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WO2019098332A1 - Composition de résine contenant de la cellulose fibreuse, feuille et article moulé - Google Patents

Composition de résine contenant de la cellulose fibreuse, feuille et article moulé Download PDF

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Publication number
WO2019098332A1
WO2019098332A1 PCT/JP2018/042509 JP2018042509W WO2019098332A1 WO 2019098332 A1 WO2019098332 A1 WO 2019098332A1 JP 2018042509 W JP2018042509 W JP 2018042509W WO 2019098332 A1 WO2019098332 A1 WO 2019098332A1
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Prior art keywords
fibrous cellulose
mass
group
sheet
fine fibrous
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English (en)
Japanese (ja)
Inventor
孟晨 趙
裕一 野口
雄右 轟
郁絵 杉山
友貴 渡部
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Oji Holdings Corp
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Oji Holdings Corp
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Priority to JP2019554315A priority Critical patent/JP7419819B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms

Definitions

  • the present invention relates to a fibrous cellulose-containing resin composition, a sheet and a molded article.
  • cellulose fibers are widely used in clothing, absorbent articles, paper products and the like.
  • cellulose fibers in addition to fibrous cellulose having a fiber diameter of 10 ⁇ m to 50 ⁇ m, fine fibrous cellulose having a fiber diameter of 1 ⁇ m or less is also known.
  • Fine fibrous cellulose is attracting attention as a new material, and its applications are diverse. For example, development of sheets and resin composites containing fine fibrous cellulose is in progress.
  • Patent Documents 1 to 4 disclose a carboxyl group-containing fine fibrous cellulose, and a complex comprising a fine fibrous cellulose to which an organic alkali is bound and a specific resin component.
  • Patent Document 5 a first step of obtaining a fine fibrous cellulose concentrate by adding a compound containing at least one selected from an alkali-soluble metal and a polyvalent metal ion to a fine fibrous cellulose slurry, and a fine fiber
  • a method for producing a fine fibrous cellulose redispersion slurry which comprises the second step of adding at least one selected from tetraalkylonium hydroxide and alkylamine to the fibrous cellulose concentrate.
  • the obtained fine fibrous cellulose is mixed with a resin component, and pKb of a conjugated base of tetraalkyl onium hydroxide is smaller than 1.0.
  • the inventors of the present invention have obtained a case where a surfactant such as an organic alkali is added to a resin composition containing fine fibrous cellulose and a resin component while advancing research on a resin complex containing fine fibrous cellulose. It was found that coloration may occur in the resin complex. Then, an object of this invention is to suppress coloring in the resin complex containing a fine fibrous cellulose.
  • the present inventors are as counter ion of the anionic functional group which fine fibrous cellulose has.
  • fills predetermined conditions it discovered that coloring of the resin complex obtained was suppressed.
  • the present invention has the following configuration.
  • a fiber width is 1000 nm or less, and contains fibrous cellulose having an anionic functional group, and a halogen-based resin,
  • the counter ion of the anionic functional group is an organic onium ion, Fibrous cellulose containing resin composition whose pKb of the conjugate base of organic onium ion is 1.0 or more.
  • FIG. 1 is a graph showing the relationship between the amount of dropped NaOH and the conductivity of a fiber material having a phosphate group.
  • FIG. 2 is a graph showing the relationship between the amount of dropped NaOH and the electrical conductivity for a fiber material having a carboxyl group.
  • the present invention relates to a fibrous cellulose-containing resin composition
  • a fibrous cellulose-containing resin composition comprising a fibrous cellulose having a fiber width of 1000 nm or less and having an anionic functional group, and a halogen-based resin.
  • the fibrous cellulose-containing resin composition contains an organic onium ion as a counter ion of an anionic functional group, and pKb of a conjugate base of the organic onium ion is 1.0 or more.
  • the fibrous cellulose containing resin composition of this invention can suppress coloring of the resin complex (sheet or molded object) formed from a fibrous cellulose containing resin composition.
  • the sheet formed from the fibrous cellulose-containing resin composition has high transparency and low yellowness.
  • coloring may be a problem in resin composites containing halogen-based resins, and the present invention has succeeded in suppressing coloring in resin composites containing halogen-based resins.
  • the total light transmittance of the sheet formed from the fibrous cellulose-containing resin composition is preferably 70% or more, more preferably 80% or more, and still more preferably 85% or more.
  • the total light transmittance of the sheet is a value measured according to JIS K 7361 using, for example, a haze meter (HM-150, manufactured by Murakami Color Research Laboratory).
  • the yellowness (YI) of the sheet formed from the fibrous cellulose-containing resin composition is preferably 40 or less, more preferably 20 or less, and still more preferably 10 or less.
  • the lower limit value of the yellowness (YI) is not particularly limited, but is preferably 0.1, for example.
  • the yellowness (YI) of the sheet is a value measured according to JIS K 7373 using, for example, Color Cute i (manufactured by Suga Test Instruments Co., Ltd.).
  • the form of the fibrous cellulose-containing resin composition of the present invention is not particularly limited, and examples thereof include liquids such as slurries, solids such as powders, pellets and gels.
  • the fibrous cellulose-containing resin composition of the present invention has a fiber width of 1000 nm or less and contains fibrous cellulose having an anionic functional group.
  • fibrous cellulose having a fiber width of 1000 nm or less is also referred to as fine fibrous cellulose.
  • the fiber width of fibrous cellulose can be measured, for example, by electron microscopic observation.
  • the average fiber width of fibrous cellulose is, for example, 1000 nm or less.
  • the average fiber width of the fibrous cellulose is, for example, preferably 2 nm or more and 1000 nm or less, more preferably 2 nm or more and 100 nm or less, still more preferably 2 nm or more and 50 nm or less, and 2 nm or more and 10 nm or less Particularly preferred.
  • the fibrous cellulose is, for example, monofibrillar cellulose.
  • the average fiber width of fibrous cellulose is measured, for example, using an electron microscope as follows. First, an aqueous suspension of fibrous cellulose having a concentration of 0.05% by mass or more and 0.1% by mass or less is prepared, and this suspension is cast on a hydrophilized carbon film-coated grid to obtain a sample for TEM observation I assume. If wide fibers are included, an SEM image of the surface cast on glass may be observed. Next, observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times or 50000 times depending on the width of the fiber to be observed. However, the sample, observation conditions and magnification are adjusted to satisfy the following conditions.
  • One straight line X is drawn at an arbitrary position in the observation image, and 20 or more fibers cross the straight line X.
  • the fiber length of the fibrous cellulose is not particularly limited, but is preferably 0.1 ⁇ m to 1000 ⁇ m, more preferably 0.1 ⁇ m to 800 ⁇ m, and still more preferably 0.1 ⁇ m to 600 ⁇ m. preferable.
  • the fiber length of fibrous cellulose can be calculated
  • the fibrous cellulose preferably has a type I crystal structure.
  • the proportion of crystalline form I in fine fibrous cellulose is, for example, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. Thereby, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion.
  • degree of crystallinity the X-ray diffraction profile is measured, and the pattern is determined by a conventional method (Seagal et al., Textile Research Journal, 29: 786, 1959).
  • the axial ratio (fiber length / fiber width) of the fibrous cellulose is not particularly limited, but is preferably 20 or more and 10000 or less, and more preferably 50 or more and 1000 or less.
  • the axial ratio is set to the above lower limit value or more, it is easy to form a sheet containing fine fibrous cellulose. In addition, sufficient viscosity can be easily obtained when the solvent dispersion is prepared.
  • the fibrous cellulose in the present embodiment has, for example, both a crystalline region and an amorphous region.
  • fine fibrous cellulose having both crystalline regions and noncrystalline regions and having a high axial ratio is realized by the method for producing fine fibrous cellulose described later.
  • Fibrous cellulose has an anionic functional group.
  • an anionic functional group for example, a phosphate group or a substituent derived from a phosphate group (also referred to simply as a phosphate group), a carboxyl group or a substituent derived from a carboxyl group (sometimes referred to as a carboxyl group) And at least one selected from a sulfone group or a substituent derived from a sulfone group (also referred to simply as a sulfone group), and at least one selected from a phosphoric acid group and a carboxyl group Is more preferred, and a phosphate group is particularly preferred.
  • a phosphate group for example, a phosphate group or a substituent derived from a phosphate group (also referred to simply as a phosphate group), a carboxyl group or a substituent derived from a carboxyl group (sometimes referred to as a carboxyl group)
  • the phosphate group is, for example, a divalent functional group corresponding to phosphoric acid from which a hydroxyl group has been removed. Specifically, it is a group represented by -PO 3 H 2 .
  • the substituent derived from the phosphate group includes a substituent such as a salt of a phosphate group and a phosphate ester group.
  • the substituent derived from a phosphoric acid group may be contained in fibrous cellulose as group (for example, pyrophosphoric acid group) which the phosphoric acid group condensed.
  • the phosphate group or the substituent derived from the phosphate group is, for example, a substituent represented by the following formula (1).
  • all of the ⁇ n and alpha 'is O - may be a.
  • R each represents a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched carbonization It is a hydrogen group, an unsaturated cyclic hydrocarbon group, an aromatic group, or a derivative thereof.
  • Examples of the saturated-linear hydrocarbon group include methyl group, ethyl group, n-propyl group, and n-butyl group, but are not particularly limited.
  • Examples of the saturated-branched hydrocarbon group include i-propyl group and t-butyl group, but are not particularly limited.
  • the saturated-cyclic hydrocarbon group may, for example, be a cyclopentyl group or a cyclohexyl group, but is not particularly limited.
  • Examples of the unsaturated-linear hydrocarbon group include, but are not particularly limited to, a vinyl group, an allyl group and the like.
  • Examples of unsaturated-branched hydrocarbon groups include i-propenyl group and 3-butenyl group, but are not particularly limited.
  • Examples of the unsaturated-cyclic hydrocarbon group include, but are not particularly limited to, cyclopentenyl group, cyclohexenyl group and the like.
  • an aromatic group although a phenyl group or a naphthyl group etc. are mentioned, it does not specifically limit.
  • a derivative group in R at least one of functional groups such as a carboxyl group, a hydroxyl group or an amino group is added or substituted to the main chain or side chain of the above various hydrocarbon groups.
  • a group is mentioned, it is not limited in particular.
  • the number of carbon atoms constituting the main chain of R is not particularly limited, but is preferably 20 or less, more preferably 10 or less.
  • ⁇ b + is a monovalent or more cation composed of an organic substance or an inorganic substance.
  • the monovalent or more monovalent cations of organic substances include aliphatic ammonium or aromatic ammonium, and the monovalent or more monovalent cations of inorganic substances include ions of alkali metals such as sodium, potassium or lithium, Examples thereof include cations of divalent metals such as calcium or magnesium, or hydrogen ions, but not particularly limited. These can also be applied combining 1 type or 2 or more types.
  • the monovalent or more monovalent cation composed of an organic substance or an inorganic substance is preferably an ion of sodium or potassium which is not easily yellowed when the fiber material containing ⁇ is heated and which is industrially easy to use, but is not particularly limited.
  • the amount of the anionic functional group introduced into the fibrous cellulose is, for example, preferably 0.10 mmol / g or more, more preferably 0.20 mmol / g or more, per 1 g (mass) of fibrous cellulose, and more preferably 0.50 mmol. It is more preferable that it is / g or more, and particularly preferable that it is 1.00 mmol / g or more.
  • the amount of the anionic functional group introduced into the fibrous cellulose is, for example, preferably 3.65 mmol / g or less, more preferably 3.50 mmol / g or less, per 1 g (mass) of fibrous cellulose. More preferably, it is not more than .00 mmol / g.
  • the introduction amount of the anionic functional group in the above range it is possible to easily make the fiber material finer, and it is possible to enhance the stability of the fibrous cellulose.
  • the introduction amount of the anionic functional group in the above range good characteristics can be exhibited in a sheet containing fibrous cellulose and the like.
  • the denominator in the unit mmol / g indicates the mass of fibrous cellulose when the counter ion of the anionic functional group is a hydrogen ion (H + ).
  • the introduction amount of the anionic functional group to the fibrous cellulose can be measured, for example, by the conductivity titration method.
  • the introduced amount is measured by determining the change in conductivity while adding an alkali such as an aqueous sodium hydroxide solution to the obtained fibrous cellulose-containing slurry.
  • FIG. 1 is a graph showing the relationship between the amount of dropped NaOH and the electrical conductivity of fibrous cellulose having a phosphate group.
  • the introduction amount of phosphate group to fibrous cellulose is measured, for example, as follows. First, a slurry containing fibrous cellulose is treated with a strongly acidic ion exchange resin. In addition, you may implement the disintegration processing similar to the below-mentioned disintegration processing process with respect to a measuring object before the processing by strongly acidic ion exchange resin as needed. Then, while the aqueous sodium hydroxide solution is added, the change in electrical conductivity is observed to obtain a titration curve as shown in FIG. As shown in FIG.
  • first region the electrical conductivity rapidly decreases
  • second region the conductivity starts to rise slightly
  • third region the increment of conductivity increases
  • the boundary point between the second area and the third area is defined as a point at which the second derivative value of the conductivity, that is, the change amount of the increment (inclination) of the conductivity is maximum.
  • the amount of alkali required in the first region is equal to the amount of strongly acidic groups in the slurry used for titration
  • the amount of alkali required in the second region is the amount of weakly acidic groups in the slurry used for titration Become equal.
  • the amount of strongly acidic groups is the same as the amount of phosphorus atoms regardless of the presence or absence of condensation.
  • the amount of introduction of a phosphate group (or amount of phosphate group) or the amount of introduction of a substituent (or amount of substituent) simply means the amount of strongly acidic group. Therefore, the value obtained by dividing the amount of alkali (mmol) required in the first region of the titration curve obtained above by the solid content (g) in the slurry to be titrated is the amount of phosphate group introduced (mmol / g).
  • the content of fibrous cellulose contained in the fibrous cellulose-containing resin composition is preferably 0.1% by mass or more based on the total mass of the solid content contained in the fibrous cellulose-containing resin composition
  • the content is more preferably 1% by mass or more, further preferably 2% by mass or more.
  • the content of fibrous cellulose is preferably 99% by mass or less, and more preferably 90% by mass or less, based on the total mass of the solid content contained in the fibrous cellulose-containing resin composition. And 80% by mass or less.
  • Fine fibrous cellulose is produced from a fiber material containing cellulose.
  • the fiber material containing cellulose is not particularly limited, but it is preferable to use pulp from the viewpoint of availability and low cost. Pulps include, for example, wood pulp, non-wood pulp, and deinked pulp. The wood pulp is not particularly limited.
  • Non-wood pulps include, but are not limited to, cotton-based pulps such as cotton linters and cotton lint, and non-wood-based pulps such as hemp, straw and bagasse.
  • the deinked pulp is not particularly limited, and examples thereof include deinked pulp using waste paper as a raw material.
  • the pulp of this embodiment may be used singly or in combination of two or more.
  • wood pulp and deinked pulp are preferable from the viewpoint of availability, for example.
  • the decomposition of cellulose in the pulp is small, and a fine fibrous cellulose of long fibers having a large axial ratio can be obtained.
  • chemical pulp is more preferable, and kraft pulp and sulfite pulp are more preferable.
  • a fiber material containing cellulose for example, cellulose contained in ascidians and bacterial cellulose produced by acetic acid bacteria can also be used. Moreover, it can replace with the fiber raw material containing a cellulose, and can also use the fiber which linear nitrogen-containing polysaccharide polymers, such as chitin and chitosan, form.
  • the phosphoric acid group introducing step is a reaction with a hydroxyl group possessed by a fiber raw material containing cellulose, so that at least one compound selected from compounds which can introduce a phosphoric acid group (hereinafter also referred to as “compound A”) Is a step of acting on the fiber material containing By this process, a phosphate group-introduced fiber is obtained.
  • the reaction of the fiber material containing cellulose and the compound A is performed in the presence of at least one selected from urea and its derivative (hereinafter, also referred to as “compound B”) May be On the other hand, the reaction of the fiber material containing cellulose and the compound A may be carried out in the absence of the compound B.
  • compound B urea and its derivative
  • a method of mixing compound A and compound B with respect to a dry, wet or slurry fiber material can be mentioned.
  • a dry or wet fiber raw material it is preferable to use a dry or wet fiber raw material, and in particular, it is preferable to use a dry fiber raw material, because the reaction uniformity is high.
  • the form of the fiber material is not particularly limited, but is preferably, for example, cotton-like or thin sheet-like.
  • the compound A and the compound B may be added to the fiber material in the form of powder or a solution dissolved in a solvent, or in the state of being melted by heating to the melting point or higher.
  • the reaction uniformity is high.
  • the compound A and the compound B may be added simultaneously to the fiber material, may be added separately, or may be added as a mixture.
  • the method of adding the compound A and the compound B is not particularly limited, but when the compound A and the compound B are in the form of a solution, the fiber raw material may be taken out after being immersed and absorbed in the solution, The solution may be dropped to the In addition, necessary amounts of Compound A and Compound B may be added to the fiber raw material, and after excess amounts of Compound A and Compound B are respectively added to the fiber raw material, excess Compound A and Compound B are added by pressing or filtration. It may be removed.
  • the compound A used in this embodiment includes, but is not particularly limited to, phosphoric acid or a salt thereof, dehydrated condensed phosphoric acid or a salt thereof, phosphoric anhydride (diphosphorus pentaoxide), and the like.
  • phosphoric acid those of various purity can be used, and for example, 100% phosphoric acid (orthophosphoric acid) or 85% phosphoric acid can be used.
  • the dehydrated condensed phosphoric acid is obtained by condensing two or more molecules of phosphoric acid by a dehydration reaction, and examples thereof include pyrophosphoric acid and polyphosphoric acid.
  • the phosphate and dehydrated condensed phosphate include lithium salt, sodium salt, potassium salt, ammonium salt and the like of phosphoric acid or dehydrated condensed phosphoric acid, and these can be made to have various degrees of neutralization.
  • phosphoric acid and phosphoric acid are preferred from the viewpoint of high efficiency of introduction of a phosphoric acid group, easy improvement of defibrillation efficiency in a fibrillation step described later, low cost, and easy industrial application.
  • Sodium salts, potassium salts of phosphoric acid or ammonium salts of phosphoric acid are preferred, and phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate or ammonium dihydrogen phosphate is more preferred.
  • the amount of compound A added to the fiber raw material is not particularly limited.
  • the amount of phosphorus atom added to the fiber raw material (absolute dry mass) is 0.5% by mass or more It is preferably 100% by mass or less, more preferably 1% by mass to 50% by mass, and still more preferably 2% by mass to 30% by mass.
  • the compound B used in this embodiment is at least one selected from urea and derivatives thereof as described above.
  • the compound B includes, for example, urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea, and 1-ethylurea.
  • the compound B is preferably used as an aqueous solution. Further, from the viewpoint of further improving the homogeneity of the reaction, it is preferable to use an aqueous solution in which both the compound A and the compound B are dissolved.
  • the addition amount of the compound B with respect to the fiber raw material is not particularly limited, but is preferably 1% by mass to 500% by mass, and more preferably 10% by mass to 400% by mass. More preferably, it is 100% by mass or more and 350% by mass or less.
  • an amide or an amine may be included in the reaction system.
  • the amides include formamide, dimethylformamide, acetamide, dimethylacetamide and the like.
  • amines include methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine and the like. Among these, triethylamine is known to work as a good reaction catalyst.
  • the phosphoric acid group introducing step it is preferable to heat treat the fiber material after adding or mixing the compound A and the like to the fiber material.
  • the heat treatment temperature it is preferable to select a temperature at which the phosphoric acid group can be efficiently introduced while suppressing the thermal decomposition or hydrolysis reaction of the fiber.
  • the heat treatment temperature is, for example, preferably 50 ° C. or more and 300 ° C. or less, more preferably 100 ° C. or more and 250 ° C. or less, and still more preferably 130 ° C. or more and 200 ° C. or less.
  • equipment having various heat media can be used.
  • stirring and drying apparatus for example, stirring and drying apparatus, rotary drying apparatus, disk drying apparatus, roll type heating apparatus, plate type heating apparatus, fluidized bed drying apparatus, air flow A drying device, a reduced pressure drying device, an infrared heating device, a far infrared heating device, or a microwave heating device can be used.
  • the heat treatment according to the present embodiment for example, after compound A is added to a thin sheet-like fiber material by a method such as impregnation, heating is performed while kneading or stirring the fiber material and compound A with a kneader or the like. Can be adopted. Thereby, it becomes possible to suppress the concentration nonuniformity of the compound A in a fiber raw material, and to introduce
  • the heating device used for the heat treatment is, for example, always the water held by the slurry, and the water produced by the dehydration condensation (phosphorylation) reaction of compound A with the hydroxyl group etc. contained in cellulose etc. It is preferable that it is an apparatus which can be discharged out of the apparatus system. As such a heating device, for example, an air-blowing oven may be mentioned.
  • a heating device for example, an air-blowing oven may be mentioned.
  • the heat treatment time is, for example, preferably 1 second to 300 minutes after substantial removal of water from the fiber raw material, more preferably 1 second to 1000 seconds, and further preferably 10 seconds to 800 seconds. It is further preferred that In the present embodiment, by setting the heating temperature and the heating time to an appropriate range, the introduction amount of the phosphate group can be set to a preferable range.
  • the phosphate group introduction step may be performed at least once, but may be repeated twice or more. By performing the phosphate group introduction step twice or more, many phosphate groups can be introduced into the fiber material. In this embodiment, the case where a phosphoric acid group introduction process is performed twice is mentioned as an example of a desirable mode.
  • the amount of phosphoric acid group introduced into the fiber raw material is, for example, preferably 0.10 mmol / g or more, more preferably 0.20 mmol / g or more, and more preferably 0.50 mmol / g per 1 g (mass) of fine fibrous cellulose. More preferably, it is g or more, and particularly preferably 1.00 mmol / g or more.
  • the amount of phosphoric acid group introduced into the fiber raw material is, for example, preferably 5.20 mmol / g or less, more preferably 3.65 mmol / g or less, per 1 g (mass) of fine fibrous cellulose. It is more preferable that it is 00 mmol / g or less.
  • the fiber raw material containing cellulose is oxidized by ozone oxidation, Fenton method, oxidation treatment such as TEMPO oxidation treatment, or a compound having a group derived from carboxylic acid or a derivative thereof, or a group derived from carboxylic acid It is carried out by treatment with an acid anhydride of the compound or a derivative thereof.
  • the compound having a carboxylic acid-derived group is not particularly limited, and examples thereof include dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid, itaconic acid, etc., citric acid, aconitic acid, etc. Tricarboxylic acid compounds are mentioned.
  • the derivative of the compound having a group derived from a carboxylic acid is not particularly limited, and examples thereof include an imidized acid anhydride of a compound having a carboxyl group, and a derivative of an acid anhydride of a compound having a carboxyl group.
  • the imide compound of the acid anhydride of the compound which has a carboxyl group is mentioned.
  • the imide compound of dicarboxylic acid compounds such as maleimide, a succinimide, phthalimide, is mentioned.
  • the acid anhydride of the compound having a group derived from carboxylic acid is not particularly limited, but, for example, dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, itaconic anhydride and the like An acid anhydride is mentioned.
  • the derivative of the acid anhydride of the compound having a group derived from a carboxylic acid is not particularly limited, but for example, a compound having a carboxyl group such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride and the like That in which at least a part of hydrogen atoms of the acid anhydride is substituted by a substituent such as an alkyl group or a phenyl group is mentioned.
  • TEMPO oxidation treatment is performed in the carboxyl group introduction step, for example, the treatment is preferably performed under the conditions of pH 6 or more and 8 or less. Such treatment is also referred to as neutral TEMPO oxidation treatment.
  • the TEMPO oxidation treatment may be carried out under the conditions of pH 10 or more and 11 or less. Such treatment is also referred to as alkaline TEMPO oxidation treatment.
  • the alkaline TEMPO oxidation treatment can be performed, for example, by adding, to a pulp as a fiber raw material, a nitroxy radical such as TEMPO as a catalyst, sodium bromide as a cocatalyst, and sodium hypochlorite as an oxidizing agent .
  • the amount of carboxyl group introduced into the fiber raw material varies depending on the type of substituent, but when introducing a carboxyl group by, for example, TEMPO oxidation, preferably 0.10 mmol / g or more per 1 g (mass) of fine fibrous cellulose It is more preferably 0.20 mmol / g or more, still more preferably 0.50 mmol / g or more, and particularly preferably 0.90 mmol / g or more. Further, it is preferably 2.50 mmol / g or less, more preferably 2.20 mmol / g or less, and still more preferably 2.00 mmol / g or less. In addition, when the substituent is a carboxymethyl group, it may be 5.8 mmol / g or less per 1 g (mass) of the fine fibrous cellulose.
  • the phosphate-containing fiber can be subjected to a washing step, if necessary.
  • the washing step is performed, for example, by washing the phosphate group-introduced fiber with water or an organic solvent.
  • the washing step may be performed after each step described later, and the number of times of washing performed in each washing step is not particularly limited.
  • an alkali treatment may be performed on the fiber raw material between the phosphoric acid group introduction step and the defibration treatment step described later.
  • the method of an alkali treatment For example, the method of immersing phosphate group introduction
  • the alkali compound contained in the alkali solution is not particularly limited, and may be an inorganic alkali compound or an organic alkali compound. In the present embodiment, it is preferable to use, for example, sodium hydroxide or potassium hydroxide as the alkali compound because of high versatility.
  • the solvent contained in the alkaline solution may be either water or an organic solvent. Among them, the solvent contained in the alkaline solution is preferably a polar solvent containing water or a polar organic solvent exemplified by alcohols, and more preferably an aqueous solvent containing at least water.
  • an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is preferable because of high versatility.
  • the temperature of the alkali solution in the alkali treatment step is not particularly limited, but is preferably 5 ° C. or more and 80 ° C. or less, and more preferably 10 ° C. or more and 60 ° C. or less.
  • the immersion time of the phosphate group-introduced fiber in the alkaline solution in the alkali treatment step is not particularly limited, but is preferably 5 minutes to 30 minutes, and more preferably 10 minutes to 20 minutes.
  • the use amount of the alkali solution in the alkali treatment is not particularly limited, but is preferably 100% by mass or more and 100000% by mass or less, for example, 1000% by mass or more and 10000% by mass or less based on the absolute dry mass of the phosphate group-introduced fiber. It is more preferable that
  • the phosphate group-introduced fiber may be washed with water or an organic solvent after the phosphate group introduction step and before the alkali treatment step. After the alkali treatment step and before the defibration treatment step, it is preferable to wash the phosphate group-introduced fiber subjected to the alkali treatment with water or an organic solvent from the viewpoint of improving the handleability.
  • the fiber raw material may be subjected to an acid treatment between the step of introducing a phosphate group and the defibration treatment step described later.
  • an acid treatment between the step of introducing a phosphate group and the defibration treatment step described later.
  • a phosphoric acid group introduction step, an acid treatment, an alkali treatment and a defibration treatment may be performed in this order.
  • the concentration of the acidic solution to be used is not particularly limited, but is preferably 10% by mass or less, and more preferably 5% by mass or less.
  • the pH of the acidic solution to be used is not particularly limited, but is preferably 0 or more and 4 or less, and more preferably 1 or more and 3 or less.
  • an acid contained in an acidic liquid an inorganic acid, sulfonic acid, carboxylic acid etc. can be used, for example.
  • Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, phosphoric acid, boric acid and the like.
  • Examples of the sulfonic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like.
  • Examples of carboxylic acids include formic acid, acetic acid, citric acid, gluconic acid, lactic acid, oxalic acid, tartaric acid and the like. Among these, it is particularly preferable to use hydrochloric acid or sulfuric acid.
  • the temperature of the acid solution in acid treatment is not particularly limited, for example, 5 ° C. or more and 100 ° C. or less is preferable, and 20 ° C. or more and 90 ° C. or less is more preferable.
  • the immersion time to the acid solution in acid treatment is not particularly limited, for example, 5 minutes or more and 120 minutes or less are preferable, and 10 minutes or more and 60 minutes or less are more preferable.
  • the use amount of the acid solution in the acid treatment is not particularly limited, but preferably 100% by mass or more and 100000% by mass or less, and more preferably 1000% by mass or more and 10000% by mass or less based on the absolute dry mass of the fiber material. Is more preferred.
  • a fine fibrous cellulose can be obtained by subjecting the phosphate group-introduced fiber to disaggregation treatment in a disintegration treatment step.
  • a defibration treatment device can be used.
  • the fibrillation treatment apparatus is not particularly limited, but for example, a high-speed fibrillation machine, a grinder (stone mill type crusher), a high pressure homogenizer or an ultrahigh pressure homogenizer, a high pressure collision type crusher, a ball mill, a bead mill, a bead mill, a disc type refiner, a conical refiner, biaxial A kneader, a vibration mill, a homomixer under high speed rotation, an ultrasonic dispersion machine, or a beater can be used.
  • a high-speed fibrillation machine a grinder (stone mill type crusher), a high pressure homogenizer or an ultrahigh pressure homogenizer, a high pressure collision type crusher, a ball mill, a bead mill, a bead mill, a disc type refiner, a conical refiner, biaxial A kneader, a vibration mill, a homomixer under high speed rotation, an ultrasonic dispersion machine, or a beater can be used.
  • a high-speed fibrillation machine it is more preferable to use a high-speed fibrillation machine, a high pressure homogenizer, or an ultrahigh pressure homogenizer which is less affected by the grinding media and less likely to contaminate.
  • the defibration treatment step for example, it is preferable to dilute the phosphate group-introduced fiber with a dispersion medium to form a slurry.
  • a dispersion medium one or more selected from water and an organic solvent such as a polar organic solvent can be used.
  • the polar organic solvent is not particularly limited but, for example, alcohols, polyhydric alcohols, ketones, ethers, esters, non-proton polar solvents and the like are preferable.
  • alcohols include methanol, ethanol, isopropanol, n-butanol, isobutyl alcohol and the like.
  • polyhydric alcohols include ethylene glycol, propylene glycol and glycerin.
  • ketones include acetone, methyl ethyl ketone (MEK) and the like.
  • ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, propylene glycol monomethyl ether and the like.
  • esters include ethyl acetate and butyl acetate.
  • the aprotic polar solvent include dimethylsulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP) and the like.
  • the solid content concentration of the fine fibrous cellulose at the time of the defibration treatment can be set appropriately.
  • solid content other than the phosphate group-introduced fiber such as urea having hydrogen bonding property may be contained.
  • an organic onium ion described later or a compound that forms an organic onium ion by neutralization is added to the fine fibrous cellulose-containing slurry obtained in the defibration treatment step.
  • organic onium ion it is preferable to add organic onium ion as a solution containing organic onium ion, and it is more preferable to add as aqueous solution containing organic onium ion.
  • An aqueous solution containing an organic onium ion usually contains an organic onium ion and a counter ion (anion).
  • organic onium ions may only form after being neutralized by an acid, such as, for example, dodecylamine. That is, the organic onium ion may be obtained by the reaction of a compound that forms the organic onium ion by neutralization and an acid.
  • examples of the acid used for neutralization include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as lactic acid, acetic acid, formic acid and oxalic acid.
  • a compound that forms an organic onium by neutralization may be directly added to the fine fibrous cellulose-containing slurry, and organic onium ionization may be performed using the phosphate group contained in the fine fibrous cellulose as a counter ion.
  • the amount of the organic onium ion added is preferably 2% by mass or more, more preferably 10% by mass or more, and still more preferably 50% by mass or more based on the total mass of the fine fibrous cellulose. It is particularly preferable that the content is 100% by mass or more. In addition, it is preferable that the addition amount of organic onium ion is 1000 mass% or less with respect to the total mass of fine fibrous cellulose.
  • the number of moles of the organic onium ion to be added is preferably 0.2 or more times the value obtained by multiplying the amount (number of moles) of the phosphate group contained in the fine fibrous cellulose by the valence, and 1.0 times It is more preferable that it is the above, and it is further more preferable that it is 2.0 times or more.
  • the number of moles of the organic onium ion to be added is preferably 10 times or less of the value obtained by multiplying the amount (number of moles) of the phosphate group contained in the fine fibrous cellulose by the valence.
  • the fine fibrous cellulose aggregate can be recovered by vacuum filtration of the fine fibrous cellulose-containing slurry in which the agglomerates are formed.
  • the obtained fine fibrous cellulose aggregate may be washed with ion exchange water. By repeatedly washing the fine fibrous cellulose aggregate with ion exchange water, excess organic onium ions and the like contained in the fine fibrous cellulose aggregate can be removed.
  • the ratio of N atom content to P atom content in the obtained fine fibrous cellulose aggregate is preferably larger than 1.2, and larger than 2.0. More preferable. Moreover, it is preferable that ratio (value of N / P) of content of N atom with respect to content of P atom in the obtained fine fibrous cellulose aggregate is 5.0 or less.
  • content of P atom in a fine fibrous cellulose aggregate and content of N atom can be suitably calculated by elemental analysis. As elemental analysis, for example, trace nitrogen analysis or molybdenum blue method can be performed after appropriate pretreatment. When the composition other than the fine fibrous cellulose aggregate contains P atoms and N atoms, elemental analysis may be performed after the composition and the fine fibrous cellulose aggregate are separated by an appropriate method.
  • the solid content concentration of the obtained fine fibrous cellulose aggregate is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more.
  • the pKb of the conjugate base of the organic onium ion is 1.0 or more, preferably 1.5 or more, and more preferably 2.0 or more.
  • the upper limit of the pKb of the conjugate base of the organic onium ion is not particularly limited, but is preferably 7.0, for example.
  • the organic onium ion and the conjugated base of the organic onium ion have the following relationship.
  • pKb of the conjugate base of the organic onium ion can be measured by the following method. First, a conjugate base of organic onium ion is separately prepared, water is added to the conjugate base of organic onium ion, and a conjugate base aqueous solution of 0.01 N organic onium ion is prepared. Thereafter, the pH of the aqueous solution at 25 ° C. is measured, and pKb of the conjugate base of the organic onium ion is calculated based on the following formulas (1) and (2). The smaller the pKb of the conjugate base, the stronger the basicity of the conjugate base aqueous solution.
  • [OH] 10- (14-pH)
  • pKb -log 10 ([OH] 2 ⁇ (0.01- [OH]))
  • [OH] represents the hydroxide ion concentration (mol / L) of a conjugate base aqueous solution of organic onium.
  • the poorly soluble organic onium conjugated base in water hardly ionizes in water and releases almost no hydroxide ion. Therefore, pKb is considered to be very large, and in the present specification, pKb is assumed to be greater than 3.0 for poorly soluble organic onium conjugated bases.
  • literature value can also be employ
  • the organic onium ion preferably satisfies at least one of the following conditions (a) and (b).
  • the hydrocarbon group having 5 or more carbon atoms is preferably an alkyl group having 5 or more carbon atoms or an alkylene group having 5 or more carbon atoms, and an alkyl group having 7 or more carbon atoms or an alkylene having 7 or more carbon atoms It is more preferably a group, and still more preferably an alkyl group having 10 or more carbon atoms or an alkylene group having 10 or more carbon atoms.
  • the organic onium ion is preferably an alkyl group having a carbon number of 5 or more, more preferably an organic onium ion having a carbon number of 5 or more and a total carbon number of 17 or more. preferable.
  • the organic onium ion containing a hydrocarbon group having 5 or more carbon atoms and the organic onium ion having 17 or more carbon atoms in total are preferably organic onium ions represented by the following general formula (A).
  • M is a nitrogen atom or a phosphorus atom
  • R 1 to R 4 each independently represent a hydrogen atom or an organic group.
  • at least one of R 1 to R 4 is an organic group having 5 or more carbon atoms, or the total carbon number of R 1 to R 4 is 17 or more.
  • M is preferably a nitrogen atom. That is, the organic onium ion is preferably an organic ammonium ion.
  • at least one of R 1 to R 4 is an alkyl group having 5 or more carbon atoms, and the total carbon number of R 1 to R 4 is 17 or more.
  • the alkyl group having 5 or more carbon atoms may have a substituent.
  • organic onium ions for example, lauryl trimethyl ammonium, cetyl trimethyl ammonium, stearyl trimethyl ammonium, octyl dimethyl ethyl ammonium, lauryl dimethyl ethyl ammonium, didecyl dimethyl ammonium, lauryl dimethyl benzyl ammonium, tributyl benzyl ammonium, methyl tri-n -Octylammonium, hexylammonium, n-octylammonium, dodecylammonium, tetradecylammonium, hexadecylammonium, stearylammonium, N, N-dimethyldodecylammonium, N, N-dimethyltetradecylammonium, N, N-dimethylhexadecyl Ammonium, N, N-Dimethyl-n-octadecyl ammonium
  • the central element of the organic onium ion is bonded to a total of four groups or hydrogen.
  • the rest are hydrogen atoms bonded to form an organic onium ion.
  • N N-didodecylmethylammonium
  • hydrogen is bonded to the remaining one to form an organic onium ion.
  • the molecular weight of the organic onium ion is preferably 2000 or less, more preferably 1800 or less.
  • the content of the organic onium ion in the fine fibrous cellulose is preferably equimolar to 2-fold molar amount with respect to the amount of phosphoric acid groups contained in the fine fibrous cellulose, but is not particularly limited.
  • the content of the organic onium ion can be measured by tracking the atoms typically contained in the organic onium ion. Specifically, when the organic onium ion is an ammonium ion, the amount of nitrogen atoms is measured, and when the organic onium ion is a phosphonium ion, the amount of phosphorus atoms is measured.
  • the fine fibrous cellulose contains a nitrogen atom or a phosphorus atom in addition to the organic onium ion
  • a method of extracting only the organic onium ion for example, an extraction operation with an acid, etc. is performed, and then the target amount of atoms It should be measured.
  • a halogen-based resin means, for example, a homopolymer, a copolymer or a polymer modified with a halogen-containing monomer.
  • the halogen-based resin is preferably at least one selected from fluorine-based resins, chlorine-based resins, and precursors of these resins, and vinyl chloride-based resins, polyvinylidene chloride, vinyl fluoride-based resins and polyvinyl fluorides. It is more preferable that it is at least 1 sort (s) selected from vinylidene fluoride, and it is still more preferable that it is at least 1 sort (s) selected from vinyl chloride resin and polyvinylidene fluoride.
  • the finely divided cellulose-containing resin composition of the present invention may contain, as the halogen-based resin, a precursor of a halogen-based resin.
  • the precursor of the halogen-based resin means a precursor used to produce the halogen-based resin.
  • the kind of precursor of halogen-type resin is not specifically limited, For example, the precursor of fluorine-type resin and chlorine-type resin can be mentioned.
  • fluorocarbon resin and chlorine resin precursor fluoroethylene, 1,1-difluoroethylene, 1,2-difluoroethylene, trifluoroethylene, tetrafluoroethylene, chloroethylene, 1,1-dichloroethylene, 1,2 Monomers such as dichloroethylene, trichloroethylene, tetrachloroethylene and the like, low molecular weight polymers obtained by polymerizing at least one of the monomers, and the like can be mentioned.
  • the fibrous cellulose-containing resin composition of the present invention may further contain a water-soluble polymer as a resin separately from the above-described resin species.
  • the water-soluble polymer include, for example, carboxyvinyl polymer, polyvinyl alcohol, alkyl methacrylate / acrylic acid copolymer, polyvinyl pyrrolidone, sodium polyacrylate, polyethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol , Water soluble polymers exemplified by polypropylene glycol, isoprene glycol, hexylene glycol, 1,3-butylene glycol, polyacrylamide, etc., xanthan gum, guar gum, tamarind gum, carrageenan, locust bean gum, quince seed, alginic acid, pullulan , Carrageenan, polysaccharide thickeners exemplified by pectin, carboxymethyl
  • the content of the resin contained in the fibrous cellulose-containing resin composition is preferably 1% by mass or more with respect to the total mass of the solid content contained in the fibrous cellulose-containing resin composition, and 10% by mass It is more preferable that it is the above, and it is further more preferable that it is 20 mass% or more.
  • the content of the resin is preferably 99.9% by mass or less and 99.0% by mass or less based on the total mass of the solid content contained in the fibrous cellulose-containing resin composition. More preferably, the content is 98.0% by mass or less.
  • the fibrous cellulose-containing resin composition of the present invention may further contain an organic solvent.
  • the fibrous cellulose-containing resin composition further containing an organic solvent may be referred to as a resin-containing fine fibrous cellulose dispersion.
  • the organic solvent is not particularly limited.
  • NMP N-methyl-2-pyrrolidone
  • DMSO dimethyl sulfoxide
  • MEK methyl ethyl ketone
  • toluene are preferably used.
  • ⁇ p organic solvent Hansen solubility parameter is preferably at 5 MPa 1/2 or more 20 MPa 1/2 or less, more preferably 10 MPa 1/2 or more 19 MPa 1/2 or less, it is more preferably 12MPa is 1/2 or more 18 MPa 1/2 or less.
  • .delta.h it is preferably, more preferably 5 MPa 1/2 or more 30 MPa 1/2 or less, 5 MPa 1/2 or 20 MPa 1/2 or less is 5 MPa 1/2 or more 40 MPa 1/2 or less Is more preferred.
  • .delta.p is in the range of 0 MPa 1/2 or 4 MPa 1/2 or less, it is also preferred to simultaneously satisfy the ⁇ h is in a range of 0 MPa 1/2 or 6 MPa 1/2 or less.
  • the content of the organic solvent is preferably 50% by mass or more and 60% by mass or more based on the total mass of the fibrous cellulose-containing resin composition Is more preferably 70% by mass or more. In addition, it is preferable that content of the organic solvent is 99 mass% or less with respect to the total mass of fibrous cellulose containing resin composition.
  • the solid content concentration of the fibrous cellulose-containing resin composition is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, and 40% by mass
  • the solid content concentration of the fibrous cellulose-containing resin composition is preferably 99% by mass or less, and more preferably 50% by mass or more.
  • the fibrous cellulose-containing resin composition may be, for example, a surfactant, an organic ion, a coupling agent, an inorganic stratiform compound, an inorganic compound, a leveling agent, an antiseptic, an antifoaming agent, in addition to the fine fibrous cellulose and the resin described above Even containing one or more selected from organic particles, lubricants, antistatic agents, ultraviolet protective agents, dyes, pigments, stabilizers, magnetic powders, orientation accelerators, plasticizers, dispersants, and crosslinking agents Good.
  • the content of the optional component contained in the fibrous cellulose-containing resin composition is preferably 40% by mass or less based on the total mass of the solid content contained in the fibrous cellulose-containing resin composition, and is 30 mass%. % Or less is more preferable, and 20% by mass or less is more preferable.
  • the water content of fibrous cellulose-containing resin composition of the present invention is preferably small.
  • the content of water in the fibrous cellulose-containing resin composition is preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the fibrous cellulose-containing resin composition.
  • content of the water in fibrous cellulose containing resin composition is 0 mass%.
  • the manufacturing process of a fibrous cellulose containing resin composition includes the process of mixing the re-dispersion liquid of the fine fibrous cellulose aggregate (concentrate) obtained by ⁇ aggregation process> mentioned above, and a resin solution.
  • an aqueous solution containing an organic onium ion having a conjugated base pKb of 1.0 or more is added to a fine fibrous cellulose dispersion having a phosphoric acid group, Forming a fibrous cellulose aggregate (concentrate), adding a solvent to the fine fibrous cellulose aggregate (concentrate), obtaining a redispersion solution of the fine fibrous cellulose, the redispersion solution and the resin solution
  • the re-dispersion liquid of the fine fibrous cellulose aggregate (concentrate) is obtained by mixing the fine fibrous cellulose aggregate (concentrate) with a solvent.
  • the type of solvent is not particularly limited, and examples thereof include water, an organic solvent, and a mixture of water and an organic solvent. Among them, the solvent is preferably an organic solvent, and examples of the organic solvent include the above-mentioned organic solvents.
  • the content of the fine fibrous cellulose in the redispersion solution is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more based on the total mass of the redispersion solution.
  • the content of the fine fibrous cellulose is preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total mass of the redispersion liquid.
  • the resin solution preferably contains a resin and a solvent.
  • the solvent is preferably the same solvent as the solvent contained in the redispersion solution of the fine fibrous cellulose aggregate (concentrate).
  • the resin concentration in the resin solution is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more based on the total mass of the resin solution.
  • the resin concentration is preferably 50% by mass or less, and more preferably 40% by mass or less, based on the total mass of the resin solution.
  • the present invention may relate to a sheet formed from the above-mentioned fibrous cellulose-containing resin composition.
  • a sheet can be obtained, for example, by performing the below-described sheet manufacturing process using the above-described fibrous cellulose-containing resin composition. That is, the sheet
  • the content of the fine fibrous cellulose in the sheet is, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 3% by mass or more based on the total mass of the sheet. Is more preferable, and 5% by mass or more is particularly preferable.
  • the content of the fine fibrous cellulose in the sheet is preferably 99% by mass or less, more preferably 90% by mass or less, and 80% by mass or more based on the total mass of the sheet. Is more preferred.
  • the sheet may also contain a solvent.
  • a solvent for example, those described above can be used.
  • the content of the solvent in the sheet is, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, based on the total mass of the sheet. preferable. This allows the sheet to be flexible.
  • the content of the solvent in the sheet is, for example, preferably 25% by mass or less, and more preferably 15% by mass or less, based on the total mass of the sheet. This makes it possible to obtain a flexible sheet.
  • the total light transmittance of the sheet is, for example, preferably 70% or more, more preferably 80% or more, and still more preferably 85% or more.
  • the upper limit of the total light transmittance of the sheet is not particularly limited, and may be, for example, 100%.
  • the total light transmittance of the sheet is a value measured according to JIS K 7361 using, for example, a haze meter (HM-150, manufactured by Murakami Color Research Laboratory).
  • the haze of the sheet is, for example, preferably 10% or less, more preferably 5% or less, and still more preferably 2% or less.
  • the lower limit value of the sheet haze is not particularly limited, and may be, for example, 0%.
  • the haze of the sheet is a value measured according to JIS K 7136, for example, using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory).
  • the yellowness (YI) of the sheet is preferably 40 or less, more preferably 20 or less, and still more preferably 10 or less.
  • the lower limit value of the yellowness (YI) is not particularly limited, but is preferably 0.1, for example.
  • the yellowness (YI) of the sheet is a value measured according to JIS K 7373 using, for example, Color Cute i (manufactured by Suga Test Instruments Co., Ltd.).
  • the thickness of the sheet is not particularly limited, but is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and still more preferably 20 ⁇ m or more.
  • the upper limit of the thickness of the sheet is not particularly limited, but can be, for example, 1000 ⁇ m.
  • the thickness of the sheet can be measured, for example, by a stylus thickness gauge (Miritron 1202D, manufactured by Marle).
  • the basis weight of the sheet is not particularly limited, but is preferably 10 g / m 2 or more, more preferably 20 g / m 2 or more, and still more preferably 30 g / m 2 or more.
  • the basis weight of the sheet is not particularly limited, but is preferably 200 g / m 2 or less, and more preferably 150 g / m 2 or less.
  • the basis weight of the sheet can be calculated, for example, in accordance with JIS P 8124.
  • the production process of the sheet includes a coating process of applying the above-mentioned fibrous cellulose-containing resin composition (slurry) onto a substrate, or a paper making process of producing the above-mentioned fibrous cellulose-containing resin composition (slurry) . Thereby, a sheet containing fine fibrous cellulose is obtained.
  • a fibrous cellulose-containing resin composition (slurry) is coated on a substrate, and the sheet is dried to peel the formed sheet from the substrate, whereby a sheet can be obtained.
  • a sheet can be continuously produced by using a coating device and a long base material.
  • the material of the substrate used in the coating step is not particularly limited, but a material having high wettability to the composition (slurry) may be capable of suppressing shrinkage of the sheet at the time of drying, etc. It is preferable to select a sheet which can be easily peeled off.
  • a resin film or plate or a metal film or plate is preferable, but is not particularly limited.
  • films or sheets of resins such as acrylic, polyethylene terephthalate, vinyl chloride, polystyrene, polyvinylidene chloride, etc., films, sheets of metals of aluminum, zinc, copper, iron, and those surfaces of which are oxidized, stainless steel A plate, a brass film or plate can be used.
  • a frame for blocking is fixed on the substrate and used to obtain a sheet of a predetermined thickness and basis weight.
  • the frame for blocking is not particularly limited, but it is preferable to select, for example, one that can easily peel off the end of the sheet that adheres after drying. From such a viewpoint, one obtained by molding a resin plate or a metal plate is more preferable.
  • resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polyvinylidene chloride plates, etc.
  • metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc. It is possible to use one which has been subjected to oxidation treatment, a stainless steel plate, a brass plate or the like.
  • the coating machine for applying the slurry to the substrate is not particularly limited, and, for example, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater or the like can be used.
  • a die coater, a curtain coater, and a spray coater are particularly preferable because the thickness of the sheet can be made more uniform.
  • the slurry temperature and the atmosphere temperature when applying the slurry to the substrate are not particularly limited, but are preferably 5 ° C. or more and 80 ° C. or less, more preferably 10 ° C. or more and 60 ° C. or less, and more preferably 15 ° C.
  • the temperature is more preferably 50 ° C. or less, and particularly preferably 20 ° C. or more and 40 ° C. or less.
  • the slurry is based so that the finished basis weight of the sheet is preferably 10 g / m 2 or more and 200 g / m 2 or less, more preferably 20 g / m 2 or more and 150 g / m 2 or less It is preferable to apply to a material.
  • strength is obtained.
  • the coating step includes the step of drying the slurry coated on the substrate as described above.
  • the step of drying the slurry is not particularly limited, but may be performed by, for example, a non-contact drying method, a method of drying while constraining the sheet, or a combination thereof.
  • the non-contact drying method is not particularly limited, but for example, a method of heating and drying with hot air, infrared rays, far infrared rays or near infrared rays (heat drying method) or a method of vacuum drying (vacuum drying method) is applied can do.
  • the heat drying method and the vacuum drying method may be combined, the heat drying method is usually applied.
  • Drying by infrared light, far infrared light or near infrared light is not particularly limited, but can be performed using, for example, an infrared light device, a far infrared light device or a near infrared light device.
  • the heating temperature in the heating and drying method is not particularly limited, but is preferably, for example, 20 ° C. or more and 150 ° C. or less, and more preferably 25 ° C. or more and 105 ° C. or less. When the heating temperature is set to the above lower limit value or more, the dispersion medium can be volatilized quickly. Moreover, if heating temperature is below the said upper limit, suppression of the cost which a heating requires, and suppression of the discoloration by the heat of fibrous cellulose are realizable.
  • the paper making process is carried out by making a slurry with a paper machine.
  • the paper machine used in the paper making process is not particularly limited, and examples thereof include continuous paper machines such as long mesh type, circular net type and inclined type, or a multilayer paper making machine combining these.
  • known paper making methods such as hand paper making may be employed.
  • the paper making process is performed by filtering and dewatering the slurry with a wire to obtain a wet paper sheet, and pressing and drying this sheet.
  • the filter cloth used when filtering and dewatering the slurry is not particularly limited, but it is more preferable that, for example, fibrous cellulose does not pass and the filtration rate does not become too slow.
  • Such a filter cloth is not particularly limited, but, for example, a sheet made of an organic polymer, a woven fabric, and a porous membrane are preferable.
  • the organic polymer is not particularly limited, but non-cellulose-based organic polymers such as polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and the like are preferable.
  • a porous film of polytetrafluoroethylene having a pore diameter of 0.1 ⁇ m to 20 ⁇ m, a woven fabric of polyethylene terephthalate or polyethylene having a pore diameter of 0.1 ⁇ m to 20 ⁇ m, and the like can be mentioned.
  • a fibrous cellulose-containing resin composition (slurry) is discharged onto the upper surface of an endless belt, and the dispersion medium is squeezed from the discharged slurry to form a web.
  • a manufacturing apparatus comprising a water squeezing section and a drying section that dries the web to produce a sheet.
  • An endless belt is disposed from the water squeezing section to the drying section, and the web generated in the water squeezing section is conveyed to the drying section while being placed on the endless belt.
  • the dewatering method used in the papermaking process is not particularly limited, and examples thereof include the dewatering method commonly used in the production of paper. Among these, a method of dewatering with a long mesh, circular net, inclined wire or the like and then dewatering with a roll press is preferable. Further, the drying method used in the paper making process is not particularly limited, and for example, the method used in the production of paper may be mentioned. Among these, a drying method using a cylinder drier, a Yankee drier, hot air drying, a near infrared heater, an infrared heater or the like is more preferable.
  • the present invention also relates to a molded product formed from the above-described fibrous cellulose-containing resin composition or the above-described sheet.
  • the molded product since the fine fibrous cellulose excellent in the compatibility with the resin is used, the molded product has an excellent flexural modulus and is also excellent in strength and dimensional stability.
  • the molded article of the present invention is also excellent in transparency.
  • the application of the fibrous cellulose-containing resin composition of the present invention is not particularly limited.
  • it can be used as a thickener, a reinforcing material, an additive, cosmetics, cement, paint, ink and the like.
  • it can also be used for the use as a reinforcing material by shape
  • it can form into a film using the re-dispersion slurry of fibrous cellulose containing resin composition, and can be used as various sheets.
  • the sheet of the present invention is suitable for use in light-transmissive substrates such as various display devices and various solar cells.
  • it is suitable for applications such as substrates of electronic devices, separators for electrochemical elements, members of household appliances, window materials of various vehicles and buildings, interior materials, exterior materials, packaging materials and the like.
  • the sheet itself is suitable for use as a reinforcing material.
  • the raw material pulp was subjected to a phosphorylation treatment as follows. First, a mixed aqueous solution of ammonium dihydrogen phosphate and urea is added to 100 parts by mass (dry mass) of the above-mentioned raw material pulp to make 45 parts by mass of ammonium dihydrogen phosphate, 120 parts by mass of urea, 150 parts by mass of water The solution was adjusted to obtain a chemical solution impregnated pulp. Next, the chemical-impregnated pulp obtained was heated for 200 seconds with a hot air drier at 165 ° C. to introduce a phosphoric acid group to the cellulose in the pulp to obtain a phosphorylated pulp.
  • the washing process is performed by repeating the operation of filtering and dewatering the pulp dispersion obtained by pouring 10 L of ion-exchanged water with respect to 100 g (absolute dry mass) of phosphorylated pulp so that the pulp can be uniformly dispersed. went.
  • the electric conductivity of the filtrate became 100 ⁇ S / cm or less, it was regarded as the washing end point.
  • neutralization treatment was performed on the washed phosphorylated pulp as follows. First, after diluting the phosphorylated pulp after washing with 10 L of ion exchanged water, a phosphated pulp slurry having a pH of 12 or more and 13 or less was obtained by gradually adding 1N aqueous sodium hydroxide solution while stirring. . Next, the phosphorylated pulp slurry was dewatered to obtain a phosphorylated pulp subjected to neutralization treatment. Next, the above-mentioned washing treatment was performed on the phosphorylated pulp after the neutralization treatment.
  • the infrared absorption spectrum of the phosphorylated pulp thus obtained was measured using FT-IR. As a result, absorption attributable to phosphate groups was observed at around 1230 cm -1 , confirming that phosphate groups were added to the pulp.
  • Ion-exchanged water was added to the obtained phosphorylated pulp to prepare a slurry having a solid content concentration of 2% by mass.
  • This slurry was treated six times at a pressure of 200 MPa with a wet atomization apparatus (Starburst, manufactured by Sugino Machine Co., Ltd.) to obtain a fine fibrous cellulose dispersion A containing fine fibrous cellulose.
  • this fine fibrous cellulose maintained cellulose type I crystals.
  • the fiber width of the fine fibrous cellulose was 3 to 5 nm as measured using a transmission electron microscope.
  • the amount of phosphoric acid groups (the amount of strongly acidic groups) measured by the measurement method described later was 2.00 mmol / g.
  • a fibrous cellulose concentrate A was obtained.
  • the counter ion of the phosphate group contained in the fine fibrous cellulose concentrate A was N, N-didodecylmethylammonium (DDMA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate A was 89% by mass.
  • the pKb of N, N-didodecylmethylamine, which is a conjugate base of DDMA + was 3 or more.
  • ⁇ Production Example 1-2> The same as Production Example 1-1 except that 100 g of an aqueous solution containing 1.83% by mass of polyoxyethylene dodecylamine (the number of oxyethylene residues is 2) was used instead of the aqueous solution of N, N-didodecylmethylamine. , And a fine fibrous cellulose concentrate B was obtained.
  • the counter ion of the phosphate group contained in the fine fibrous cellulose concentrate B was polyoxyethylene dodecyl ammonium (POEDA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate B was 93% by mass.
  • the pKb of polyoxyethylene dodecylamine which is a conjugate base of POEDA + was 3 or more.
  • Fine fibrous cellulose concentrate in the same manner as in Production Example 1-1 except that 100 g of a 2.06% by weight aqueous solution of N, N-didecylmethylamine was used instead of the aqueous solution of N, N-didodecylmethylamine. I got C.
  • the counter ion of the phosphate group contained in the fine fibrous cellulose concentrate C was N, N-didecylmethylammonium (DMA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate C was 90% by mass.
  • the pKb of N, N-didecylmethylamine, which is a conjugate base of DMA + was 3 or more.
  • a fine fibrous cellulose dispersion A was obtained in the same manner as in Production Example 1-1. 100 g of a fine fibrous cellulose dispersion A was separated, and 0.39 g of aluminum sulfate was added while stirring. Stirring was further continued for 5 hours, and aggregates of fine fibrous cellulose were observed. Next, the fine fibrous cellulose dispersion was filtered and then pressed with filter paper to obtain fine fibrous cellulose aggregates. The obtained fine fibrous cellulose aggregate was resuspended in ion exchange water so that the content of fine fibrous cellulose was 2.0% by mass. Then, it wash
  • the raw pulp was subjected to TEMPO oxidation as follows. First, the above raw material pulp equivalent to a dry mass of 100 parts by mass, 1.6 parts by mass of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl), 10 parts by mass of sodium bromide and 10000 parts by mass of water It was dispersed in the department. Then, a 13% by mass aqueous solution of sodium hypochlorite was added to 10 mmol per 1.0 g of pulp to start the reaction. During the reaction, 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10 or more and 10.5 or less, and when no change was observed in the pH, the reaction was regarded as complete.
  • the obtained TEMPO oxidized pulp was washed. Washing is performed by dewatering the pulp slurry after TEMPO oxidation to obtain a dewatered sheet, pouring 5000 parts by mass of ion exchanged water, stirring and uniformly dispersing, and then repeating the operation of filtering and dewatering. The The washing was finished when the conductivity of the filtrate became 100 ⁇ S / cm or less.
  • Ion-exchanged water was added to the obtained TEMPO oxidized pulp to prepare a slurry having a solid content concentration of 2% by mass.
  • This slurry was treated six times at a pressure of 200 MPa with a wet atomization apparatus (starburst, manufactured by Sugino Machine Co., Ltd.) to obtain a fine fibrous cellulose dispersion B containing fine fibrous cellulose.
  • this fine fibrous cellulose maintained cellulose type I crystals.
  • the fiber width of the fine fibrous cellulose was 3 to 5 nm as measured using a transmission electron microscope.
  • the amount of carboxyl groups measured by the measuring method mentioned later was 1.80 mmol / g.
  • the obtained fine fibrous cellulose dispersion B is used in place of the fine fibrous cellulose dispersion A, and 3.60 mL of 1 N hydrochloric acid is added to 100 g of a 1.32 mass% N, N-didodecylmethylamine aqueous solution.
  • a fine fibrous cellulose concentrate E was obtained in the same manner as in Production Example 1-1, except that it was neutralized and neutralized and then added to the fine fibrous cellulose dispersion B.
  • the counter ion of the carboxyl group contained in the fine fibrous cellulose concentrate E was N, N-didodecylmethylammonium (DDMA + ).
  • the solid content concentration of the obtained fine fibrous cellulose concentrate E was 89% by mass.
  • a fine fibrous cellulose dispersion B was obtained in the same manner as in Production Example 2-1. In the same manner as in Production Example 1-4, except that the obtained fine fibrous cellulose dispersion B is used instead of the fine fibrous cellulose dispersion A, and the addition amount of aluminum sulfate is 0.22 g, A fine fibrous cellulose concentrate F was obtained. The solid content concentration of the fine fibrous cellulose concentrate F was 20% by mass.
  • Example 1 [Re-dispersion of fine fibrous cellulose concentrate] N-methyl-2-pyrrolidone (NMP) was added to the fine fibrous cellulose concentrate A so that the content of fine fibrous cellulose was 2.0% by mass. Thereafter, ultrasonication was performed for 10 minutes using an ultrasonic treatment apparatus (UP400S, manufactured by Hielscher) to obtain a fine fibrous cellulose redispersion slurry.
  • NMP N-methyl-2-pyrrolidone
  • the polyvinylidene fluoride resin solution is added to the obtained fine fibrous cellulose redispersion slurry so that the polyvinylidene fluoride resin is 90 parts by mass with respect to 10 parts by mass of the fine fibrous cellulose, and the solid content concentration is 2.0 mass% A resin-containing fine fibrous cellulose dispersion is obtained.
  • the resin-containing fine fibrous cellulose dispersion was weighed so that the finished basis weight of the sheet would be 100 g / m 2 , poured onto a glass petri dish, and dried with a hot air dryer at 100 ° C. for 24 hours to obtain a sheet .
  • the total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • Example 2 A sheet was obtained in the same manner as in Example 1 except that polyvinyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of polyvinylidene fluoride.
  • the total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • Example 3 A sheet was obtained in the same manner as in Example 1 except that the fine fibrous cellulose concentrate B was used instead of the fine fibrous cellulose concentrate A.
  • the total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • Example 4 A sheet was obtained in the same manner as in Example 1 except that the fine fibrous cellulose concentrate C was used instead of the fine fibrous cellulose concentrate A.
  • the total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • Example 5 A sheet was obtained in the same manner as in Example 1 except that the fine fibrous cellulose concentrate E was used instead of the fine fibrous cellulose concentrate A.
  • the total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • Example 6 A sheet was obtained in the same manner as in Example 5 except that polyvinyl chloride was used instead of polyvinylidene fluoride. The total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • Comparative Example 1 3.96 g of a 55% aqueous solution of tetrabutylammonium hydroxide was added to 11.2 g of a fine fibrous cellulose concentrate D, and N-methyl-2-pyrrolidone was added so that the content of fine fibrous cellulose was 1.0% by mass. Added. Then, it was treated with an ultrasonic homogenizer (manufactured by hielscher, UP400S) for 10 minutes to obtain a fine fibrous cellulose redispersed slurry. As a result, from the state in which the phosphate group was crosslinked by the aluminum ion and aggregated, the counter ion was converted to tetrabutyl ammonium ion (TBA + ) and dispersed.
  • TSA + tetrabutyl ammonium ion
  • N-methyl-2-pyrrolidone was added and stirred so that the concentration of polyvinylidene fluoride (Sorbay 60L, made by Solvay) would be 2.0 mass%, to obtain a polyvinylidene fluoride resin solution.
  • the pKb of tetrabutylammonium hydroxide was 0.5.
  • the polyvinylidene fluoride resin solution is added to the obtained fine fibrous cellulose redispersion slurry so that the polyvinylidene fluoride resin is 90 parts by mass with respect to 10 parts by mass of the fine fibrous cellulose, and the solid content concentration is 1.0 mass%
  • a resin-containing fine fibrous cellulose dispersion was obtained by further adding N-methyl-2-pyrrolidone to give The resin-containing fine fibrous cellulose dispersion was weighed so that the finished basis weight of the sheet would be 100 g / m 2 , poured onto a glass petri dish, and dried with a hot air dryer at 100 ° C. for 24 hours to obtain a sheet .
  • the total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • Comparative Example 2 A sheet was obtained in the same manner as Comparative Example 1 except that polyvinyl chloride was used instead of polyvinylidene fluoride. The total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • Comparative Example 3 A sheet was obtained in the same manner as in Comparative Example 1 except that the fine fibrous cellulose concentrate F was used instead of the fine fibrous cellulose concentrate D. The total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • Comparative Example 4 A sheet was obtained in the same manner as in Comparative Example 3 except that polyvinyl chloride was used instead of polyvinylidene fluoride. The total light transmittance and the degree of yellowness (YI) of the obtained sheet were measured by the method described later.
  • the phosphoric acid group content of the fine fibrous cellulose is prepared by diluting the fine fibrous cellulose dispersion containing the fine fibrous cellulose to be treated with ion exchanged water so that the content is 0.2% by mass.
  • the cellulose-containing slurry was treated with an ion exchange resin and then measured by titration with an alkali.
  • the treatment with ion exchange resin is carried out by adding 1/10 strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) to the above fibrous cellulose-containing slurry and shaking it for 1 hour It was carried out by pouring on a mesh of 90 ⁇ m mesh to separate resin and slurry.
  • titration using an alkali is carried out by adding an aqueous solution of 0.1 N sodium hydroxide to the fibrous cellulose-containing slurry after treatment with an ion exchange resin, while adding 50 ⁇ L each once for every 30 seconds. This was done by measuring the change in the value of.
  • the amount of phosphate group (mmol / g) is obtained by dividing the amount of alkali (mmol) required in the region corresponding to the first region shown in FIG. 1 among the measurement results by the solid content (g) in the slurry to be titrated. Calculated.
  • the carboxyl group content of the fine fibrous cellulose is prepared by diluting the fine fibrous cellulose dispersion containing the fine fibrous cellulose to be treated with ion exchange water so that the content becomes 0.2% by mass. After the treatment with the ion exchange resin was performed on the contained slurry, it was measured by performing titration using an alkali. The treatment with ion exchange resin is carried out by adding 1/10 strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) to the above fibrous cellulose-containing slurry and shaking it for 1 hour It was carried out by pouring on a mesh of 90 ⁇ m mesh to separate resin and slurry.
  • 1/10 strongly acidic ion exchange resin Amberjet 1024; Organo Corporation, conditioned
  • titration using an alkali is carried out by adding an aqueous solution of 0.1 N sodium hydroxide solution once in 30 seconds to the fibrous cellulose-containing slurry treated with the ion exchange resin, while adding 50 ⁇ L of the aqueous solution to the slurry. It did by measuring the change of value.
  • the carboxyl group amount (mmol / g) is obtained by dividing the alkali amount (mmol) required in the region corresponding to the first region shown in FIG. 2 among the measurement results by the solid content (g) in the slurry to be titrated. Calculated.
  • [OH] 10- (14-pH)
  • pKb -log 10 ([OH] 2 ⁇ (0.01- [OH]))
  • [OH] represents the hydroxide ion concentration (mol / L) of a conjugate base aqueous solution of organic onium.
  • the poorly soluble organic onium conjugated base in water hardly ionizes in water and releases almost no hydroxide ion. Therefore, pKb is considered to be very large, and for poorly soluble organic onium conjugated bases, pKb was made greater than 3.0.
  • the coloring of the sheet is suppressed because the total light transmittance is high and the YI value is low.
  • the transparency of the sheet is inferior, the degree of yellowness is high, and the sheet is colored.

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Abstract

La présente invention a pour objet un composite de résine contenant de la cellulose microfibreuse dont la décoloration est évitée. À cet effet la présente invention porte sur une composition de résine contenant de la cellulose fibreuse qui contient une résine halogénée et une cellulose fibreuse ayant une largeur de fibre inférieure ou égale à 1000 nm et un groupe fonctionnel anionique. Le contre-ion pour le groupe fonctionnel anionique est un ion onium organique et le pKb de la base conjuguée de l'ion onium organique est d'au moins 1,0.
PCT/JP2018/042509 2017-11-17 2018-11-16 Composition de résine contenant de la cellulose fibreuse, feuille et article moulé Ceased WO2019098332A1 (fr)

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WO2020050349A1 (fr) * 2018-09-06 2020-03-12 王子ホールディングス株式会社 Matière solide et composition contenant de la cellulose fibreuse
JP2021017560A (ja) * 2019-07-23 2021-02-15 株式会社コバヤシ フィルム形成用組成物、及びプラスチゾル組成物
JP2021138871A (ja) * 2020-03-06 2021-09-16 王子ホールディングス株式会社 繊維状セルロース、繊維状セルロース含有物、繊維状セルロース含有液状組成物及び成形体

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JP2021017560A (ja) * 2019-07-23 2021-02-15 株式会社コバヤシ フィルム形成用組成物、及びプラスチゾル組成物
JP2021138871A (ja) * 2020-03-06 2021-09-16 王子ホールディングス株式会社 繊維状セルロース、繊維状セルロース含有物、繊維状セルロース含有液状組成物及び成形体
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