellulose fiber and at least one of the resin and the resin precursor in the raw material dispersion is not particularly limited, but the handling property that the viscosity or liquid stability of the obtained fine cellulose fiber dispersion is suitable.
- the content of the cellulose fiber is preferably 2.5% by weight or more, more preferably 3% by weight or more, with respect to the total amount (100% by weight) of at least one of the cellulose fiber and the resin and the resin precursor. 5 wt% or more is more preferable, 97.5 wt% or less is preferable, 97 wt% or less is more preferable, and 95 wt% or less is more preferable.
- the method for defibrating the cellulose fiber in the defibrating step is not particularly limited. Specifically, for example, a ceramic bead having a diameter of about 1 mm is used with a cellulose fiber concentration of 0.5 to 50% by weight, for example, about 1% by weight. And a method of defibrating cellulose fibers by applying vibration using a media mill such as a paint shaker or a bead mill.
- a rotating main shaft and a rotating sub shaft that rotates in conjunction with the rotation of the main shaft and a ring that fibrillates fibers as a grinding medium can be cited.
- a method of defibrating cellulose fibers for example, a method of defibration (high-speed rotating homogenizer) using a shearing force through such a raw material dispersion between a blender type disperser or a slit rotating at high speed, A method in which shearing force is generated between cellulose fibers by suddenly depressurizing from a high pressure (high pressure homogenizer method), and a method using a counter collision type disperser (Masuko Sangyo) such as Massomizer X Etc.
- defibrating treatment by a media mill such as a bead mill
- defibrating (spreading) by jetting defibrating by a rotary defibrating method
- ultrasonic treatment examples include defibrating treatment.
- the treatment with a bead mill improves the efficiency of defibration and further improves the dispersibility of fine cellulose fibers.
- the solid content concentration in the raw material dispersion (total amount of cellulose fibers and resin or precursor thereof) is not particularly limited, but is preferably 2.5% by weight or more. % By weight or more is more preferable, 99% by weight or less is preferable, and 50% by weight or less is more preferable. If the solid content concentration in the raw material dispersion used in the defibrating step is too low, the amount of liquid is too large with respect to the amount of cellulose to be treated, and the efficiency deteriorates. If the solid content concentration is too high, the fluidity deteriorates.
- a known device can be used as a device for performing the bead mill.
- UAM ultra apex mill UAM
- DAM dual apex mill DAM
- star mill manufactured by Ashizawa Finetech
- OB mill turbo
- the material of the beads to be used is not particularly limited, and examples thereof include glass and zirconia.
- the particle size of the beads is not particularly limited, and is usually about 0.01 to 5 mm in diameter.
- the conditions for performing the bead mill are appropriately selected according to the type of solvent and the materials used, such as the fiber diameter of the cellulose fiber, but are usually 1 to 5 hours at a peripheral speed of 4 to 16 m / sec. It is preferable to perform to the extent.
- cellulose fibers when cellulose fibers are defibrated with a bead mill, it may be performed multiple times under different conditions.
- a rotation speed for example, 10,000 rpm or more is preferable, 15000 rpm or more is more preferable, and 20000 rpm or more is particularly preferable.
- the upper limit of the rotational speed is not particularly limited, but is preferably 30000 rpm or less from the viewpoint of the performance of the apparatus.
- the treatment time is preferably 1 minute or longer, more preferably 5 minutes or longer, and particularly preferably 10 minutes or longer.
- the treatment time is preferably 6 hours or less from the viewpoint of productivity.
- heat is generated by shearing, it is preferable to cool the solution so as not to exceed 50 ° C.
- the raw material dispersion is preferably pressurized by a pressure intensifier to 30 MPa or more, more preferably 100 MPa or more, further preferably 150 MPa or more, particularly preferably 220 MPa or more, and ejected from a nozzle having a pore diameter of 50 ⁇ m or more. It is preferable to reduce the pressure so that the pressure difference is preferably 30 MPa or more, more preferably 80 MPa or more, and even more preferably 90 MPa or more.
- the cellulose fiber can be defibrated by the cleavage phenomenon caused by the pressure difference.
- the pressure under the high pressure condition is low, or when the pressure difference from the high pressure to the decompression condition is small, the defibrating efficiency is lowered, and it is necessary to increase the number of repeated ejections to obtain a desired fiber diameter. Absent.
- the ejection of the raw material dispersion is repeated a plurality of times as necessary, thereby increasing the degree of refinement and obtaining fine cellulose fibers having a desired fiber diameter.
- the number of repetitions is usually preferably 1 or more, more preferably 3 or more, and usually preferably 20 or less, more preferably 15 or less.
- the degree of miniaturization can be increased.
- an excessively large number of passes is not preferable because the cost increases.
- the apparatus of the high-pressure homogenizer is not particularly limited, and for example, a “Starburst system” manufactured by Gaulin or Sugino Machine can be used.
- the upper limit of the apparatus specification is 245 MPa or less.
- the pressure difference from the high pressure condition to the reduced pressure is large, but generally, the upper limit of the pressure difference is usually 245 MPa or less by ejecting from the pressurizing condition by the pressure intensifier to the atmospheric pressure. It is preferable.
- the temperature at the time of ejection is not particularly limited, but it is usually preferably 5 ° C or higher and 100 ° C or lower. By setting the temperature to 100 ° C. or lower, it is possible to suppress the deterioration of the apparatus, specifically, the liquid feed pump and the high-pressure seal part.
- the number of ejection nozzles may be one or two, and the ejected raw material dispersion may be hit against a wall, ball or ring provided at the ejection destination. Furthermore, when there are two nozzles, the raw material dispersions may collide with each other at the ejection destination.
- the cellulose concentration in the raw material dispersion that has been subjected to the ultrasonic treatment and that has been subjected to the defibrating treatment (hereinafter, referred to as the raw material dispersion for ultrasonic treatment as appropriate) is 0 with respect to the total amount of the liquid.
- 0.5 wt% or more is preferable, 1 wt% or more is more preferable, 50 wt% or less is preferable, and 40 wt% or less is more preferable.
- the number average fiber diameter of the fine cellulose fibers in the fine cellulose fiber dispersion obtained by the above method can be determined by measuring by observing with SEM or TEM after drying and removing the dispersion medium in the dispersion. it can.
- the number average fiber diameter of the fine cellulose fibers defibrated obtained by the present invention is preferably 100 nm or less, and more preferably 80 nm or less, from the viewpoint that the obtained composite exhibits better low linear expansion.
- the minimum of this number average fiber diameter is 4 nm or more normally.
- the number average fiber diameter was observed with SEM, TEM or the like, a line was drawn on the diagonal line of the photograph, and 12 fibers in the vicinity were randomly extracted to remove the thickest and thinnest fibers. It is the value obtained by measuring points and averaging.
- the content of fine cellulose fibers in the fine cellulose fiber dispersion is appropriately adjusted depending on the amount of cellulose fiber that is the starting material used. From the viewpoint of the stability of the dispersion, % By weight or more is preferable, 1% by weight or more is more preferable, 50% by weight or less is preferable, 40% by weight or less is more preferable, and 30% by weight or less is more preferable.
- the content of at least one of the organic solvent, the resin, and the resin precursor in the fine cellulose fiber dispersion is the same as the content of each component of the raw material dispersion described above, and the preferred range is also the same.
- the weight ratio of the fine cellulose fiber to at least one of the resin and the resin precursor is the same as the weight ratio of the cellulose fiber to at least one of the resin and the resin precursor. Furthermore, the weight ratio of at least one of the resin and the resin precursor to the organic solvent is also as described above.
- Cellulose type I crystal It is preferable that the fine cellulose fiber obtained by the said defibration process has a cellulose I type crystal structure.
- Cellulose I-type crystals have a higher crystal elastic modulus than other crystal structures, and are therefore preferable because of high elastic modulus, high strength, and low linear expansion coefficient.
- the manufacturing method of a cellulose fiber composite is not specifically limited, It is preferable that it is a manufacturing method including the following two processes (an addition process and a composite process).
- An addition process and a composite process At least one of heat treatment and exposure treatment is added to the fine cellulose fiber dispersion obtained in the step of adding at least one of resin and resin precursor to the fine cellulose fiber dispersion (compositing step) addition step. Step of applying and removing the solvent to obtain a cellulose fiber composite containing fine cellulose fibers and resin
- the addition step may not be performed. That is, the adding step is an optional step.
- the adding step is a step of further adding at least one of a resin and a resin precursor to the fine cellulose fiber dispersion. As described above, through this step, a fine cellulose fiber dispersion satisfying a desired weight ratio between the fine cellulose fibers and at least one of the resin and the resin precursor can be obtained. The amount of at least one of the resin to be added and the resin precursor is appropriately adjusted according to the application to be used.
- additives such as the above-described curing agent may be added together.
- an epoxy resin curing agent may be added in the step.
- a solvent may be added instead of at least one of the resin and the resin precursor. Further, at least one of the resin and the resin precursor and the solvent may be added together.
- At least one of the resin and resin precursor added here, and the specific example of a solvent are at least one of the resin and resin precursor which are contained in the fine cellulose fiber dispersion obtained by the manufacturing method of the said invention. As well as the solvent.
- the complexing step is a step of obtaining a cellulose fiber composite containing fine cellulose fibers and a resin by subjecting the fine cellulose fiber dispersion to at least one of heat treatment and exposure treatment and removing the solvent. By passing through this step, a cellulose fiber composite exhibiting excellent low linear expansion can be obtained.
- the precursor is cured through the step to become a resin.
- the fine cellulose fiber dispersion may be applied onto the substrate to form a coating film, or may be poured into a mold.
- a drying treatment may be performed to remove the solvent.
- the conditions for the heat treatment are not particularly limited, and when a resin precursor is used, it may be at or above the temperature at which the precursor is cured.
- the heating temperature is preferably 60 ° C. or higher, more preferably 100 ° C. or higher, from the viewpoint that the solvent can be volatilized and removed.
- 250 degrees C or less is preferable and 200 degrees C or less is more preferable.
- the heating time is preferably 60 to 180 minutes from the viewpoint of productivity.
- the heat treatment may be performed multiple times by changing the temperature and heating time. Specifically, primary heating at 60 to 100 ° C. for 30 to 60 minutes, secondary heating at 130 to 160 ° C. for 30 to 60 minutes, and 30 to 150 ° C., which is 40 to 60 ° C. higher than the secondary heating temperature. It is preferable to carry out by a three-stage treatment with tertiary heating for ⁇ 60 minutes in that the solvent is completely removed, the surface shape of the composite is reduced, and the composite is completely cured. In addition, at least two stages of heating is preferable.
- light such as infrared rays, visible rays, and ultraviolet rays, and radiation such as electron beams are used.
- Light is preferable, and ultraviolet rays are more preferable.
- the wavelength of light is preferably 200 to 450 nm, and more preferably 300 to 400 nm.
- the amount of light to be irradiated is appropriately selected depending on the resin precursor or photopolymerization initiator used. Specifically, for example, the case of irradiation with ultraviolet rays having a wavelength of 300 ⁇ 450 nm, preferably the dose is in the range of 0.1 J / cm 2 or more 200 J / cm 2 or less, 1 J / cm 2 or more 20 J / cm 2 The following range is more preferable.
- the lamp used include a metal halide lamp, a high-pressure mercury lamp, an ultraviolet LED lamp, and the like.
- At least one of an epoxy resin and its precursor is used as at least one of the resin and the resin precursor, at least one of an epoxy resin curing agent and a curing accelerator is added to the dispersion and cured to produce a composite. It is preferable.
- the high molecular weight epoxy resin has a low epoxy group concentration, it is preferable to add a polyfunctional epoxy resin to increase the epoxy group concentration and increase the crosslinking density in order to cure.
- the curing accelerator is preferably blended in an amount of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the total epoxy resin.
- the following curing methods I and II are preferably exemplified.
- Curing Method I When the weight average molecular weight (Mw) of the epoxy resin component in the dispersion is 200 to 6,000, after adding an epoxy resin curing agent to the dispersion and heating and mixing at a temperature of 100 to 200 ° C. for 5 minutes Then, a curing accelerator is quickly mixed to prepare a resin composition. The composition is defoamed by removing the solvent component under reduced pressure, poured into a mold, and heated at 120 to 200 ° C. for 2 to 5 hours to obtain a composite.
- Mw weight average molecular weight
- Curing method II When the weight average molecular weight (Mw) of the epoxy resin component in the dispersion is more than 6,000 but not more than 90,000, a polyfunctional epoxy resin and a curing accelerator are mixed into the dispersion to prepare a varnish. Using an applicator with a slit width of 300 ⁇ m, draw a coating film on PTFE tape (Chuko Kasei Kogyo Co., Ltd .: Chuko Flow Skived Tape MSF-100), hold it at 60 ° C. for 60 minutes with a hot air dryer, and 160 ° C. For 60 minutes and further at 200 ° C. for 60 minutes to obtain a composite.
- PTFE tape Choko Kasei Kogyo Co., Ltd .: Chuko Flow Skived Tape MSF-100
- ⁇ Cellulose fiber composite> (Fine cellulose fiber content)
- the content of the fine cellulose fiber in the cellulose fiber composite obtained by the production method of the present invention is not particularly limited. % By weight or more is preferable, 5% by weight or more is more preferable, 10% by weight is further preferable, 99% by weight or less is preferable, 80% by weight or less is more preferable, and 70% by weight or less is more preferable.
- the effect of reducing the linear thermal expansion coefficient of the cellulose fiber composite by the fine cellulose fiber becomes sufficient.
- the content of fine cellulose fibers in the composite to the upper limit or less, adhesion between fibers by resin or filling of spaces between fibers becomes sufficient, and the strength or transparency of the cellulose fiber composite, hardening The flatness of the surface can be improved.
- the content of the resin in the cellulose fiber composite obtained by the production method of the present invention is not particularly limited, but is preferably 1% by weight or more, more preferably 20% by weight or more, and more preferably 30% by weight or more from the viewpoint of moldability. More preferably, it is preferably 97.5% by weight or less, more preferably 95% by weight or less, and further preferably 90% by weight or less.
- the cellulose fiber composite is substantially composed of cellulose fibers and a resin.
- the content of the fine cellulose fibers and the resin in the cellulose fiber composite can be determined from, for example, the weight of cellulose before complexing and the weight of cellulose after complexing.
- the cellulose fiber composite is immersed in a solvent in which the resin is soluble to remove only the resin, and the weight can be obtained from the remaining fine cellulose fibers.
- it can also be obtained by a method for obtaining from the specific gravity of the resin and a method for obtaining the functional group of the resin or fine cellulose fiber by quantification using NMR or IR.
- the thickness is preferably 10 ⁇ m or more and 10 cm or less, and by setting such thickness, strength as a structural material can be maintained. it can. Further, it is more preferably 50 ⁇ m or more and 1 cm or less, and further preferably 80 ⁇ m or more and 250 ⁇ m or less.
- the film generally means the plate-shaped object whose thickness is 200 micrometers or less, and a sheet
- the cellulose fiber composite obtained by the present invention exhibits a low coefficient of linear expansion (elongation rate per 1K).
- the linear expansion coefficient of the cellulose fiber composite is preferably 1 to 70 ppm / K, more preferably 1 to 60 ppm / K, and particularly preferably 1 to 50 ppm / K.
- the linear expansion coefficient of an inorganic thin film transistor is about 15 ppm / K
- the linear expansion coefficient of a cellulose fiber composite is 50 ppm / K or less.
- the linear expansion coefficient of the cellulose fiber composite is particularly preferably 1 to 50 ppm / K.
- the cellulose fiber composite obtained by the present invention has an effect of increasing the Tg (glass transition temperature) of the resin by uniformly dispersing the cellulose fibers in the resin.
- Tg glass transition temperature
- a material having a high Tg suitable for the use described later can be obtained.
- an epoxy resin is used, the effect becomes remarkable.
- an increase in Tg of the composite by 3 to 4 ° C. is a great merit.
- ⁇ Application> You may use the cellulose fiber composite obtained by the manufacturing method of this invention with substrates, such as resin, as a laminated body. You may manufacture a laminated body by apply
- the cellulose fiber composite or the laminate obtained by the production method of the present invention can be used in various applications, such as adhesives, paints, building materials for civil engineering and construction, and insulating materials for electrical or electronic parts. It is done.
- the measuring method of various physical properties of the fine cellulose fiber dispersion and the cellulose fiber composite is as follows.
- a fine cellulose fiber dispersion was prepared, and the presence or absence of sedimentation immediately after the preparation and after standing at room temperature for 10 days was visually evaluated according to the following criteria. “A with no settling” AA, “A with almost no settling” A, “A with some settling or with some agglomerates in the liquid” B, “A very large amount of sedimentation or a large amount of aggregates in the liquid” was C, and AA and A were acceptable.
- the number average fiber diameter of the fine cellulose fibers was determined by observing with an optical microscope, SEM or TEM. Specifically, after removing the organic solvent from the dispersion by drying, a line is drawn on the diagonal line of the SEM photograph magnified 30,000 times, and 12 fibers in the vicinity are extracted at random, and the thickest fiber and the most The average of 10 measured values from which fine fibers were removed was taken as the number average fiber diameter.
- Example 4 the “film forming property” evaluation in Example 4 described later is intended to evaluate the moldability of the dispersion in a predetermined mold, and “AA” indicates that the moldability is excellent, and the surface smoothness is impaired. The case where a molding defect such as that occurred was evaluated as “C”.
- Tg was obtained from the measured value from 40 ° C. to 200 ° C. at the second temperature increase.
- Wood flour (Miyashita Wood Co., Ltd., Yonematsu 100, particle size 50-250 ⁇ m, average particle size 138 ⁇ m) was degreased with a 2% by weight aqueous solution of sodium carbonate at 80 ° C. for 6 hours. This was washed with demineralized water and then delignified with sodium chlorite under acetic acid acidity at 80 ° C. for 5.5 hours. This was washed with demineralized water and then immersed in a 5% by weight aqueous solution of potassium hydroxide for 16 hours for dehemicellulose treatment. This was washed with demineralized water to obtain cellulose fibers (number average fiber diameter 60 ⁇ m).
- the chemical modification rate of the obtained acetylated cellulose fiber was determined according to the above-described method for measuring the chemical modification rate and found to be 16 mol%.
- the chemical modification rate of the benzoylated cellulose fiber was determined as described above and was 37 mol%.
- NNKP Softwood kraft pulp
- Example 1 The water-containing acetylated cellulose fiber obtained in Production Example 2 (fiber content 7% by weight, the balance being mainly water) was dehydrated by filtration. The step of dispersing this in methyl ethyl ketone and filtering was performed three times, and water was replaced with methyl ethyl ketone.
- an epoxy resin prepared by adding methyl ethyl ketone and cyclohexanone to a composition containing 30% by weight of a modified biphenol type epoxy resin, 35% by weight of methyl ethyl ketone, and 35% by weight of cyclohexanone (YX6954BH30 manufactured by JER) to give a resin content of 20% by weight.
- a solution modified biphenol type epoxy resin 20% by weight, methyl ethyl ketone 40% by weight, cyclohexanone 40% by weight was prepared.
- the cellulose fiber dispersion is mixed with the epoxy resin solid content so that the content of acetylated cellulose fiber is 25% by weight. (Raw material dispersion) was prepared.
- the obtained raw material dispersion is processed with a rotary high-speed homogenizer (CLEAMIX 2.2S manufactured by M Technique Co., Ltd.) at 20000 rpm for 30 minutes to defibrate cellulose fibers and fine cellulose fibers in which fine cellulose fibers are dispersed. A dispersion was obtained. The number average fiber diameter of the obtained fine cellulose fibers was 80 nm. Table 1 shows various measurement results.
- Example 2 To the fine cellulose fiber dispersion obtained in Example 1, 5% by weight of a special novolac type epoxy resin (corresponding to an epoxy resin curing agent, 157S65 manufactured by JER) based on the solid content of the epoxy resin in the fine cellulose fiber dispersion. ) 0.05% by weight of 2-ethyl-4 (5) -methylimidazole (curing accelerator, EMI-24 manufactured by JER) based on the total amount of the epoxy resin solids and the special novolac type epoxy resin. After adding and mixing uniformly, a part of the solvent was volatilized and a film was formed by an applicator to obtain a coating film (thickness: 200 ⁇ m).
- a special novolac type epoxy resin corresponding to an epoxy resin curing agent, 157S65 manufactured by JER
- 2-ethyl-4 (5) -methylimidazole curing accelerator, EMI-24 manufactured by JER
- the coating film was heated at 60 ° C. for 1 hour, further heated at 160 ° C. for 1 hour, and further heated at 200 ° C. for 1 hour to be cured to obtain a cellulose fiber composite.
- the number average fiber diameter of the fine cellulose fibers in the composite was 80 nm as described above. Table 1 shows various measurement results.
- Example 3 The water-containing benzoylated cellulose fiber obtained in Production Example 3 (fiber content 7% by weight, the balance being mainly water) was dehydrated by filtration. The step of dispersing this in methyl ethyl ketone and filtering was performed three times, and water was replaced with methyl ethyl ketone.
- methyl ethyl ketone was added to bisphenol A type epoxy resin (828EL manufactured by JER) to prepare an epoxy resin solution (bisphenol A type epoxy resin 50% by weight, methyl ethyl ketone 50% by weight) prepared to a resin content of 50% by weight.
- the benzoylated cellulose fiber substituted with methyl ethyl ketone and the epoxy resin solution was mixed at 25% by weight with respect to the epoxy resin solid content to prepare a cellulose fiber dispersion.
- the obtained raw material dispersion is processed with a rotary high-speed homogenizer (CLEAMIX 2.2S manufactured by M Technique Co., Ltd.) at 20000 rpm for 30 minutes to defibrate cellulose fibers and fine cellulose fibers in which fine cellulose fibers are dispersed. A dispersion was obtained. The number average fiber diameter of the obtained fine cellulose fibers was 75 nm. Table 1 shows various measurement results.
- a rotary high-speed homogenizer (CLEAMIX 2.2S manufactured by M Technique Co., Ltd.) at 20000 rpm for 30 minutes to defibrate cellulose fibers and fine cellulose fibers in which fine cellulose fibers are dispersed.
- a dispersion was obtained.
- the number average fiber diameter of the obtained fine cellulose fibers was 75 nm. Table 1 shows various measurement results.
- Example 4 63 parts of bisphenol A type novolak resin (corresponding to an epoxy resin curing agent, YLH129 manufactured by JER) is added to 100 parts of the epoxy resin in the fine cellulose fiber dispersion obtained in Example 3, and the mixture is mixed.
- the methyl ethyl ketone was volatilized at 90 ° C. under a reduced pressure of 0.15 KPa for 15 minutes using an evaporator (Bota-made Rota Vapor: R-124). Thereafter, 1% by weight of 2-ethyl-4 (5) -methylimidazole (curing accelerator, EMI-24 manufactured by JER) was added to the total amount of epoxy resin solids and bisphenol A type novolak resin. The resulting mixture was uniformly mixed to prepare a resin mixture.
- 2-ethyl-4 (5) -methylimidazole curing accelerator, EMI-24 manufactured by JER
- the resin mixed solution is poured into a casting plate having a thickness of 2 mm ⁇ length 100 mm ⁇ width 30 mm, which is heated at 160 ° C. for 1 hour, and further heated at 200 ° C. for 1 hour to be cured to obtain a cellulose fiber composite. It was.
- the number average fiber diameter of the fine cellulose fibers in the composite was 75 nm as described above. Table 1 shows various measurement results.
- Example 5 A fine cellulose fiber dispersion was obtained in the same manner as in Example 1 except that the cellulose fiber obtained in Production Example 1 was used. The number average fiber diameter of the obtained fine cellulose fibers was 95 nm. Table 1 shows various measurement results.
- Example 6 In the fine cellulose fiber dispersion obtained in Example 5, 5% by weight of a special novolac type epoxy resin (corresponding to an epoxy resin curing agent, 157S65 manufactured by JER) based on the epoxy resin solid content in the fine cellulose fiber dispersion. ) And 0.05% by weight of 2-ethyl-4 (5) -methylimidazole (curing accelerator, EMI-24 manufactured by JER) based on the total amount of epoxy resin solids and special novolac type epoxy resin Were added and mixed uniformly, and then a part of the solvent was volatilized to form a film with an applicator to obtain a coating film (thickness: 200 ⁇ m).
- a special novolac type epoxy resin corresponding to an epoxy resin curing agent, 157S65 manufactured by JER
- 2-ethyl-4 (5) -methylimidazole curing accelerator, EMI-24 manufactured by JER
- the coating film was heated at 60 ° C. for 1 hour, further heated at 160 ° C. for 1 hour, and further heated at 200 ° C. for 1 hour to be cured to obtain a cellulose fiber composite.
- the number average fiber diameter of the fine cellulose fibers in the composite was 95 nm as described above. Table 1 shows various measurement results.
- Example 7 In the same manner as in Example 1, the water-containing acetylated cellulose fiber obtained in Production Example 2 (fiber content: 7% by weight, the balance being mainly water) was adjusted to a content of acetylated cellulose fiber of 25 with respect to the epoxy resin solid content. A cellulose fiber dispersion was prepared by mixing so as to have a weight%.
- the obtained raw material dispersion was treated with a bead mill (Ultra Apex Mill UAM-015 manufactured by Kotobuki Industries Co., Ltd.) at a bead diameter of 0.3 mm and a peripheral speed of 11.4 m / sec for 4 hours, and further a bead diameter of 0.05 mm and a peripheral speed.
- Cellulose fibers were defibrillated by treatment at 11.4 m / sec for 4 hours to obtain a fine cellulose fiber dispersion in which fine cellulose fibers were dispersed.
- the number average fiber diameter of the obtained fine cellulose fiber was 50 nm. Table 1 shows various measurement results.
- Example 8 A curing agent and a curing accelerator were added to the fine cellulose fiber dispersion obtained in Example 7 and cured in the same manner as in Example 2 to obtain a cellulose fiber composite.
- the number average fiber diameter of the fine cellulose fibers in the composite was 50 nm as described above. Table 1 shows various measurement results.
- Example 9 The water-containing acetylated cellulose fiber obtained in Production Example 2 (fiber content 7% by weight, the balance being mainly water) was treated in the same manner as in Example 1 to adjust the content of acetylated cellulose fiber to 30% of the epoxy resin solid content.
- a cellulose fiber dispersion was prepared by mixing so as to have a weight%.
- the obtained raw material dispersion is treated with a multi-ring medium type pulverizer (MIC-0 type, Nara Machinery Co., Ltd.) at 1000 rpm for 40 minutes to defibrate cellulose fibers, and fine cellulose fiber dispersion in which fine cellulose fibers are dispersed.
- a multi-ring medium type pulverizer MIC-0 type, Nara Machinery Co., Ltd.
- Table 1 shows various measurement results.
- Example 10 The fine cellulose fiber dispersion obtained in Example 9 was cured in the same manner as in Example 2 to obtain a cellulose fiber composite. Table 1 shows various measurement results.
- Example 11 A fine cellulose fiber dispersion in which fine cellulose fibers were dispersed was obtained in the same manner as in Example 9 except that the rotation speed was 2000 rpm and the treatment time was 20 minutes. The number average fiber diameter of the obtained fine cellulose fibers was 70 nm. Table 1 shows various measurement results.
- Example 12 The fine cellulose fiber dispersion obtained in Example 11 was cured in the same manner as in Example 2 to obtain a cellulose fiber composite.
- the number average fiber diameter of the fine cellulose fibers in the composite was 70 nm as described above. Table 1 shows various measurement results.
- Example 13 The water-containing acetylated cellulose fiber obtained in Production Example 2 (fiber content 7% by weight, the balance being mainly water) was dehydrated by filtration. The step of dispersing this in methylene chloride and filtering was performed three times, and water was replaced with methylene chloride. On the other hand, cellulose acetate (manufactured by Daicel Chemical Industries) was dissolved in methylene chloride and adjusted to 10% by weight.
- cellulose fiber dispersion A liquid was prepared.
- the obtained raw material dispersion was treated with a bead mill (Ultra Apex Mill UAM-015 manufactured by Kotobuki Industries Co., Ltd.) at a bead diameter of 0.3 mm and a peripheral speed of 11.4 m / sec for 4 hours to defibrate cellulose fibers and finely A fine cellulose fiber dispersion in which cellulose fibers were dispersed was obtained.
- a bead mill Ultra Apex Mill UAM-015 manufactured by Kotobuki Industries Co., Ltd.
- the number average fiber diameter of the obtained fine cellulose fibers was 50 nm. Table 1 shows various measurement results.
- Example 14 The fine cellulose fiber dispersion obtained in Example 13 was formed into a film with an applicator to obtain a coating film (thickness: 200 ⁇ m). This coating film was heated at 60 ° C. for 1 hour to obtain a cellulose fiber composite. The number average fiber diameter of the fine cellulose fibers in the composite was 50 nm as described above. Table 1 shows various measurement results.
- Example 15 Cellulose fiber obtained in Production Example 1 containing cellulose fiber content of 0.5% by weight and polyvinyl alcohol (Nippon Synthetic Chemical Industry AH-17, saponification degree 97-98.5%, average polymerization degree 1700) It adjusted with water so that the quantity might be 1 weight%, and the cellulose fiber dispersion liquid was obtained.
- polyvinyl alcohol Nippon Synthetic Chemical Industry AH-17, saponification degree 97-98.5%, average polymerization degree 1700
- the obtained raw material dispersion is treated with a rotary high-speed homogenizer (CLEAMIX 2.2S manufactured by M Technique Co., Ltd.) at 20000 rpm for 60 minutes to defibrate cellulose fibers, and fine cellulose fibers in which fine cellulose fibers are dispersed. A dispersion was obtained. Table 2 shows various measurement results.
- Example 16 The fine cellulose fiber dispersion obtained in Example 15 was cast on an optool-treated glass petri dish, defoamed under vacuum, and then left in an oven at 105 ° C. for 2 hours to evaporate water. A composite in which cellulose was uniformly dispersed in polyvinyl alcohol could be peeled off.
- Example 17 A fine cellulose fiber dispersion in which fine cellulose fibers were dispersed was obtained in the same manner as in Example 15 except that the cellulose fiber content was 0.5 wt% and the polyvinyl alcohol content was 0.5 wt%. The number average fiber diameter of the obtained fine cellulose fiber was 30 nm. Table 2 shows various measurement results.
- Example 18 In the same manner as in Example 16, a cellulose fiber composite was obtained from the fine cellulose dispersion obtained in Example 17. Table 2 shows various measurement results.
- Example 19 A fine cellulose fiber dispersion in which fine cellulose fibers were dispersed was obtained in the same manner as in Example 15 except that the cellulose fiber content was 0.5 wt% and the polyvinyl alcohol content was 0.1 wt%. Table 2 shows various measurement results.
- Example 20 In the same manner as in Example 16, a cellulose fiber composite was obtained from the fine cellulose dispersion obtained in Example 19. Table 2 shows various measurement results.
- Example 21 A fine cellulose fiber dispersion in which fine cellulose fibers were dispersed was obtained in the same manner as in Example 15 except that the cellulose fiber content was 0.5 wt% and the polyvinyl alcohol content was 0.05 wt%. Table 2 shows various measurement results.
- Example 22 In the same manner as in Example 16, a cellulose fiber composite was obtained from the fine cellulose dispersion obtained in Example 21. Table 2 shows various measurement results.
- ⁇ Comparative Example 1 100 parts by weight of bisphenol A type epoxy resin (JER827 made by JER), which is an epoxy compound of a thermosetting resin precursor, is melted at 120 ° C. and mixed with 18 parts by weight of a curing agent (m-xylylenediamine). A liquid was obtained.
- JER827 made by JER
- a curing agent m-xylylenediamine
- the cellulose nonwoven fabric obtained in Production Example 4 is impregnated with the mixed solution (impregnation time: within 5 minutes), and thermosetting (curing time: 100 ° C. under a pressure of 9.8 MPa) in a press. For 1 hour) to obtain a cellulose fiber composite.
- the thickness was about 30 ⁇ m. From the weight, the cellulose fiber in the composite was 29% by weight.
- solid content means components other than solvents, such as a cellulose, an epoxy resin, and a hardening
- the water-containing benzoylated cellulose fiber obtained in Production Example 3 was dehydrated by filtration.
- the step of dispersing this in methyl ethyl ketone and filtering was performed three times, and water was replaced with methyl ethyl ketone. This was dispersed in methyl ethyl ketone to prepare a cellulose fiber at 1.4% by weight.
- the obtained raw material dispersion was treated at 20000 rpm for 60 minutes with a rotary high-speed homogenizer (Cleamix 2.2S manufactured by M Technique Co., Ltd.) to defibrate cellulose fibers.
- the dispersion after defibration contains 30% by weight of modified biphenol type epoxy resin, 35% by weight of methyl ethyl ketone, and 35% by weight of cyclohexanone so that the content of benzoylated cellulose fiber is 25% by weight with respect to the solid content of the epoxy resin.
- the composition (YX6954BH30 manufactured by JER) was added and mixed.
- the number average fiber diameter of the obtained cellulose fibers was 300 nm. Table 2 shows various measurement results.
- the obtained dispersion was mixed with 5% by weight of a special novolac type epoxy resin (corresponding to an epoxy resin curing agent, 157S65 manufactured by JER), epoxy resin solids and JER based on the epoxy resin solids in the dispersion.
- a special novolac type epoxy resin corresponding to an epoxy resin curing agent, 157S65 manufactured by JER
- Accelerator JER EMI-24 is added to the total amount of 157S65 manufactured by Komatsu Ltd. and mixed uniformly, and then a part of the solvent is volatilized to form a film with an applicator.
- a membrane was obtained.
- the coating film was heated at 60 ° C. for 1 hour, further heated at 160 ° C. for 1 hour, and further heated at 200 ° C. for 1 hour to be cured to obtain a cellulose fiber composite.
- the number average fiber diameter of the cellulose fibers in the composite was 300 nm as described above. Table 2 shows various measurement results.
- ⁇ Comparative Example 5> The cellulose fiber obtained in Production Example 1 was adjusted with water so that the cellulose fiber content was 0.5% by weight to obtain a cellulose fiber dispersion.
- the obtained raw material dispersion is treated with a rotary high-speed homogenizer (CLEAMIX 2.2S manufactured by M Technique Co., Ltd.) at 20000 rpm for 60 minutes to defibrate cellulose fibers and fine cellulose fibers in which fine cellulose fibers are dispersed. A dispersion was obtained.
- a rotary high-speed homogenizer (CLEAMIX 2.2S manufactured by M Technique Co., Ltd.) at 20000 rpm for 60 minutes to defibrate cellulose fibers and fine cellulose fibers in which fine cellulose fibers are dispersed.
- a dispersion was obtained.
- Example 16 In the same manner as in Example 16, the mixed dispersion was cast on an optool-treated glass petri dish, and after defoaming, water was evaporated by leaving it in an oven at 105 ° C. for 2 hours or more. The obtained cellulose fiber composite could not be peeled off from the glass petri dish.
- cellulose fibers (or modified cellulose fibers) are defibrated in an organic solvent together with an epoxy resin. A fine cellulose fiber dispersion excellent in dispersion stability could be obtained.
- the obtained composite showed an excellent linear expansion coefficient and further showed a higher Tg as compared with the Tg (137 ° C.) of the resin itself used.
- Example 8 images of the cellulose fiber composite films obtained in Examples 2 and 8 taken with a microscope are shown in FIGS. 1 and 2, respectively. From the obtained images of FIGS. 1 and 2, the area ratio (%) of the portion where there was no cellulose in one field of view was calculated. As a result, the value of Example 8 was smaller than that of Example 2. That is, the aspect of Example 8 means that fine cellulose fibers are uniformly distributed in the film.
- the fine cellulose fibers are more uniformly dispersed.
- the dispersibility of the fine cellulose fibers is more excellent. It was found that a cellulose fiber composite can be obtained.
- the method of Comparative Example 1 has a drawback that it cannot be applied, so that it was not possible to form a film to obtain a composite having a desired shape (film forming property: C). Furthermore, in the method of Comparative Example 1, there are problems that it is difficult to control the blending ratio between the cellulose fiber and the resin, and that other components cannot be added afterwards. In addition, since the composite body obtained by the method of Comparative Example 1 has a layered structure of a resin layer and a cellulose fiber layer, there is a concern that delamination may occur during heating due to the difference in the linear expansion coefficient of each layer.
- the production time in the Example is about 10 to 30% shorter than the production time of the Comparative Example. It has been found that the method of using the dispersion is preferable from a more industrial viewpoint.
- Comparative Example 3 even when an organic solvent is added to the composition containing the cellulose fiber and the epoxy resin obtained in Comparative Example 2, the stability of the desired dispersion can be obtained. There wasn't.
- cellulose fibers were defibrated in an organic solvent in which no epoxy resin (at least one of a resin and a resin precursor) was present, and then an epoxy resin was added to produce a dispersion.
- the epoxy resin due to the aggregation of the cellulose fibers, the epoxy resin was not easily mixed, and a dispersion having sufficient dispersion stability could not be obtained.
- satisfactory results were not obtained in terms of film forming properties and dispersibility of cellulose fibers in the composite.
Abstract
Description
1.微細セルロース繊維と、樹脂および樹脂前駆体の少なくとも一方と、有機溶媒とを含有する微細セルロース繊維分散液の製造方法であって、
セルロース繊維と、樹脂および樹脂前駆体の少なくとも一方と、有機溶媒とを含有する原料分散液中で、セルロース繊維を解繊して、微細セルロース繊維を得る解繊工程を含む、微細セルロース繊維分散液の製造方法。
2.前記セルロース繊維が、化学修飾されたセルロース繊維である、前項1に記載の微細セルロース繊維分散液の製造方法。
3.前記樹脂および樹脂前駆体の少なくとも一方が、熱可塑性樹脂、熱硬化性樹脂および光硬化性樹脂並びにこれらの前駆体からなる群から選ばれる、前項1または2に記載の微細セルロース繊維分散液の製造方法。
4.前記樹脂および樹脂前駆体の少なくとも一方が、エポキシ樹脂およびその前駆体の少なくとも一方である、前項1~3のいずれか1つに記載の微細セルロース繊維分散液の製造方法。
5.前項1~4のいずれか1つに記載の微細セルロース繊維分散液の製造方法より得られる、微細セルロース繊維分散液。
6.前項5に記載の微細セルロース繊維分散液に、さらに樹脂および樹脂前駆体の少なくとも一方を添加して得られる、微細セルロース繊維分散液。
7.前項5または6に記載の微細セルロース繊維分散液に、さらに有機溶媒を添加して得られる、微細セルロース繊維分散液。
8.前項5~7のいずれか1つに記載の微細セルロース繊維分散液を用いて得られる、微細セルロース繊維と樹脂とを含有するセルロース繊維複合体。
9.前項5~7のいずれか1つに記載の微細セルロース繊維分散液に加熱処理および露光処理の少なくとも一方を施し、前記有機溶媒を除去して、微細セルロース繊維と樹脂とを含有するセルロース繊維複合体を得る複合化工程を含む、セルロース繊維複合体の製造方法。
10.前記複合化工程前に、前記微細セルロース繊維分散液にさらに樹脂および樹脂前駆体の少なくとも一方を添加する添加工程を含む、前項9に記載のセルロース繊維複合体の製造方法。
11.微細セルロース繊維と樹脂とを含有するセルロース繊維複合体の製造方法であって、
セルロース繊維と、樹脂および樹脂前駆体の少なくとも一方と、溶媒とを含有する原料分散液中で、セルロース繊維を解繊して、微細セルロース繊維を得る解繊工程、および、
該微細セルロース繊維を含有する分散液に、加熱処理および露光処理の少なくとも一方を施し、
前記溶媒を除去して、微細セルロース繊維と樹脂とを含有するセルロース繊維複合体を得る複合化工程を含む、セルロース繊維複合体の製造方法。
12.前項9~11のいずれか1つに記載の製造方法により製造された、セルロース繊維複合体。
13.基板及び前項8または12に記載のセルロース繊維複合体を含む積層体。
14.さらに保護フィルムを含む、前項13に記載の積層体。
15.前項13または14に記載の積層体を含む配線基板。
16.微細セルロース繊維と、樹脂および樹脂前駆体の少なくとも一方と、有機溶媒とを含有する微細セルロース繊維分散液であって、下記(1)を満たす微細セルロース繊維分散液。
(1)分散液を室温で10日間静置した後、分散液中の沈降の有無を目視により観察する沈降性試験において、沈降が観察されない。
本発明で使用するセルロース繊維は、微細セルロール繊維の原料となる材料(セルロース繊維原料)であり、セルロースを含有する物質(セルロース含有物)であればその種類は特に限定はされない。
本発明に用いられるセルロース繊維の繊維径は特に制限されるものではなく、後述する解繊処理時の解繊効率、および取扱い性の点から、数平均繊維径としては10μm~100mmであることが好ましく、50μm~0.5mmであることがより好ましい。一般的な精製を経たものは数百μm程度(50~500μmが好ましい)であり、また一般的な方法によりセルロースを解繊したものは数nm~1μmである。
本発明においては、使用するセルロース繊維に精製処理を施して(精製工程)、原料中のセルロース以外の物質、例えば、リグニン、ヘミセルロースまたは樹脂(ヤニ)などを除去することが好ましい。つまり、精製処理が施されたセルロース繊維を使用することが好ましい。
本発明においては、使用されるセルロース繊維は、化学修飾によって誘導化されたもの(化学修飾されたセルロース繊維)であってもよい。化学修飾とは、セルロース中の水酸基が化学修飾剤と反応して化学修飾されたものである。
修飾方法は、特に限定されるものではないが、セルロースと次に挙げるような化学修飾剤とを反応させる方法がある。
セルロース繊維の化学修飾は、公知の方法によって実施することができる。すなわち、常法に従って、セルロースと化学修飾剤とを反応させることによって、化学修飾を実施できる。この際、必要に応じて溶媒または触媒を使用してもよく、加熱および減圧等を行ってもよい。
化学修飾率とは、セルロース中の全水酸基のうちの化学修飾されたものの割合を示し、化学修飾率は下記の滴定法によって測定することができる。
本発明で使用する溶媒は、使用する樹脂または樹脂前駆体が溶解または分散すれば特に限定されず、水などの水性媒体でも有機溶媒でもよいが、有機溶媒が好ましい。
本発明で使用する樹脂または樹脂前駆体は、後述の微細セルロース繊維と複合化できる樹脂または樹脂前駆体であれば特に制限されない。樹脂または樹脂前駆体としては、例えば、熱可塑性樹脂、熱硬化性樹脂、光(活性エネルギー線)硬化性樹脂、またはこれらの前駆体が挙げられる。また、樹脂または樹脂前駆体としては、例えば、アルコール系樹脂、アミド系樹脂、エーテル系樹脂、アミン系樹脂、芳香族系樹脂またはこれらの前駆体が挙げられる。また、樹脂または樹脂前駆体としては、例えば、セルロース誘導体が挙げられる。
熱可塑性樹脂としては、例えば、スチレン系樹脂、アクリル系樹脂、芳香族ポリカーボネート系樹脂、脂肪族ポリカーボネート系樹脂、芳香族ポリエステル系樹脂、脂肪族ポリエステル系樹脂、脂肪族ポリオレフィン系樹脂、環状オレフィン系樹脂、ポリアミド系樹脂、ポリフェニレンエーテル系樹脂、熱可塑性ポリイミド系樹脂、ポリアセタール系樹脂、ポリスルホン系樹脂および非晶性フッ素系樹脂等が挙げられる。これらの熱可塑性樹脂は、1種を単独で用いてもよく、2種以上を併用してもよい。
熱硬化性樹脂、光(活性エネルギー線)硬化性樹脂とは、熱または光により硬化する樹脂のことを意味する。硬化性樹脂の前駆体とは、通常、常温では液状、半固体状または固形状であって、常温下または加熱下で流動性を示す物質を意味する。これらは、硬化剤、触媒、熱または光の作用によって重合反応または架橋反応を起こして分子量を増大させながら、網目状の三次元構造を形成してなる不溶不融の樹脂となり得る。
本発明における熱硬化性樹脂またはその前駆体は特に限定されないが、例えば、エポキシ樹脂、アクリル樹脂、オキセタン樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、珪素樹脂、ポリウレタン樹脂、ジアリルフタレート樹脂および熱硬化性ポリイミド樹脂等の樹脂またはその前駆体が挙げられる。
本発明における光硬化性樹脂またはその前駆体は特に限定されないが、例えば、上述の熱硬化性樹脂の説明において例示した、エポキシ樹脂、アクリル樹脂およびオキセタン樹脂等の樹脂またはその前駆体が挙げられる。
アルコール系樹脂としては、例えば、ポリエチレングリコール、ポリエーテルポリオール、ポリエステルポリオール、ポリビニルアルコール、アミロース、アミロペクチン、ソルビトル、ポリカプロラクトン、ポリバレロラクトン、ポリブチロラクトン、ポリグリコールおよびポリ乳酸等が挙げられる。
アミド系樹脂としては、例えば、ポリアクリルアミド、キチン、キトサン、ポリビニルピロリドンおよびポリカプロラクタム等が挙げられる。
エーテル系樹脂としては、例えば、クラウンエーテル、ポリエチレングリコールおよびポリプロピレングリコール等が挙げられる。
アミン系樹脂としては、例えば、ポリアリルアミン、ポリリジンおよび各種のアミン変性アクリルコポリマー等が挙げられる。
芳香族系樹脂としては、例えば、ポリフェニレンオキサイド、カテキン、タンニンおよびテルペン等が挙げられる。この中では、アルコール系樹脂およびアミド系樹脂が好ましく、特に、ポリビニルアルコールおよびポリビニルピロリドンなどが好ましい。
セルロース誘導体としては、例えば、セルロース有機酸エステル、セルロースエーテル、アルキルセルロース、ヒドロキシアルキルセルロースおよびイオン性の置換基を持つセルロースエーテルが挙げられる。
本発明においては上述した化合物以外に、必要に応じて、連鎖移動剤、紫外線吸収剤、充填剤、シランカップリング剤、光・熱重合開始剤、硬化剤および硬化促進剤などの化合物を使用してもよい。該化合物は後述する解繊工程時に共存させてもよいし、解繊工程後の分散液に添加して使用してもよい。
本発明の製造方法の解繊工程は、セルロース繊維と、樹脂および樹脂前駆体の少なくとも一方と、溶媒とを含有する原料分散液中で、セルロース繊維の解繊処理を行い、微細セルロース繊維を得る工程である。
(混合工程) 溶媒置換工程で得られた分散液と樹脂および樹脂前駆体の少なくとも一方とを混合する工程
解繊工程においてセルロース繊維を解繊する方法は、特に制限されないが、具体的には、例えば、直径1mm程度のセラミック製ビーズをセルロース繊維濃度0.5~50重量%、例えば、1重量%程度の原料分散液に入れ、ペイントシェーカーまたはビーズミルなどのメディアミル等を用いて振動を与え、セルロース繊維を解繊する方法などが挙げられる。
上記解繊工程を経て得られた微細セルロース繊維分散液中には、微細セルロース繊維が均一に分散しており、微細セルロース繊維の凝集および沈降が抑制され、優れた液安定性を有する。具体的には、通常、該分散液を室温にて10日間静置しても、目視において沈降物などは確認できないことが好ましい。
上記方法によって得られた微細セルロース繊維分散液中の微細セルロース繊維の数平均繊維径は、分散液中の分散媒を乾燥除去した後、SEMまたはTEM等で観察することにより計測して求めることができる。
上記解繊工程によって得られる微細セルロース繊維は、セルロースI型結晶構造を有することが好ましい。セルロースI型結晶は、他の結晶構造より結晶弾性率が高いため、高弾性率、高強度および低線膨張係数であり好ましい。
上述した微細セルロース繊維分散液を用いることにより、微細セルロース繊維が樹脂中に均一に分散したセルロース繊維複合体を得ることができる。
(添加工程)微細セルロース繊維分散液に、さらに樹脂および樹脂前駆体の少なくとも一方を添加する工程
(複合化工程)添加工程で得られた微細セルロース繊維分散液に加熱処理および露光処理の少なくとも一方を施し、溶媒を除去して、微細セルロース繊維と樹脂とを含有するセルロース繊維複合体を得る工程
添加工程は、微細セルロース繊維分散液に、さらに樹脂および樹脂前駆体の少なくとも一方を添加する工程である。上述の通り、該工程を経て、微細セルロース繊維と樹脂および樹脂前駆体の少なくとも一方との所望の重量比を満たす微細セルロース繊維分散液を得ることができる。添加する樹脂および樹脂前駆体の少なくとも一方の量は、使用される用途などに応じて適宜調整する。
複合化工程は、微細セルロース繊維分散液に加熱処理および露光処理の少なくとも一方を施し、溶媒を除去して、微細セルロース繊維と樹脂とを含有するセルロース繊維複合体を得る工程である。該工程を経ることにより、優れた低線膨張性を示すセルロース繊維複合体を得ることができる。なお、樹脂前駆体を使用した場合は、該工程を経て該前駆体が硬化されて、樹脂となる。
(微細セルロース繊維含有量)
本発明の製造方法により得られるセルロース繊維複合体中の微細セルロース繊維の含有量は、特に制限されないが、微細セルロース繊維の好適な含有量としては、セルロース繊維複合体全量に対して、2.5重量%以上が好ましく、5重量%以上がより好ましく、10重量%がさらに好ましく、99重量%以下が好ましく、80重量%以下がより好ましく、70重量%以下がさらに好ましい。
本発明の製造方法により得られるセルロース繊維複合体中における樹脂の含有量は特に制限されないが、成型性の点から、1重量%以上が好ましく、20重量%以上がより好ましく、30重量%以上がさらに好ましく、97.5重量%以下が好ましく、95重量%以下がより好ましく、90重量%以下がさらに好ましい。
本発明の製造方法により得られるセルロース繊維複合体の形状は、特に限定されず、板状、または曲面を有する板状とすることもできる。また、その他の異形形状であってもよい。また、厚さは必ずしも均一である必要はなく、部分的に異なっていてもよい。
本発明により得られるセルロース繊維複合体は、低い線膨張係数(1Kあたりの伸び率)を示す。このセルロース繊維複合体の線膨張係数は、1~70ppm/Kが好ましく、1~60ppm/Kがより好ましく、1~50ppm/Kが特に好ましい。
本発明により得られるセルロース繊維複合体では、セルロース繊維が樹脂中に均一に分散することによって、樹脂のTg(ガラス転移温度)を上昇させる効果を有する。該効果によって、後述する用途に好適な高いTgを示す材料を得ることができる。特に、エポキシ樹脂を使用した場合は、その効果が顕著となる。なお、電材用途においては、複合体のTgが3~4℃上昇することは、大きなメリットとなる。
本発明の製造方法により得られるセルロース繊維複合体を樹脂などの基板とともに積層体として使用してもよい。該基板上に本発明の微細セルロース繊維分散液を塗布し、上記のとおり、加熱処理および露光処理等を施すことにより、積層体を製造してもよい。また、該積層体は保護フィルムを有していてもよい。
微細セルロース繊維分散液を調製し、調製直後、および室温で10日間静置後の沈降の有無を、以下の基準に従って、目視により評価した。「全く沈降の見られないもの」をAA、「ほとんど沈降の見られないもの」をA、「やや沈降の見られるもの、または、液中の一部に凝集物が見られるもの」をB、「極めて多くの沈降が見られるもの、または、液中の大部分に凝集物が見られるもの」をCとし、AA及びAを合格とした。
微細セルロース繊維の数平均繊維径は、光学顕微鏡、SEMまたはTEM等で観察することにより計測して求めた。具体的には、分散液から有機溶媒を乾燥除去した後、30,000倍に拡大したSEM写真の対角線に線を引き、その近傍にある繊維をランダムに12点抽出し、最も太い繊維と最も細い繊維を除去した10点の測定値の平均を数平均繊維径とした。
微細セルロース繊維分散液からセルロース繊維複合体へ製膜する際の製膜性を、以下の基準に従って評価した。「均一に製膜できるもの」をAA、「ほぼ均一に製膜できるもの」をA、「ピンホールなどが生じて、やや不均一に製膜できるもの」をB、「ピンホールが多数生じるものや、製膜自体ができないもの」をCとし、AAおよびAを合格とした。
セルロース繊維複合体中の微細セルロース繊維の分散性を、以下の基準に従って、目視で評価した。微細セルロース繊維が「光を透過して、目視で繊維を確認できないもの」をAAA、微細セルロース繊維が「均一に分散しているもの」をAA、「ほぼ均一に分散しているもの」をA、「やや凝集しているもの」をB、「不均一なもの」をCとし、AAA、AAおよびAを合格とした。
セルロース繊維複合体をマイクロスコープで撮像し、撮像した画像を二値化して、一視野中のセルロースの存在しない部分の面積率(%)を算出した。
セルロース繊維複合体中の微細セルロース繊維の分散状態を、複合体の表面および断面方向からSEMにて3,000倍で観察し分散性を評価した。微細セルロース繊維が「均一に分散しているもの」をAA、「ほぼ均一に分散しているもの」をA、「大きさ50μm以上の凝集体が見られるもの」をB、「大きさ50μm以上の凝集体が多数見られるもの」をCとし、AAおよびAを合格とした。
セルロース繊維複合体を、2.5mm幅×20mm長にカットした。これをSII製TMA「EXSTAR6000」を用いて引張モードでチャック間10mm、荷重30mN、窒素雰囲気下、室温から150℃まで10℃/分間で昇温し、次いで150℃から20℃まで10℃/分間で降温し、更に20℃から200℃まで5℃/分間で昇温した際の2度目の昇温時の40℃から110℃の測定値から線膨張係数を求めた。
木粉((株)宮下木材、米松100、粒径50~250μm、平均粒径138μm)を炭酸ナトリウム2重量%水溶液で80℃にて6時間脱脂した。これを脱塩水で洗浄した後、亜塩素酸ナトリウムを用いて酢酸酸性下、80℃にて5.5時間脱リグニンした。これを脱塩水で洗浄した後、水酸化カリウム5重量%水溶液に16時間浸漬して、脱ヘミセルロース処理を行った。これを脱塩水で洗浄し、セルロース繊維(数平均繊維径60μm)を得た。
製造例1において、脱ヘミセルロースして、脱塩水洗浄したセルロース繊維を濾過により脱水した。これを酢酸中に分散して濾過する工程を3度行い、水を酢酸に置換した。トルエン25ml、酢酸20ml、60%過塩素酸水溶液0.1mlを混合しておき、そこに酢酸置換したセルロース繊維1gを添加した後、無水酢酸1.3mlを添加し、攪拌しながら1時間反応させた。反応後、反応液を濾過して、メタノール、脱塩水の順で洗浄した。
製造例1において、脱ヘミセルロースして、脱塩水洗浄したセルロース繊維を濾過により脱水した。これを酢酸中に分散して濾過する工程を3度行い、水を酢酸に置換した。30gの酢酸に酢酸ナトリウム1gを溶解させ、ここに得られたセルロース繊維1gを分散させた。この分散液を80℃に加温し、ベンゾイルクロライドを2.1g添加し、攪拌しながら5時間反応させた。反応後、反応液を濾過して、メタノール、脱塩水の順で洗浄した。
精製したコットンリンターを水に分散させて0.5重量%とし、これを超高圧ホモジナイザー(スギノマシン製アルティマイザー)に245MPaで10回通した。この微細セルロース繊維水分散液を0.2重量%に希釈し、孔径1μmのPTFEを用いた90mm径の濾過器に坪量11g/m2となるように投入して減圧濾過を行った。水が濾過された後にiso-ブタノールを静かに30ml投入し、PTFE上のセルロース不織布中の水をiso-ブタノールに置換した。その後、120℃、0.14MPaで5分間プレス乾燥して白色のセルロース不織布を得た。(膜厚:20μm、空孔率:61%、セルロース繊維の数平均繊維径:100nm)
針葉樹クラフトパルプ(NBKP)を、水に分散させて0.5重量%とし、これを超高圧ホモジナイザー(スギノマシン製アルティマイザー)に245MPaで10回通して、セルロースが分散した水分散液を得た(セルロースの数平均繊維径:80nm)。
製造例2で得られた含水アセチル化セルロース繊維(繊維含有量7重量%、残部は主に水)を濾過により脱水した。これをメチルエチルケトン中に分散して濾過する工程を3度行い、水をメチルエチルケトンに置換した。
実施例1で得られた微細セルロース繊維分散液に、この微細セルロース繊維分散液中のエポキシ樹脂固形分に対して5重量%の特殊ノボラック型エポキシ樹脂(エポキシ樹脂硬化剤に該当、JER社製157S65)、エポキシ樹脂固形分と特殊ノボラック型エポキシ樹脂との合計量に対して、0.05重量%の2-エチル-4(5)-メチルイミダゾール(硬化促進剤、JER社製EMI-24)を添加し、均一に混合した後溶媒の一部を揮発させ、アプリケーターで製膜して塗膜(厚さ:200μm)を得た。
製造例3で得られた含水ベンゾイル化セルロース繊維(繊維含有量7重量%、残部は主に水)を濾過により脱水した。これをメチルエチルケトン中に分散して濾過する工程を3度行い、水をメチルエチルケトンに置換した。
実施例3で得られた微細セルロース繊維分散液中のエポキシ樹脂100部に対して63部のビスフェノールA型ノボラック樹脂(エポキシ樹脂硬化剤に該当、JER社製YLH129)を添加し、この混合液中のメチルエチルケトンをエバポレーター(BUCHI製 Rota Vapor:R-124)を使用し、90℃で減圧度0.15KPaにて15分揮発させた。その後、エポキシ樹脂固形分とビスフェノールA型ノボラック樹脂との合計量に対して、1重量%の2-エチル-4(5)-メチルイミダゾール(硬化促進剤、JER社製EMI-24)を添加し、均一に混合して樹脂混合液を調製した。
製造例1で得られたセルロース繊維を用いること以外は、実施例1と同様にして、微細セルロース繊維分散液を得た。得られた微細セルロース繊維の数平均繊維径は、95nmであった。表1に各種測定結果を示す。
実施例5で得られた微細セルロース繊維分散液に、この微細セルロース繊維分散液中のエポキシ樹脂固形分に対して5重量%の特殊ノボラック型エポキシ樹脂(エポキシ樹脂硬化剤に該当、JER社製157S65)と、エポキシ樹脂固形分と特殊ノボラック型エポキシ樹脂との合計量に対して、0.05重量%の2-エチル-4(5)-メチルイミダゾール(硬化促進剤、JER社製EMI-24)とを添加し、均一に混合した後、溶媒の一部を揮発させアプリケーターで製膜して塗膜(厚さ:200μm)を得た。
製造例2で得られた含水アセチル化セルロース繊維(繊維含有量7重量%、残部は主に水)を実施例1と同様にしてエポキシ樹脂固形分に対してアセチル化セルロース繊維の含有量を25重量%となるように混合して、セルロース繊維分散液を調製した。
実施例7で得られた微細セルロース繊維分散液に、実施例2と同様にして硬化剤、硬化促進剤を添加し、硬化させ、セルロース繊維複合体を得た。複合体中の微細セルロース繊維の数平均繊維径は、上記と同じく、50nmであった。表1に各種測定結果を示す。
製造例2で得られた含水アセチル化セルロース繊維(繊維含有量7重量%、残部は主に水)を実施例1と同様にしてエポキシ樹脂固形分に対してアセチル化セルロース繊維の含有量を30重量%となるように混合して、セルロース繊維分散液を調製した。
実施例9で得られた微細セルロース繊維分散液を、実施例2と同様にして硬化させセルロース繊維複合体を得た。表1に各種測定結果を示す。
回転数を2000rpm、処理時間を20分間とした以外は実施例9と同様にして微細セルロース繊維が分散した微細セルロース繊維分散液を得た。得られた微細セルロース繊維の数平均繊維径は、70nmであった。表1に各種測定結果を示す。
実施例11で得られた微細セルロース繊維分散液を、実施例2と同様にして硬化させセルロース繊維複合体を得た。複合体中の微細セルロース繊維の数平均繊維径は、上記と同じく、70nmであった。表1に各種測定結果を示す。
製造例2で得られた含水アセチル化セルロース繊維(繊維含有量7重量%、残部は主に水)を濾過により脱水した。これを塩化メチレン中に分散して濾過する工程を3度行い、水を塩化メチレンに置換した。一方、酢酸セルロース(ダイセル化学工業社製)を塩化メチレンに溶解させ10重量%に調整した。
実施例13で得られた微細セルロース繊維分散液を、アプリケーターで製膜して塗膜(厚さ:200μm)を得た。この塗膜を60℃で1時間加熱し、セルロース繊維複合体を得た。複合体中の微細セルロース繊維の数平均繊維径は、上記と同じく、50nmであった。表1に各種測定結果を示す。
製造例1で得られたセルロース繊維を、セルロース繊維含有量0.5重量%、ポリビニルアルコール(日本合成化学工業社製AH-17、ケン化度97~98.5%、平均重合度1700)含有量1重量%となるように水で調整し、セルロース繊維分散液を得た。
実施例15で得られた微細セルロース繊維分散液を、オプツール処理したガラスシャーレに流延し、真空下で脱泡後、105℃のオーブンで2時間以上おくことで水を蒸発させた。ポリビニルアルコール中にセルロースが均一に分散した複合体を剥がすことができた。
セルロース繊維含有量0.5重量%、ポリビニルアルコール含有量0.5重量%とした以外は実施例15と同様にして微細セルロース繊維が分散した微細セルロース繊維分散液を得た。得られた微細セルロース繊維の数平均繊維径は、30nmであった。表2に各種測定結果を示す。
実施例16と同様にして、実施例17で得られた微細セルロース分散液からセルロース繊維複合体を得た。表2に各種測定結果を示す。
セルロース繊維含有量0.5重量%、ポリビニルアルコール含有量0.1重量%とした以外は実施例15と同様にして微細セルロース繊維が分散した微細セルロース繊維分散液を得た。表2に各種測定結果を示す。
実施例16と同様にして、実施例19で得られた微細セルロース分散液からセルロース繊維複合体を得た。表2に各種測定結果を示す。
セルロース繊維含有量0.5重量%、ポリビニルアルコール含有量0.05重量%とした以外は実施例15と同様にして微細セルロース繊維が分散した微細セルロース繊維分散液を得た。表2に各種測定結果を示す。
実施例16と同様にして、実施例21で得られた微細セルロース分散液からセルロース繊維複合体を得た。表2に各種測定結果を示す。
熱硬化性樹脂前駆体のエポキシ化合物であるビスフェノールA型エポキシ樹脂(JER社製jER827)100重量部を120℃で融解させ、硬化剤(m-キシリレンジアミン)18重量部と混合して、混合液を得た。
製造例5で得られた分散液とビスフェノールA型エポキシ樹脂(JER社製エピコート YL6810)とを混合して、スリーワンモーターで攪拌しながら減圧し、水をエポキシ樹脂に置換した。
比較例2で得られた組成物に、全固形分濃度が10重量%になるようにメチルエチルケトンを加え、組成物を30分攪拌した。しかしながら、攪拌をとめると固形分が沈降してしまい、分散液の液安定性に欠けていた。
樹脂および樹脂前駆体が存在しない系において、セルロース繊維の解繊を行った例を以下に詳述する。
製造例1で得られたセルロース繊維を、セルロース繊維含有量0.5重量%となるように水で調整し、セルロース繊維分散液を得た。得られた原料分散液を回転式高速ホモジナイザー(エム・テクニック社製クレアミックス2.2S)にて20000rpmで60分処理して、セルロース繊維の解繊を行い、微細セルロース繊維が分散した微細セルロース繊維分散液を得た。
本出願は、2010年4月1日出願の日本特許出願2010-085357、2010年10月29日出願の日本特許出願2010-243046に基づくものであり、その内容はここに参照として取り込まれる。
Claims (16)
- 微細セルロース繊維と、樹脂および樹脂前駆体の少なくとも一方と、有機溶媒とを含有する微細セルロース繊維分散液の製造方法であって、
セルロース繊維と、樹脂および樹脂前駆体の少なくとも一方と、有機溶媒とを含有する原料分散液中で、セルロース繊維を解繊して、微細セルロース繊維を得る解繊工程を含む、微細セルロース繊維分散液の製造方法。 - 前記セルロース繊維が、化学修飾されたセルロース繊維である、請求項1に記載の微細セルロース繊維分散液の製造方法。
- 前記樹脂および樹脂前駆体の少なくとも一方が、熱可塑性樹脂、熱硬化性樹脂および光硬化性樹脂並びにこれらの前駆体からなる群から選ばれる、請求項1または2に記載の微細セルロース繊維分散液の製造方法。
- 前記樹脂および樹脂前駆体の少なくとも一方が、エポキシ樹脂およびその前駆体の少なくとも一方である、請求項1~3のいずれか1項に記載の微細セルロース繊維分散液の製造方法。
- 請求項1~4のいずれか1項に記載の微細セルロース繊維分散液の製造方法より得られる、微細セルロース繊維分散液。
- 請求項5に記載の微細セルロース繊維分散液に、さらに樹脂および樹脂前駆体の少なくとも一方を添加して得られる、微細セルロース繊維分散液。
- 請求項5または6に記載の微細セルロース繊維分散液に、さらに有機溶媒を添加して得られる、微細セルロース繊維分散液。
- 請求項5~7のいずれか1項に記載の微細セルロース繊維分散液を用いて得られる、微細セルロース繊維と樹脂とを含有するセルロース繊維複合体。
- 請求項5~7のいずれか1項に記載の微細セルロース繊維分散液に加熱処理および露光処理の少なくとも一方を施し、前記有機溶媒を除去して、微細セルロース繊維と樹脂とを含有するセルロース繊維複合体を得る複合化工程を含む、セルロース繊維複合体の製造方法。
- 前記複合化工程前に、前記微細セルロース繊維分散液にさらに樹脂および樹脂前駆体の少なくとも一方を添加する添加工程を含む、請求項9に記載のセルロース繊維複合体の製造方法。
- 微細セルロース繊維と樹脂とを含有するセルロース繊維複合体の製造方法であって、
セルロース繊維と、樹脂および樹脂前駆体の少なくとも一方と、溶媒とを含有する原料分散液中で、セルロース繊維を解繊して、微細セルロース繊維を得る解繊工程、および、
該微細セルロース繊維を含有する分散液に、加熱処理および露光処理の少なくとも一方を施し、
前記溶媒を除去して、微細セルロース繊維と樹脂とを含有するセルロース繊維複合体を得る複合化工程を含む、セルロース繊維複合体の製造方法。 - 請求項9~11のいずれか1項に記載の製造方法により製造された、セルロース繊維複合体。
- 基板及び請求項8または12に記載のセルロース繊維複合体を含む積層体。
- さらに保護フィルムを含む、請求項13に記載の積層体。
- 請求項13または14に記載の積層体を含む配線基板。
- 微細セルロース繊維と、樹脂および樹脂前駆体の少なくとも一方と、有機溶媒とを含有する微細セルロース繊維分散液であって、下記(1)を満たす微細セルロース繊維分散液。
(1)分散液を室温で10日間静置した後、分散液中の沈降の有無を目視により観察する沈降性試験において、沈降が観察されない。
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Also Published As
Publication number | Publication date |
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EP2554588A1 (en) | 2013-02-06 |
TWI522368B (zh) | 2016-02-21 |
TW201139460A (en) | 2011-11-16 |
EP2554588A4 (en) | 2014-01-15 |
JPWO2011125801A1 (ja) | 2013-07-11 |
US20130025920A1 (en) | 2013-01-31 |
CN102834448A (zh) | 2012-12-19 |
EP2554588B1 (en) | 2017-07-12 |
CN102834448B (zh) | 2015-04-22 |
JP5712422B2 (ja) | 2015-05-07 |
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