WO2017138589A1 - シート - Google Patents
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- WO2017138589A1 WO2017138589A1 PCT/JP2017/004663 JP2017004663W WO2017138589A1 WO 2017138589 A1 WO2017138589 A1 WO 2017138589A1 JP 2017004663 W JP2017004663 W JP 2017004663W WO 2017138589 A1 WO2017138589 A1 WO 2017138589A1
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- fibrous cellulose
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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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
- C08J5/18—Manufacture of films or sheets
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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
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/72—Coated paper characterised by the paper substrate
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
Definitions
- the present invention relates to a sheet. Specifically, the present invention relates to a sheet containing fine fibrous cellulose.
- fibrous cellulose having a fiber diameter of 10 ⁇ m or more and 50 ⁇ m or less, in particular, fibrous cellulose (pulp) derived from wood has been widely used mainly as a paper product so far.
- fine fibrous cellulose having a fiber diameter of 1 ⁇ m or less is also known.
- a sheet composed of such fine fibrous cellulose and a composite sheet containing a fine fibrous cellulose-containing sheet and a resin have been developed.
- seat and composite sheet containing a fine fibrous cellulose since the contact point of fibers increases remarkably, it is known that tensile strength etc. will improve large. It has also been studied to increase the strength of the sheet by adding various additives (for example, Patent Documents 1 to 3).
- Patent Documents 1 and 2 disclose a sheet containing fine fibrous cellulose and a polyacrylamide resin.
- an anionic polyacrylamide resin is mainly used as a polyacrylamide resin.
- Patent Document 2 discloses a sheet containing fine fibrous cellulose having a carboxyl group, a nonionic polyacrylamide resin, and the like.
- Patent Document 3 discloses a sheet containing fine fibrous cellulose having a carboxyl group and a cationic aqueous resin.
- polyamine polyamide epihalohydrin resin, polyamine epihalohydrin resin, and polyacrylamide resin are used as the cationic aqueous resin.
- the present inventors proceeded with a study for the purpose of providing a fine fibrous cellulose-containing sheet having improved water resistance in a highly transparent sheet. .
- the present inventors added a cationic resin to a sheet containing fibrous cellulose having a fiber width of 1000 nm or less, and further reduced the haze of the sheet to a predetermined value or less. It has been found that a sheet excellent in transparency and water resistance can be obtained by controlling.
- the present invention has the following configuration.
- W d weight after immersing the sheet in ion-exchanged water for 24 hours
- W d weight after conditioning the sheet for 24 hours at 23 ° C. and 50% relative humidity
- [4] The sheet according to any one of [1] to [3], wherein the total light transmittance is 85% or more.
- [5] The sheet according to any one of [1] to [4], wherein the tensile modulus after conditioning for 24 hours at 23 ° C. and a relative humidity of 50% is 5 GPa or more.
- [6] The sheet according to any one of [1] to [5], comprising 0.1 to 15 parts by mass of polyamine polyamide epihalohydrin with respect to 100 parts by mass of fibrous cellulose.
- [8] The sheet according to [7], wherein the polyacrylamide resin is an ionic polyacrylamide resin.
- seat of this invention is a sheet
- FIG. 1 is a graph showing the relationship between the amount of dropped NaOH and electrical conductivity for a fiber material having a phosphate group.
- FIG. 2 is a graph showing the relationship between the amount of dropped NaOH and electrical conductivity for a fiber material having a carboxyl group.
- the present invention relates to a sheet containing fibrous cellulose having a fiber width of 1000 nm or less and a cationic resin.
- the sheet of the present invention preferably relates to a sheet containing fibrous cellulose having a fiber width of 1000 nm or less and polyamine polyamide epihalohydrin.
- the haze of the sheet of the present invention is 6% or less. Since the sheet
- the haze of the sheet of the present invention may be 6% or less, preferably 5% or less, more preferably 3% or less, further preferably 2% or less, and 1.5% or less. It is particularly preferred that the haze may be 0%.
- seat can be improved more by making the haze of a sheet
- the haze of the sheet is a value measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K 7136.
- the sheet of the present invention has a low water absorption rate.
- the low water absorption of the sheet means excellent water resistance.
- the water absorption rate (% ) Is a value represented by (W ⁇ W d ) / W d ⁇ 100.
- the water absorption is preferably 5000% or less, more preferably 3000% or less, still more preferably 1000% or less, still more preferably 500% or less, and 300% or less. Is particularly preferred.
- the water absorption rate of the sheet may be 0%.
- the sheet of the present invention is also characterized by high total light transmittance.
- the total light transmittance of the sheet of the present invention is preferably 85% or more, more preferably 89% or more, and further preferably 91% or more.
- seat can be improved more by making the total light transmittance of a sheet
- the total light transmittance of the sheet is a value measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-150) in accordance with JIS K 7361.
- the yellowness of the sheet of the present invention is preferably 2.5 or less, more preferably 1.5 or less, further preferably 1.2 or less, and particularly preferably 1.0 or less. preferable.
- the yellowness is a value measured according to JIS K 7373, and by setting the yellowness to the above range, the transparency of the sheet can be further increased, and a high-quality sheet can be obtained.
- the tensile strength of the sheet of the present invention is preferably 50 MPa or more, more preferably 70 MPa or more, and further preferably 75 MPa or more. Although the upper limit of tensile strength is not specifically limited, For example, it can be 500 Mpa or less.
- the tensile modulus of the sheet of the present invention is preferably 5 GPa or more, more preferably 6 GPa or more, and further preferably 7 GPa or more. Although the upper limit of a tensile elasticity modulus is not specifically limited, For example, it can be 50 GPa or less.
- the elongation of the sheet of the present invention is preferably 1% or more, more preferably 2% or more, and further preferably 3% or more.
- the elongation of the sheet is preferably 20% or less, and more preferably 15% or less.
- the tensile strength, tensile elastic modulus, and elongation are as follows.
- Tensillon tensile tester manufactured by A & D Co., Ltd.
- JIS P8113 After placing the sheet under conditions of 23 ° C. and 50% relative humidity for 24 hours. It is the value measured using.
- the conditions of 23 ° C. and 50% relative humidity are humidity conditioning conditions (drying conditions), and the tensile strength, tensile elastic modulus, and elongation are the tensile strength after standing for 24 hours under humidity conditioning conditions.
- Strength, tensile modulus and elongation are as follows.
- Tensillon tensile tester manufactured by A & D Co., Ltd.
- the conditions of 23 ° C. and 50% relative humidity are humidity conditioning conditions (drying conditions)
- the tensile strength, tensile elastic modulus, and elongation are the ten
- the density of the sheet of the present invention is preferably 1.0 g / cm 3 or more, more preferably 1.2 g / cm 3 or more, and further preferably 1.5 g / cm 3 or more. Further, the density of the sheet is preferably 7.0 g / cm 3 or less.
- the density of the sheet is calculated according to JIS P 8118 from the basis weight and thickness of the sheet. The basis weight of the sheet can be calculated in accordance with JIS P 8124.
- seat is a density containing other components other than a fine fibrous cellulose.
- the thickness of the sheet of the present invention is not particularly limited, but is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further 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 or less.
- seat of this invention contains a cationic resin.
- the cationic resin is fixed to the cellulose fiber, and the water resistance of the sheet is considered to be improved by the hydrophobic portion of the cationic resin.
- the cationic resin examples include polyamine polyamide epihalohydrin, polyalkylene polyamines such as polyethylene polyamine and polypropylene polyamine or derivatives thereof; acrylic polymers having secondary or tertiary amino groups and quaternary ammonium groups, or their Copolymers of acrylamide; polyvinylamines and polyvinylamidines, dicyan-based cationic compounds typified by dicyandiamide-formalin copolymer; polyamine-based cationic compounds typified by dicyandiamide-polyethyleneamine copolymer; epichlorohydrin-dimethyl Amine copolymer, diallyldimethylammonium-SO 2 polycondensate, diallylamine salt-SO 2 polycondensate, diallyldimethylammonium chloride polymer, allylamine salt And a copolymer of dialkylaminoethyl (meth) acrylate, a quaternary salt copolymer, an acrylamide
- the cationic resin is preferably polyamine polyamide epihalohydrin, and particularly preferably polyamine polyamide epichlorohydrin.
- Polyamine polyamide epihalohydrin is a cationic thermosetting resin obtained by synthesizing polyamidopolyamine by heat condensation of an aliphatic dibasic carboxylic acid or its derivative and a polyalkylene polyamine, and then reacting the polyamidopolyamine with epihalohydrin. It is.
- the polyamine polyamide epihalohydrin is an aqueous resin, and it is preferable to add the polyamine polyamide epihalohydrin as an aqueous solution when producing a sheet.
- polyamine polyamide epihalohydrin examples include polyamine polyamide epichlorohydrin, polyamine polyamide epibromohydrin, polyamine polyamide epiiohydrin, and the like. Among these, polyamine polyamide epichlorohydrin is preferably used. The reason why polyamine polyamide epichlorohydrin is particularly preferable is considered as follows. Polyamine polyamide epichlorohydrin can be obtained by addition reaction of polyamine polyamide resin and epichlorohydrin. Since the polyamine polyamide resin has a cationic group and a hydrophobic group, it can be fixed on the cellulose fiber and exhibit water resistance. Epichlorohydrin also binds to cellulose and contributes to improving water resistance.
- Polyamine polyamide epichlorohydrin obtained by addition reaction of such polyamine polyamide resin and epichlorohydrin is an aqueous resin, and by adding polyamine polyamide epichlorohydrin as an aqueous solution to fine fiber cellulose, Water resistance can be exhibited without inhibiting the transparency of fine fiber cellulose.
- the content of the polyamine polyamide epihalohydrin is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the fine fibrous cellulose, and 2 parts by mass or more. More preferably, the amount is more preferably 5 parts by mass or more. Moreover, it is preferable that content of polyamine polyamide epihalohydrin is 15 mass parts or less, and it is more preferable that it is 12 mass parts or less.
- the haze value of the sheet can be set within a desired range.
- seat and transparency can be improved effectively.
- the content of polyamine polyamide epihalohydrin can be analyzed using, for example, NMR measurement, MS fragment analysis, UV analysis, or the like.
- a in the following structural formula represents a halogen atom.
- the sheet of the present invention contains fibrous cellulose having a fiber width of 1000 nm or less (hereinafter also referred to as fine fibrous cellulose).
- the content of fine fibrous cellulose contained in the sheet is preferably 60% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more with respect to the total mass of the sheet. More preferably, it is particularly preferably 90% by mass or more.
- pulp Although it does not specifically limit as a fibrous cellulose raw material for obtaining a fine fibrous cellulose, It is preferable to use a pulp from the point of being easy to acquire and cheap.
- the pulp include wood pulp, non-wood pulp, and deinked pulp.
- wood pulp include hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), sulfite pulp (SP), dissolved pulp (DP), soda pulp (AP), unbleached kraft pulp (UKP), oxygen bleached craft Chemical pulps such as pulp (OKP) are listed.
- semi-chemical pulps such as semi-chemical pulp (SCP) and chemi-ground wood pulp (CGP), mechanical pulps such as ground wood pulp (GP) and thermomechanical pulp (TMP, BCTMP), and the like are exemplified, but not particularly limited.
- Non-wood pulp includes cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw and bagasse, cellulose isolated from sea squirts and seaweed, chitin, chitosan, etc., but is not particularly limited.
- the deinking pulp includes deinking pulp made from waste paper, but is not particularly limited. The pulp of this embodiment may be used alone or in combination of two or more.
- wood pulp containing cellulose and deinked pulp are preferable in terms of availability.
- chemical pulp has a large cellulose ratio, so the yield of fine fibrous cellulose during fiber refinement (defibration) is high, and the degradation of cellulose in the pulp is small, and the fineness of long fibers with a large axial ratio is high. It is preferable at the point from which fibrous cellulose is obtained.
- kraft pulp and sulfite pulp are most preferably selected. Sheets containing long fibrous fine fibrous cellulose having a large axial ratio tend to provide high strength.
- the average fiber width of the fine fibrous cellulose is 1000 nm or less as observed with an electron microscope.
- the average fiber width is preferably 2 nm or more and 1000 nm or less, more preferably 2 nm or more and 100 nm or less, more preferably 2 nm or more and 50 nm or less, and further preferably 2 nm or more and 10 nm or less, but is not particularly limited.
- the average fiber width of the fine fibrous cellulose is less than 2 nm, the physical properties (strength, rigidity, dimensional stability) as the fine fibrous cellulose tend to be difficult to be expressed because the cellulose molecules are dissolved in water. .
- the fine fibrous cellulose is monofilamentous cellulose having a fiber width of 1000 nm or less, for example.
- Measurement of the fiber width of the fine fibrous cellulose by electron microscope observation is performed as follows. An aqueous suspension of fine fibrous cellulose having a concentration of 0.05% by mass or more and 0.1% by mass or less is prepared, and the suspension is cast on a carbon film-coated grid subjected to a hydrophilic treatment to prepare a sample for TEM observation. To do. When a wide fiber is included, an SEM image of the surface cast on glass may be observed. 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 constituent fibers. However, the sample, observation conditions, and magnification are adjusted to satisfy the following conditions.
- One straight line X is drawn at an arbitrary location in the observation image, and 20 or more fibers intersect the straight line X.
- a straight line Y perpendicular to the straight line is drawn in the same image, and 20 or more fibers intersect the straight line Y.
- the average fiber width (sometimes simply referred to as “fiber width”) of fine fibrous cellulose is an average value of the fiber widths read in this way.
- the fiber length of the fine fibrous cellulose is not particularly limited, but is preferably 0.1 ⁇ m or more and 1000 ⁇ m or less, more preferably 0.1 ⁇ m or more and 800 ⁇ m or less, and particularly preferably 0.1 ⁇ m or more and 600 ⁇ m or less.
- the fiber length of the fine fibrous cellulose can be determined by image analysis using TEM, SEM, or AFM.
- the fine fibrous cellulose preferably has an I-type crystal structure.
- the proportion of the I-type crystal structure in the fine fibrous cellulose is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more.
- the ratio of the crystal parts contained in the fine fibrous cellulose is not particularly limited in the present invention, but it is preferable to use cellulose having a crystallinity obtained by X-ray diffraction of 60% or more.
- the degree of crystallinity is preferably 65% or more, more preferably 70% or more. In this case, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion.
- the degree of crystallinity is obtained by measuring an X-ray diffraction profile and determining the crystallinity by an ordinary method (Seagal et al., Textile Research Journal, 29, 786, 1959).
- the fine fibrous cellulose is preferably a fiber having an ionic functional group.
- the ionic functional group is preferably an anionic functional group (hereinafter also referred to as an anionic group).
- the anionic group include a phosphate group or a substituent derived from a phosphate group (sometimes simply referred to as a phosphate group), a carboxyl group or a substituent derived from a carboxyl group (sometimes simply referred to as a carboxyl group), And at least one selected from a sulfone group or a substituent derived from a sulfone group (sometimes simply referred to as a sulfone group), and at least one selected from a phosphate group and a carboxyl group It is more preferable that it is a phosphate group.
- the fine fibrous cellulose is preferably one having a phosphate group or a substituent derived from a phosphate group.
- the phosphoric acid group is a divalent functional group equivalent to the phosphoric acid obtained by removing the hydroxyl group. Specifically, it is a group represented by —PO 3 H 2 .
- Substituents derived from phosphoric acid groups include substituents such as groups obtained by polycondensation of phosphoric acid groups, salts of phosphoric acid groups, and phosphoric acid ester groups. It may be a group.
- the phosphate group or the substituent derived from the phosphate group may be a substituent represented by the following formula (1).
- R 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 hydrocarbon group.
- ⁇ is a monovalent or higher cation composed of an organic substance or an inorganic substance.
- a fiber raw material containing cellulose is reacted with at least one selected from a compound having a phosphate group and a salt thereof (hereinafter referred to as “phosphorylation reagent” or “compound A”).
- phosphorylation reagent may be mixed in a powder or aqueous solution with a dry or wet fiber raw material.
- a phosphorylating reagent powder or an aqueous solution may be added to the fiber raw material slurry.
- the phosphoric acid group introduction step can be performed by reacting a fiber raw material containing cellulose with at least one selected from a phosphoric acid group-containing compound and a salt thereof (phosphorylation reagent or compound A). This reaction may be carried out in the presence of at least one selected from urea and derivatives thereof (hereinafter referred to as “compound B”).
- An example of a method for causing compound A to act on the fiber raw material in the presence of compound B is a method of mixing powder or an aqueous solution of compound A and compound B with a dry or wet fiber raw material.
- Another example is a method in which powders and aqueous solutions of Compound A and Compound B are added to the fiber raw material slurry.
- a method of adding an aqueous solution of Compound A and Compound B to a dry fiber material, or a powder or an aqueous solution of Compound A and Compound B to a wet fiber material is preferred.
- the compound A and the compound B may be added simultaneously, or may be added separately.
- the form of the fiber raw material is preferably cotton or thin sheet, but is not particularly limited.
- Compound A used in this embodiment is at least one selected from a compound having a phosphate group and a salt thereof.
- the compound having a phosphate group include, but are not limited to, phosphoric acid, lithium salt of phosphoric acid, sodium salt of phosphoric acid, potassium salt of phosphoric acid, ammonium salt of phosphoric acid, and the like.
- the lithium salt of phosphoric acid include lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate.
- Examples of the sodium salt of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, and sodium polyphosphate.
- Examples of the potassium salt of phosphoric acid include potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate.
- Examples of the ammonium salt of phosphoric acid include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate.
- phosphoric acid and phosphoric acid are introduced efficiently from the viewpoint that the introduction efficiency of phosphate groups is high, the fibrillation efficiency is easily improved in the fibrillation process described later, the cost is low, and the industrial application is easy.
- Sodium salt, potassium salt of phosphoric acid, and ammonium salt of phosphoric acid are preferable.
- Sodium dihydrogen phosphate or disodium hydrogen phosphate is more preferable.
- the compound A is preferably used as an aqueous solution because the uniformity of the reaction is increased and the efficiency of introducing a phosphate group is increased.
- the pH of the aqueous solution of Compound A is not particularly limited, but is preferably 7 or less because the efficiency of introduction of phosphate groups is increased, and more preferably pH 3 or more and pH 7 or less from the viewpoint of suppressing the hydrolysis of pulp fibers.
- the pH of the aqueous solution of Compound A may be adjusted by, for example, using a phosphoric acid group-containing compound that exhibits acidity and an alkalinity, and changing the amount ratio thereof. You may adjust pH of the aqueous solution of the compound A by adding an inorganic alkali or an organic alkali to the thing which shows acidity among the compounds which have a phosphoric acid group.
- the amount of compound A added to the fiber raw material is not particularly limited, but when the amount of compound A added is converted to phosphorus atomic weight, the amount of phosphorus atom added to the fiber raw material (absolute dry mass) is 0.5 mass% to 100 mass%. Or less, more preferably 1% by mass or more and 50% by mass or less, and most preferably 2% by mass or more and 30% by mass or less. If the amount of phosphorus atoms added to the fiber raw material is within the above range, the yield of fine fibrous cellulose can be further improved. When the addition amount of phosphorus atoms with respect to the fiber raw material exceeds 100% by mass, the effect of improving the yield reaches a peak and the cost of the compound A to be used increases. On the other hand, a yield can be raised by making the addition amount of the phosphorus atom with respect to a fiber raw material more than the said lower limit.
- Compound B used in this embodiment includes urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea, 1-ethylurea and the like.
- Compound B is preferably used as an aqueous solution like Compound A. Moreover, since the uniformity of reaction increases, it is preferable to use the aqueous solution in which both compound A and compound B are dissolved.
- the amount of Compound B added to the fiber raw material is preferably 1% by mass or more and 500% by mass or less, more preferably 10% by mass or more and 400% by mass or less, and 100% by mass or more and 350% by mass or less. More preferably, it is more preferably 150% by mass or more and 300% by mass or less.
- amides or amines may be included in the reaction system.
- 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 heat treatment temperature it is preferable to select a temperature at which a phosphate group can be efficiently introduced while suppressing thermal decomposition and hydrolysis reaction of the fiber. Specifically, it is preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower, and further preferably 130 ° C. or higher and 200 ° C. or lower. Moreover, you may use a vacuum dryer, an infrared heating apparatus, and a microwave heating apparatus for a heating.
- the concentration of the compound A in the fiber raw material may be uneven, and the introduction of phosphate groups on the fiber surface may not proceed uniformly.
- a very thin sheet-like fiber material is used, or the fiber material and Compound A are kneaded or stirred with a kneader or the like and dried by heating or reduced pressure. The method should be taken.
- the heating device used for the heat treatment is preferably a device that can always discharge the moisture retained by the slurry and the moisture generated by the addition reaction of the fibers such as phosphate groups to the hydroxyl group of the fiber, such as a blower oven. Etc. are preferred. If water in the system is always discharged, the hydrolysis reaction of the phosphate ester bond, which is the reverse reaction of the esterification, can be suppressed, and the acid hydrolysis of the sugar chain in the fiber can also be suppressed. A fine fiber having a high axial ratio can be obtained.
- the heat treatment time is also affected by the heating temperature, but it is preferably 1 second or more and 300 minutes or less, preferably 1 second or more and 1000 seconds or less after moisture is substantially removed from the fiber raw material slurry. Preferably, it is 10 seconds or more and 800 seconds or less.
- the amount of phosphate groups introduced can be within a preferred range by setting the heating temperature and the heating time to appropriate ranges.
- the amount of phosphate group introduced is preferably 0.1 mmol / g or more and 3.65 mmol / g or less, more preferably 0.14 mmol / g or more and 3.5 mmol / g or less per 1 g (mass) of fine fibrous cellulose.
- 0.2 mmol / g or more and 3.2 mmol / g or less is more preferable, 0.4 mmol / g or more and 3.0 mmol / g or less is particularly preferable, and most preferably 0.6 mmol / g or more and 2.5 mmol / g or less.
- the fiber raw material can be easily refined, and the stability of the fine fibrous cellulose can be enhanced.
- the introduction amount of phosphoric acid groups within the above-mentioned range it is possible to leave hydrogen bonds between fine fibrous celluloses while being easily miniaturized, and good strength can be expected.
- the amount of phosphate group introduced into the fiber material can be measured by a conductivity titration method. Specifically, by performing the defibration process step, after treating the resulting fine fibrous cellulose-containing slurry with an ion exchange resin, by determining the change in electrical conductivity while adding an aqueous sodium hydroxide solution, The amount introduced can be measured.
- first region the electrical conductivity rapidly decreases
- second region the conductivity starts to increase slightly
- third region the conductivity increment increases (hereinafter referred to as “third region”). That is, three areas appear.
- the boundary point between the second region and the third region is defined as a point at which the amount of change in conductivity twice, that is, the increase (inclination) in conductivity is maximized.
- 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. Will be equal.
- the amount of alkali required in the second region is reduced compared to the amount of alkali required in the first region.
- the amount of strongly acidic groups coincides with the amount of phosphorus atoms regardless of the presence or absence of condensation, so that the amount of phosphate groups introduced (or the amount of phosphate groups) or the amount of substituent introduced (or the amount of substituents) is simply When said, it represents the amount of strongly acidic group. That is, the alkali amount (mmol) required in the first region of the curve shown in FIG. 1 is divided by the solid content (g) in the titration target slurry to obtain the substituent introduction amount (mmol / g).
- the phosphate group introduction step may be performed at least once, but may be repeated a plurality of times. In this case, more phosphoric acid groups are introduced, which is preferable.
- the fine fibrous cellulose when it has a carboxyl group, it is treated with an oxidation treatment such as a TEMPO oxidation treatment or a compound having a carboxylic acid-derived group, a derivative thereof, or an acid anhydride or a derivative thereof. By doing so, a carboxyl group can be introduced.
- an oxidation treatment such as a TEMPO oxidation treatment or a compound having a carboxylic acid-derived group, a derivative thereof, or an acid anhydride or a derivative thereof.
- the compound having a carboxyl 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 and itaconic acid, and tricarboxylic acid compounds such as citric acid and aconitic acid. .
- the acid anhydride of the compound having a carboxyl group is not particularly limited, but examples thereof include acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride. It is done.
- the derivative of the compound having a carboxyl group is not particularly limited, and examples thereof include an acid anhydride imidized compound having a carboxyl group and an acid anhydride derivative of a compound having a carboxyl group. Although it does not specifically limit as an acid anhydride imidation thing of a compound which has a carboxyl group, Imidation thing of dicarboxylic acid compounds, such as maleimide, succinic acid imide, and phthalic acid imide, is mentioned.
- the acid anhydride derivative of the compound having a carboxyl group is not particularly limited.
- at least some of the hydrogen atoms of the acid anhydride of the compound having a carboxyl group such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride, etc. are substituted (for example, alkyl group, phenyl group, etc. ) Are substituted.
- the amount of carboxyl groups introduced is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and 0.3 mmol / g or more per 1 g (mass) of fine fibrous cellulose. Is more preferably 0.5 mmol / g or more.
- the amount of carboxyl group introduced is preferably 3.5 mmol / g or less, more preferably 3.0 mmol / g or less, further preferably 2.5 mmol / g or less, and 2.0 mmol / g. It is particularly preferred that it is g or less.
- a cationic substituent may be introduced into the fine fibrous cellulose as an ionic functional group.
- a cationic substituent can be introduced into the fiber raw material by adding a cationizing agent and an alkali compound to the fiber raw material and reacting them.
- the cationizing agent one having a quaternary ammonium group and a group that reacts with a hydroxyl group of cellulose can be used.
- the group that reacts with the hydroxyl group of cellulose include an epoxy group, a functional group having a halohydrin structure, a vinyl group, and a halogen group.
- the cationizing agent include glycidyltrialkylammonium halides such as glycidyltrimethylammonium chloride and 3-chloro-2-hydroxypropyltrimethylammonium chloride or halohydrin type compounds thereof.
- the alkali compound contributes to the promotion of the cationization reaction.
- Alkali compounds include alkali metal hydroxides or alkaline earth metal hydroxides, alkali metal carbonates or alkaline earth metal carbonates, alkali metal phosphates or alkaline earth metal phosphates, etc.
- Organic alkali compounds such as ammonia, aliphatic amines, aromatic amines, aliphatic ammoniums, aromatic ammoniums, heterocyclic compounds and their hydroxides, carbonates, phosphates, etc. It may be.
- the introduction amount of the cationic substituent can be measured using, for example, elemental analysis.
- alkali treatment When manufacturing a fine fibrous cellulose, you may perform an alkali treatment between an ionic functional group introduction
- the alkali compound contained in the alkali solution is not particularly limited, but may be an inorganic alkali compound or an organic alkali compound.
- the solvent in the alkaline solution may be either water or an organic solvent.
- the solvent is preferably a polar solvent (polar organic solvent such as water or alcohol), and more preferably an aqueous solvent containing at least water.
- a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is particularly preferred because of its high versatility.
- the temperature of the alkali solution in an alkali treatment process is not specifically limited, 5 to 80 degreeC is preferable and 10 to 60 degreeC is more preferable.
- the immersion time in the alkaline solution in the alkali treatment step is not particularly limited, but is preferably 5 minutes or longer and 30 minutes or shorter, and more preferably 10 minutes or longer and 20 minutes or shorter.
- the usage-amount of the alkaline solution in an alkali treatment is not specifically limited, It is preferable that it is 100 mass% or more and 100,000 mass% or less with respect to the absolute dry mass of a phosphate group introduction
- the phosphate group-introduced fiber may be washed with water or an organic solvent before the alkali treatment step.
- the alkali treatment in order to improve the handleability, it is preferable to wash the alkali-treated phosphate group-introduced fiber with water or an organic solvent before the defibrating treatment step.
- the phosphate group-introduced fiber is defibrated in the defibrating process.
- the fiber is usually defibrated using a defibrating apparatus to obtain a fine fibrous cellulose-containing slurry, but the processing apparatus and the processing method are not particularly limited.
- a defibrating apparatus a high-speed defibrator, a grinder (stone mill type pulverizer), a high-pressure homogenizer, an ultra-high pressure homogenizer, a high-pressure collision type pulverizer, a ball mill, a bead mill, or the like can be used.
- a device for wet grinding such as a disk type refiner, a conical refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, or a beater should be used. You can also.
- the defibrating apparatus is not limited to the above.
- Preferable defibrating treatment methods include a high-speed defibrator, a high-pressure homogenizer, and an ultra-high pressure homogenizer that are less affected by the grinding media and less concerned about contamination.
- a polar organic solvent in addition to water, a polar organic solvent can be used.
- polar organic solvents include alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and the like, but are not particularly limited.
- alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butyl alcohol.
- ketones include acetone and methyl ethyl ketone (MEK).
- ethers include diethyl ether and tetrahydrofuran (THF).
- THF tetrahydrofuran
- the dispersion medium may be one type or two or more types. Further, the dispersion medium may contain a solid content other than the fiber raw material, such as urea having hydrogen bonding property.
- the fine fibrous cellulose-containing slurry of the present invention may be obtained by once concentrating and / or drying the fine fibrous cellulose-containing slurry obtained by the defibrating treatment and then performing the defibrating treatment again.
- the concentration and drying methods are not particularly limited, and examples thereof include a method of adding a concentrating agent to a slurry containing fine fibrous cellulose, a generally used dehydrator, a press, and a method using a dryer.
- a well-known method for example, the method described in WO2014 / 024876, WO2012 / 107642, and WO2013 / 121086 can be used.
- it can concentrate and dry by making a fine fibrous cellulose containing slurry into a sheet
- a high-speed defibrator As a device used when the fine fibrous cellulose slurry is concentrated and / or dried and then defibrated (pulverized) again, a high-speed defibrator, a grinder (stone mill pulverizer), a high-pressure homogenizer, an ultra-high pressure homogenizer, Use wet grinding equipment such as high-pressure collision type pulverizer, ball mill, bead mill, disk type refiner, conical refiner, twin-screw kneader, vibration mill, homomixer under high-speed rotation, ultrasonic disperser, beater, etc. However, it is not particularly limited.
- the fine fibrous cellulose-containing product having a phosphoric acid group obtained by the above-described method is a fine fibrous cellulose-containing slurry, which may be diluted with water so as to have a desired concentration.
- the sheet of the present invention preferably further contains a polyacrylamide resin.
- polyacrylamide resins include acrylamide homopolymers (polyacrylamide) and copolymers containing acrylamide as a main component.
- the polyacrylamide resin is preferably a copolymer having acrylamide as a main component, and among the units constituting the copolymer, 50% by mass or more of units derived from acrylamide are included. Is preferred.
- monomers copolymerizable with acrylamide include nonionic monomers, anionic monomers, and cationic monomers.
- nonionic monomers examples include diacetone acrylamide, alkyl acrylate, hydroxy acrylate, vinyl acetate, styrene, ⁇ -methyl styrene, and the like.
- anionic monomers include monocarboxylic acid monomers (eg, acrylic acid, methacrylic acid, crotonic acid, etc.), dicarboxylic acid monomers (eg, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc.), vinyl groups
- organic acid monomers such as sulfonic acid monomers having a carboxylic acid (eg, vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropanoic acid).
- salts of these organic acid monomers such as sodium salt and potassium salt can also be used.
- Examples of the cationic monomer include a monomer having a tertiary amino group.
- (meth) acrylic acid ester derivatives having a tertiary amino group for example, dialkylaminoethyl (meth) acrylate (for example, dimethylaminoethyl acrylate), dialkylaminopropyl (meth) acrylate, etc.
- (meth) acrylamide derivatives having a tertiary amino group for example, dialkylaminoethyl (meth) acrylamide, dialkylaminopropyl (meth) acrylamide, (meth) acrylamide-3-methylbutyldimethylamine
- the salt of the monomer which has the said tertiary amino group can also be used.
- the salt include inorganic salts such as hydrochloride and sulfate, and organic salts such as formate and acetate.
- organic salts such as formate and acetate.
- a quaternary salt in which a tertiary amino group is quaternized with methyl chloride (methyl chloride), methyl bromide, benzyl chloride, benzyl bromide, dimethyl sulfate, epichlorohydrin and the like can be mentioned.
- a nonionic monomer is used as a monomer to be copolymerized with acrylamide, a nonionic polyacrylamide resin is obtained, and if an anionic monomer is used, an anionic polyacrylamide resin is obtained. Furthermore, when an anionic monomer and a cationic monomer are used in combination as monomers to be copolymerized with acrylamide, an amphoteric polyacrylamide resin can be obtained.
- the polyacrylamide resin is preferably an ionic polyacrylamide resin, and more preferably an anionic polyacrylamide resin.
- the content of the polyacrylamide-based resin is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of fine fibrous cellulose, and 1 part by mass or more. More preferably, it is more preferably 5 parts by mass or more. Moreover, it is preferable that content of polyacrylamide type resin is 50 mass parts or less, and it is more preferable that it is 30 mass parts or less.
- the content of the polyacrylamide resin can be analyzed using, for example, NMR measurement, MS fragment analysis, UV analysis, or the like.
- seat of this invention can further contain other resin except the resin mentioned above, for example.
- thermoplastic resin a thermosetting resin (a cured product obtained by polymerization and curing of a thermosetting resin precursor), or a photocurable resin (a photocurable resin precursor is radiation ( And a cured product obtained by polymerization and curing by irradiation with ultraviolet rays or electron beams).
- thermosetting resin a cured product obtained by polymerization and curing of a thermosetting resin precursor
- photocurable resin precursor is radiation ( And a cured product obtained by polymerization and curing by irradiation with ultraviolet rays or electron beams).
- the thermoplastic resin is not particularly limited.
- olefin resins for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene- ⁇ olefin copolymer, propylene- ⁇ Olefin copolymers, etc.
- polyvinyl chloride for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene- ⁇ olefin copolymer, propylene- ⁇ Olefin copolymers, etc.
- polyvinyl chloride for example, polyethylene-propylene copolymer, ethylene- ⁇ olefin copolymer, propylene- ⁇ Olefin copolymers, etc.
- polyvinyl chloride for example, polyethylene-propylene copolymer, ethylene- ⁇ olefin copolymer, propylene- ⁇ Olefin copolymers, etc.
- polyvinyl chloride for example, polyethylene-propylene copoly
- thermosetting resin is not particularly limited, but epoxy resin, acrylic resin, oxetane resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, silicon resin, polyurethane resin, silsesquioxane resin Or diallyl phthalate resin.
- the photocurable resin is not particularly limited, and examples thereof include the epoxy resin, acrylic resin, silsesquioxane resin, or oxetane resin exemplified as the above-mentioned thermosetting resin.
- thermoplastic resins thermosetting resins
- photocurable resins include those described in JP-A-2009-299043.
- polyamine polyamide epihalohydrin, polyacrylamide resin and other resins can be added as an emulsion.
- these resins are added as an emulsion, in the obtained sheet, for example, the emulsion is melted by heating, but part of the granular resin can remain.
- the said other resin even if it adds the said other resin as an emulsion, it is mentioned as a preferable aspect.
- the particle size of the resin emulsion to be added is preferably 10 nm or more and 10 ⁇ m or less, more preferably 10 nm or more and 1 ⁇ m or less, and further preferably 20 nm or more and 200 nm or less.
- the particle diameter of the resin emulsion is preferably 10 nm or more and 10 ⁇ m or less, more preferably 10 nm or more and 1 ⁇ m or less, and further preferably 20 nm or more and 200 nm or less.
- the sheet may contain an optional component other than the components described above.
- optional components include antifoaming agents, lubricants, ultraviolet absorbers, dyes, pigments, stabilizers, and surfactants.
- a hydrophilic polymer, an organic ion, etc. are mentioned, for example.
- the hydrophilic polymer is preferably a hydrophilic oxygen-containing organic compound (however, excluding the cellulose fiber).
- the oxygen-containing organic compound is preferably non-fibrous, and such non-fibrous oxygen-containing organic compound does not contain fine fibrous cellulose or thermoplastic resin fibers.
- the oxygen-containing organic compound is preferably a hydrophilic organic compound.
- the hydrophilic oxygen-containing organic compound can improve the strength, density and chemical resistance of the fiber layer.
- the hydrophilic oxygen-containing organic compound preferably has, for example, an SP value of 9.0 or more.
- the hydrophilic oxygen-containing organic compound is preferably one in which 1 g or more of the oxygen-containing organic compound is dissolved in, for example, 100 ml of ion exchange water.
- oxygen-containing organic compound examples include polyethylene glycol, polyethylene oxide, casein, dextrin, starch, modified starch, polyvinyl alcohol, modified polyvinyl alcohol (acetoacetylated polyvinyl alcohol, etc.), polyethylene oxide, polyvinyl pyrrolidone, polyvinyl methyl ether, poly Hydrophilic polymers such as acrylates, alkyl acrylate copolymers, urethane copolymers, cellulose derivatives (hydroxyethylcellulose, carboxyethylcellulose, carboxymethylcellulose, etc.); hydrophilic low molecules, such as glycerin, sorbitol, ethylene glycol Is mentioned.
- polyethylene glycol, polyethylene oxide, glycerin, and sorbitol are preferable from the viewpoint of improving the strength, density, chemical resistance, and the like of the fiber layer, and more preferably at least one selected from polyethylene glycol and polyethylene oxide. preferable.
- the oxygen-containing organic compound is preferably an organic compound polymer having a molecular weight of 50,000 to 8,000,000.
- the molecular weight of the oxygen-containing organic compound is preferably 100,000 to 5,000,000, but may be a low molecule having a molecular weight of less than 1,000, for example.
- the content of the oxygen-containing organic compound contained in the fiber layer is preferably 1 part by mass or more and 40 parts by mass or less, with respect to 100 parts by mass of the fine fibrous cellulose contained in the fiber layer. More preferably, the amount is 15 parts by mass or more and 25 parts by mass or less.
- organic ions include tetraalkylammonium ions and tetraalkylphosphonium ions.
- tetraalkylammonium ions include tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, tetraheptylammonium ion, tributylmethylammonium ion, and lauryltrimethyl.
- Examples include ammonium ion, cetyltrimethylammonium ion, stearyltrimethylammonium ion, octyldimethylethylammonium ion, lauryldimethylethylammonium ion, didecyldimethylammonium ion, lauryldimethylbenzylammonium ion, and tributylbenzylammonium ion.
- tetraalkylphosphonium ions examples include tetramethylphosphonium ions, tetraethylphosphonium ions, tetrapropylphosphonium ions, tetrabutylphosphonium ions, and lauryltrimethylphosphonium ions.
- examples of the tetrapropylonium ion and the tetrabutylonium ion include tetra n-propylonium ion and tetra n-butylonium ion, respectively.
- seat includes the process of obtaining the slurry containing the fibrous cellulose whose fiber width is 1000 nm or less, and a cationic resin, the process of apply
- the sheet manufacturing process preferably includes a step of applying a slurry containing fine fibrous cellulose and a cationic resin (hereinafter sometimes simply referred to as a slurry) on a substrate. More preferably, the method includes a step of applying a slurry containing polyamine polyamide epihalohydrin on a substrate.
- the step of obtaining the slurry it is preferable to add 0.1 parts by mass or more, and 0.5 parts by mass or more of the cation resin to 100 parts by mass of fibrous cellulose having a fiber width of 1000 nm or less contained in the slurry. It is more preferable to add 2 parts by mass or more, and it is more preferable to add 5 parts by mass or more. Moreover, it is preferable that the addition amount of a cation resin is 15 mass parts or less, and it is more preferable that it is 12 mass parts or less.
- the step of obtaining the slurry it is preferable to add 0.1 part by mass or more, and 0.5 part by mass or more of polyamine polyamide epihalohydrin to 100 parts by mass of fibrous cellulose having a fiber width of 1000 nm or less contained in the slurry. It is more preferable to add 2 parts by mass or more, and it is more preferable to add 5 parts by mass or more. Moreover, it is preferable that the addition amount of polyamine polyamide epihalohydrin is 15 mass parts or less, and it is more preferable that it is 12 mass parts or less.
- a polyacrylamide resin may be further added.
- the polyacrylamide resin is preferably added before the polyamine polyamide epihalohydrin is added.
- polyamine polyamide epihalohydrin it is preferable to add polyamine polyamide epihalohydrin after the polyacrylamide resin is uniformly dispersed.
- the polyamine polyamide epihalohydrin is preferably added after 30 seconds or longer after the addition of the polyacrylamide resin.
- the amount of addition of the polyacrylamide resin is 0.1 parts by mass or more with respect to 100 parts by mass of fibrous cellulose having a fiber width of 1000 nm or less contained in the slurry. Is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and particularly preferably 5 parts by mass or more. Moreover, it is preferable that the addition amount of polyacrylamide type resin is 50 mass parts or less, and it is more preferable that it is 30 mass parts or less.
- polyamine polyamide epihalohydrin and polyacrylamide resin may be added as a resin emulsion.
- a resin excluding polyamine polyamide epihalohydrin and polyacrylamide resin may be added, and the resin may be added as a resin emulsion.
- ⁇ Coating process> a slurry containing fibrous cellulose having a fiber width of 1000 nm or less and a cationic resin is coated on a substrate, and the sheet formed by drying this is peeled off from the substrate. It is a process to obtain. By using a coating apparatus and a long base material, sheets can be continuously produced.
- the quality of the base material used in the coating process is not particularly limited, but the one with higher wettability to the slurry may be able to suppress the shrinkage of the sheet during drying, but the sheet formed after drying is easier It is preferable to select one that can be peeled off.
- a resin plate or a metal plate is preferable, but is not particularly limited.
- resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc., and those whose surfaces are oxidized, stainless steel A plate, a brass plate or the like can be used.
- a damming frame may be fixed on the base material to obtain a sheet having a predetermined thickness and basis weight. Good.
- the quality of the damming frame is not particularly limited, but it is preferable to select one that can easily peel off the edge of the sheet attached after drying. Among them, a molded resin plate or metal plate is preferable, but is not particularly limited.
- resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc., and those whose surfaces are oxidized, stainless steel
- resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc., and those whose surfaces are oxidized, stainless steel
- a molded plate, brass plate, or the like can be used.
- a coating machine for applying the slurry 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 preferable because the thickness can be made more uniform.
- the coating temperature is not particularly limited, but is preferably 20 ° C or higher and 45 ° C or lower, more preferably 25 ° C or higher and 40 ° C or lower, and further preferably 27 ° C or higher and 35 ° C or lower. If the coating temperature is not less than the above lower limit value, the slurry can be easily applied, and if it is not more than the above upper limit value, volatilization of the dispersion medium during coating can be suppressed.
- the coating step it is preferable to apply the slurry so that the finished basis weight of the sheet is 10 g / m 2 or more and 100 g / m 2 or less, preferably 20 g / m 2 or more and 50 g / m 2 or less.
- the basis weight is within the above range, a sheet having excellent strength can be obtained.
- the coating step preferably includes a step of drying the slurry coated on the substrate.
- a drying method Either a non-contact drying method or the method of drying while restraining a sheet
- the non-contact drying method is not particularly limited, but a method of drying by heating with hot air, infrared rays, far infrared rays or near infrared rays (heating drying method) or a method of drying in vacuum (vacuum drying method) is applied. Can do. Although the heat drying method and the vacuum drying method may be combined, the heat drying method is usually applied. Although drying by infrared rays, far infrared rays, or near infrared rays can be performed using an infrared device, a far infrared device, or a near infrared device, it is not particularly limited.
- the heating temperature in the heat drying method is not particularly limited, but is preferably 20 ° C. or higher and 150 ° C.
- the heating temperature is not less than the above lower limit value, the dispersion medium can be volatilized quickly, and if it is not more than the above upper limit value, it is possible to suppress the cost required for heating and to prevent the fine fibrous cellulose from being discolored by heat. .
- the manufacturing process of the sheet of the present invention may include a process of making a slurry.
- Examples of the paper machine in the paper making process include a continuous paper machine such as a long-mesh type, a circular net type, and an inclined type, and a multi-layered paper machine combining these.
- known paper making such as hand making may be performed.
- the slurry is filtered and dehydrated on a wire to obtain a wet paper sheet, and then the sheet is obtained by pressing and drying.
- the filter cloth at the time of filtration is not particularly limited, but it is important that a cationic resin such as fine fibrous cellulose or polyamine polyamide epihalohydrin does not pass through and the filtration rate is not too slow.
- a cationic resin such as fine fibrous cellulose or polyamine polyamide epihalohydrin
- seat, fabric, and porous film which consist of organic polymers are preferable.
- the organic polymer is not particularly limited, but non-cellulosic organic polymers such as polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and the like are preferable. Specific examples include a porous film of polytetrafluoroethylene having a pore size of 0.1 ⁇ m to 20 ⁇ m, for example, 1 ⁇ m, polyethylene terephthalate or polyethylene woven fabric having a pore size of 0.1 ⁇ m to 20 ⁇ m, for example, 1 ⁇ m, but is not particularly limited.
- non-cellulosic organic polymers such as polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and the like are preferable. Specific examples include a porous film of polytetrafluoroethylene having a pore size of 0.1 ⁇ m to 20 ⁇ m, for example, 1 ⁇ m, polyethylene terephthalate or polyethylene woven fabric having a
- This manufacturing apparatus discharges a slurry containing fine fibrous cellulose onto the upper surface of an endless belt, squeezes a dispersion medium from the discharged slurry, generates a web, and dries the web to dry the fiber sheet. And a drying section to produce.
- An endless belt is disposed from the squeezing section to the drying section, and the web generated in the squeezing section is conveyed to the drying section while being placed on the endless belt.
- the dehydration method that can be employed is not particularly limited, and examples include a dehydration method that is normally used in paper manufacture.
- a method of dehydrating with a long net, circular net, inclined wire, etc., and then dehydrating with a roll press is preferable.
- the drying method is not particularly limited, and examples thereof include methods used in paper production. For example, methods such as a cylinder dryer, a Yankee dryer, hot air drying, a near infrared heater, and an infrared heater are preferable.
- the present invention may relate to a laminate having a structure in which another layer is further laminated on a sheet. Such other layers may be provided on both surfaces of the sheet, but may be provided only on one surface of the sheet.
- a resin layer and an inorganic layer can be mentioned, for example.
- the resin layer is a layer mainly composed of natural resin or synthetic resin.
- a main component refers to the component contained 50 mass% or more with respect to the total mass of a resin layer.
- the content of the resin is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass with respect to the total mass of the resin layer. The above is particularly preferable.
- content of resin can also be 100 mass%, and may be 95 mass% or less.
- Examples of natural resins include rosin resins such as rosin, rosin ester, and hydrogenated rosin ester.
- the synthetic resin is preferably at least one selected from, for example, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, polyimide resin, polystyrene resin, and acrylic resin.
- the synthetic resin is preferably at least one selected from polycarbonate resin and acrylic resin, and more preferably polycarbonate resin.
- the acrylic resin is preferably at least one selected from polyacrylonitrile and poly (meth) acrylate.
- polycarbonate resin constituting the resin layer examples include an aromatic polycarbonate resin and an aliphatic polycarbonate resin. These specific polycarbonate resins are known and include, for example, the polycarbonate resins described in JP 2010-023275 A.
- the resin constituting the resin layer one kind may be used alone, or a copolymer obtained by copolymerization or graft polymerization of a plurality of resin components may be used. Moreover, you may use as a blend material which mixed the some resin component with the physical process.
- the adhesive layer may be provided between the sheet and the resin layer, or the adhesive layer may not be provided, and the sheet and the resin layer may be in direct contact with each other.
- an acrylic resin can be used as an adhesive constituting the adhesive layer.
- adhesives other than acrylic resins include vinyl chloride resin, (meth) acrylate resin, styrene / acrylate copolymer resin, vinyl acetate resin, vinyl acetate / (meth) acrylate ester.
- Examples include polymer resins, urethane resins, silicone resins, epoxy resins, ethylene / vinyl acetate copolymer resins, polyester resins, polyvinyl alcohol resins, ethylene vinyl alcohol copolymer resins, and rubber emulsions such as SBR and NBR. It is done.
- the resin layer may have an adhesion assistant, and surface treatment such as hydrophilic treatment may be performed on the surface of the resin layer.
- the adhesion assistant include a compound containing at least one selected from an isocyanate group, a carbodiimide group, an epoxy group, an oxazoline group, an amino group, and a silanol group, and an organosilicon compound.
- the adhesion assistant is preferably at least one selected from a compound containing an isocyanate group (isocyanate compound) and an organosilicon compound.
- organosilicon compounds include silane coupling agent condensates and silane coupling agents.
- the surface treatment method include corona treatment, plasma discharge treatment, UV irradiation treatment, electron beam irradiation treatment, and flame treatment.
- the material constituting the inorganic layer is not particularly limited, but for example, aluminum, silicon, magnesium, zinc, tin, nickel, titanium, platinum, gold, silver; these oxides, carbides, nitrides, oxycarbides, oxynitrides Or oxycarbonitrides; or mixtures thereof. From the standpoint that high moisture resistance can be stably maintained, silicon oxide, silicon nitride, silicon oxide carbide, silicon oxynitride, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxide carbide, aluminum oxynitride, indium tin oxide (ITO) or mixtures thereof are preferred.
- ITO indium tin oxide
- the method for forming the inorganic layer is not particularly limited.
- a method for forming a thin film is roughly classified into a chemical vapor deposition method (chemical vapor deposition, CVD) and a physical film deposition method (physical vapor deposition, PVD), and either method may be adopted.
- CVD method include plasma CVD using plasma, and catalytic chemical vapor deposition (Cat-CVD) in which a material gas is contact pyrolyzed using a heating catalyst.
- Cat-CVD catalytic chemical vapor deposition
- PVD method include vacuum deposition, ion plating, and sputtering.
- an atomic layer deposition method (Atomic Layer Deposition, ALD) can also be employed.
- the ALD method is a method of forming a thin film in units of atomic layers by alternately supplying source gases of respective elements constituting a film to be formed to a surface on which a layer is formed.
- the film forming speed is slow, there is an advantage that it is possible to form a thin film with few defects because it can cleanly cover even a complicated surface more than the plasma CVD method.
- the ALD method has an advantage that the film thickness can be controlled on the nano order and it is relatively easy to cover a wide surface.
- the ALD method can be expected to improve the reaction rate, lower the temperature, and reduce the unreacted gas by using plasma.
- the sheet of the present invention is a sheet excellent in transparency and water resistance. From the viewpoint of making use of the above characteristics, it is suitable for applications of light transmissive substrates such as various display devices and various solar cells. It is also suitable for applications such as substrates for electronic devices, members of household appliances, various vehicles and building windows, interior materials, exterior materials, packaging materials, and the like. Furthermore, it is also suitable for applications in which the sheet itself is used as a reinforcing material in addition to threads, filters, fabrics, cushioning materials, sponges, abrasives, and the like.
- Example 1 ⁇ Production of phosphate group-introduced cellulose fiber>
- Oji Paper's pulp solid content 93% basis weight 208 g / m 2 sheet-like Canadian standard freeness (CSF) 700 ml, which was disaggregated and measured according to JIS P 8121
- 100 parts by mass of the above softwood kraft pulp absolute dry mass
- a mixed aqueous solution of ammonium dihydrogen phosphate and urea is impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea, and compressed to 49 parts by mass of ammonium dihydrogen phosphate and 130 parts by mass of urea. Pulp was obtained.
- the obtained chemical solution-impregnated pulp was dried with a dryer at 105 ° C. to evaporate the moisture and pre-dried. Then, it heated for 10 minutes with the ventilation dryer set to 140 degreeC, the phosphate group was introduce
- the dispersion was weighed so that the finished basis weight of the sheet was 45 g / m 2 , applied to a commercially available acrylic plate, and dried with a dryer at 70 ° C. for 24 hours.
- the board for damming was arrange
- seat was obtained by the above procedure and the thickness was 30 micrometers.
- Example 2 A sheet was obtained in the same manner as in Example 1 except that the amount of polyamine polyamide epichlorohydrin added was 2.5 parts by mass.
- Example 3 A sheet was obtained in the same manner as in Example 1 except that the amount of polyamine polyamide epichlorohydrin added was 5 parts by mass.
- Example 4 A sheet was obtained in the same manner as in Example 1 except that the amount of polyamine polyamide epichlorohydrin added was 10 parts by mass.
- Example 5 20 parts by mass of polyethylene glycol was added to the fine fibrous cellulose dispersion of Example 1. Thereafter, anionic polyacrylamide (manufactured by Seiko PMC Co., Ltd., paper strength agent DA4104) was added to the dispersion so as to be 1.0 part by mass with respect to 100 parts by mass of fine fibrous cellulose. 30 seconds after the addition of polyacrylamide, polyamine polyamide epichlorohydrin was added to 0.5 parts by mass with respect to 100 parts by mass of fine fibrous cellulose. A sheet was obtained in the same manner as in Example 1 except that this dispersion was used as a sheet.
- anionic polyacrylamide manufactured by Seiko PMC Co., Ltd., paper strength agent DA4104
- polyamine polyamide epichlorohydrin was added to 0.5 parts by mass with respect to 100 parts by mass of fine fibrous cellulose.
- Example 6 A sheet was obtained in the same manner as in Example 5 except that the addition amount of polyamine polyamide epichlorohydrin was 2.5 parts by mass and the addition amount of polyacrylamide was 5 parts by mass.
- Example 7 A sheet was obtained in the same manner as in Example 5 except that the addition amount of polyamine polyamide epichlorohydrin was 5 parts by mass and the addition amount of polyacrylamide was 10 parts by mass.
- Example 8 A sheet was obtained in the same manner as in Example 5 except that the addition amount of polyamine polyamide epichlorohydrin was 10 parts by mass and the addition amount of polyacrylamide was 20 parts by mass.
- Example 9 A sheet was obtained in the same manner as in Example 6 except that polyacrylamide was nonionic (manufactured by Seiko PMC Co., Ltd., paper strength agent DH4162).
- Example 10 A sheet was obtained in the same manner as in Example 9 except that the addition amount of polyamine polyamide epichlorohydrin was 5 parts by mass and the addition amount of polyacrylamide was 10 parts by mass.
- Example 11 A sheet was obtained in the same manner as in Example 9 except that polyacrylamide was cationic (manufactured by Seiko PMC Co., Ltd., paper strength agent DS4433).
- Example 12 A sheet was obtained in the same manner as in Example 11 except that the addition amount of polyamine polyamide epichlorohydrin was 5 parts by mass and the addition amount of polyacrylamide was 10 parts by mass.
- Example 13 A sheet was obtained in the same manner as in Example 6, except that a polypropylene resin emulsion (Toho Chemical Co., Ltd., HYTEC P-5060P, particle size 30 nm) was used instead of polyacrylamide.
- a polypropylene resin emulsion Toho Chemical Co., Ltd., HYTEC P-5060P, particle size 30 nm
- Example 14 Undried softwood bleached kraft pulp equivalent to 100 parts by weight of dry weight, 1.6 parts by weight of TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl), 10 parts by weight of sodium bromide, 10000 water Dispersed in parts by mass. Subsequently, 13 mass% sodium hypochlorite aqueous solution was added so that the quantity of sodium hypochlorite might be 3.5 mmol with respect to 1.0 g of pulp, and reaction was started. During the reaction, a 1.0 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10 or more and 11 or less. When no change was observed in the pH, the reaction was regarded as completed, and carboxyl groups were introduced into the pulp.
- TEMPO 2,2,6,6-tetramethylpiperidine 1-oxyl
- the pulp slurry was dehydrated to obtain a dehydrated sheet, and then 5000 parts by mass of ion-exchanged water was poured and stirred to disperse uniformly. Then, filtration dehydration and the process of obtaining a dehydration sheet were repeated twice, and the carboxyl group-modified cellulose fiber was obtained.
- the resulting carboxyl group-modified cellulose fiber had a carboxyl group introduction amount of 1.01 mmol / g.
- a sheet was obtained in the same manner as in Example 3 except that this was used as a raw material.
- Substituent group measurement on cellulose surface The amount of phosphate groups introduced was measured by diluting cellulose with ion-exchanged water so that the content was 0.2% by mass, and then treating with ion-exchange resin and titration with alkali. In the treatment with an ion exchange resin, 1/10 by volume of a strongly acidic ion exchange resin (manufactured by Organo Corporation, Amberjet 1024: conditioned) is added to the 0.2 mass% cellulose-containing slurry, followed by shaking treatment for 1 hour. went. Thereafter, the mixture was poured onto a mesh having an opening of 90 ⁇ m to separate the resin and the slurry.
- a strongly acidic ion exchange resin manufactured by Organo Corporation, Amberjet 1024: conditioned
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Abstract
Description
しかしながら、特許文献1及び2で得られた微細繊維状セルロース含有シートにおいては、耐水性が十分ではない場合があり改善が求められていた。また、特許文献3の実施例で得られた微細繊維状セルロース含有シートにおいては、透明性が低下することが本発明者らの検討により明らかとなった。すなわち、従来技術で得られた微細繊維状セルロース含有シートにおいては、耐水性と透明性が両立されておらず改善が求められていた。
具体的に、本発明は、以下の構成を有する。
[2]カチオン樹脂が、ポリアミンポリアミドエピハロヒドリンを含む[1]に記載のシート。
[3] シートをイオン交換水に24時間浸漬した後の質量をWとし、シートを23℃、相対湿度50%で24時間調湿した後の質量をWdとした場合、(W-Wd)/Wd×100で表される吸水率が5000%以下である[1]又は[2]に記載のシート。
[4] 全光線透過率が85%以上である[1]~[3]のいずれかに記載のシート。
[5] 23℃、相対湿度50%の条件下で24時間調湿した後の引張弾性率が5GPa以上である[1]~[4]のいずれかに記載のシート。
[6] 繊維状セルロース100質量部に対して、ポリアミンポリアミドエピハロヒドリンを0.1質量部以上15質量部以下含む[1]~[5]いずれかに記載のシート。
[7] ポリアクリルアミド系樹脂をさらに含む[1]~[6]いずれかに記載のシート。
[8] ポリアクリルアミド系樹脂は、イオン性のポリアクリルアミド系樹脂である[7]に記載のシート。
[9] ポリアクリルアミド系樹脂は、ノニオン性のポリアクリルアミド系樹脂である[7]に記載のシート。
[10] 繊維状セルロースは、イオン性官能基を有する[1]~[9]のいずれかに記載のシート。
[11] イオン性官能基はリン酸基である[10]に記載のシート。
[12] JIS K 7373に準拠して測定した黄色度が1.2以下である[1]~[11]のいずれかに記載のシート。
[13] 粒状の樹脂を含む[1]~[12]のいずれかに記載のシート。
本発明は、繊維幅が1000nm以下の繊維状セルロースと、カチオン樹脂とを含むシートに関する。本発明のシートは、繊維幅が1000nm以下の繊維状セルロースと、ポリアミンポリアミドエピハロヒドリンとを含むシートに関するものであることが好ましい。ここで、本発明のシートのヘーズは6%以下である。
本発明のシートは上記構成を有するため、透明性の高いシートにおいて優れた耐水性を発揮するものである。また、本発明のシートは透明性と耐水性に加えて、十分な強度を有するものであり、十分な引張強度と引張弾性率を有するものである。
本発明のシートの引張弾性率は、5GPa以上であることが好ましく、6GPa以上であることがより好ましく、7GPa以上であることがさらに好ましい。引張弾性率の上限値は、特に限定されないが、たとえば50GPa以下とすることができる。
本発明のシートの伸度は、1%以上であることが好ましく、2%以上であることがより好ましく、3%以上であることがさらに好ましい。シートの伸度は、20%以下であることが好ましく、15%以下であることがより好ましい。
上記引張強度、引張弾性率及び伸度は、シートを23℃、相対湿度50%の条件下に24時間置いた後にJIS P 8113に準拠し、引張試験機テンシロン(エー・アンド・デイ社製)を用いて測定をした値である。本願明細書においては、23℃、相対湿度50%の条件は調湿条件(乾燥条件)であり、上記引張強度、引張弾性率及び伸度は調湿条件下に24時間静置した後の引張強度、引張弾性率及び伸度である。
本発明のシートは、カチオン樹脂を含む。本発明のシートにおいては、カチオン樹脂がセルロース繊維に定着し、当該カチオン樹脂の疎水部分によってシートの耐水性が向上すると考えられる。
ポリアミンポリアミドエピハロヒドリンは、脂肪族二塩基性カルボン酸又はその誘導体と、ポリアルキレンポリアミンを加熱縮合させてポリアミドポリアミンを合成し、次いで該ポリアミドポリアミンとエピハロヒドリンを反応させることで得られるカチオン性熱硬化性樹脂である。なお、ポリアミンポリアミドエピハロヒドリンは水性樹脂であり、シートを製造する際にはポリアミンポリアミドエピハロヒドリンは水溶液として添加することが好ましい。
ポリアミンポリアミドエピクロロヒドリンが特に好ましい理由は、次のとおりと考えられる。ポリアミンポリアミドエピクロロヒドリンは、ポリアミンポリアミド樹脂とエピクロロヒドリンを付加反応させることにより得られる。ポリアミンポリアミド樹脂は、カチオン基と疎水基を有するため、セルロース繊維に定着し、耐水性を発揮することが出来る。また、エピクロロヒドリンも、セルロースと結合し、耐水性を高めることに寄与する。このようなポリアミンポリアミド樹脂とエピクロロヒドリンを付加反応させることにより得られるポリアミンポリアミドエピクロロヒドリンは、水性樹脂であり、ポリアミンポリアミドエピクロロヒドリンを水溶液として微細繊維セルロースに添加することにより、微細繊維セルロースの透明性を阻害することなく、耐水性を発揮することが出来る。
なお、ポリアミンポリアミドエピハロヒドリンの含有量は、例えば、NMR測定やMSのフラグメント解析、UV解析などを用いて分析することができる。
本発明のシートは、繊維幅が1000nm以下の繊維状セルロース(以下、微細繊維状セルロースともいう)を含む。シートに含まれる微細繊維状セルロースの含有量は、シートの全質量に対して、60質量%以上であることが好ましく、70質量%以上であることがより好ましく、80質量%以上であることがさらに好ましく、90質量%以上であることが特に好ましい。
(2)同じ画像内で該直線と垂直に交差する直線Yを引き、該直線Yに対し、20本以上の繊維が交差する。
微細繊維状セルロースに占めるI型結晶構造の割合は30%以上であることが好ましく、より好ましくは50%以上、さらに好ましくは70%以上である。
リン酸基導入工程は、セルロースを含む繊維原料に対し、リン酸基を有する化合物及びその塩から選択される少なくとも1種(以下、「リン酸化試薬」又は「化合物A」という)を反応させることにより行うことができる。このようなリン酸化試薬は、乾燥状態または湿潤状態の繊維原料に粉末や水溶液の状態で混合してもよい。また別の例としては、繊維原料のスラリーにリン酸化試薬の粉末や水溶液を添加してもよい。
リン酸基を有する化合物としては、リン酸、リン酸のリチウム塩、リン酸のナトリウム塩、リン酸のカリウム塩、リン酸のアンモニウム塩などが挙げられるが、特に限定されない。リン酸のリチウム塩としては、リン酸二水素リチウム、リン酸水素二リチウム、リン酸三リチウム、ピロリン酸リチウム、またはポリリン酸リチウムなどが挙げられる。リン酸のナトリウム塩としてはリン酸二水素ナトリウム、リン酸水素二ナトリウム、リン酸三ナトリウム、ピロリン酸ナトリウム、またはポリリン酸ナトリウムなどが挙げられる。リン酸のカリウム塩としてはリン酸二水素カリウム、リン酸水素二カリウム、リン酸三カリウム、ピロリン酸カリウム、またはポリリン酸カリウムなどが挙げられる。リン酸のアンモニウム塩としては、リン酸二水素アンモニウム、リン酸水素二アンモニウム、リン酸三アンモニウム、ピロリン酸アンモニウム、ポリリン酸アンモニウムなどが挙げられる。
本発明においては、微細繊維状セルロースがカルボキシル基を有するものである場合、たとえばTEMPO酸化処理などの酸化処理やカルボン酸由来の基を有する化合物、その誘導体、またはその酸無水物もしくはその誘導体によって処理することで、カルボキシル基を導入することができる。
カルボキシル基の導入量は、微細繊維状セルロース1g(質量)あたり0.1mmol/g以上であることが好ましく、0.2mmol/g以上であることがより好ましく、0.3mmol/g以上であることがさらに好ましく、0.5mmol/g以上であることが特に好ましい。また、カルボキシル基の導入量は3.5mmol/g以下であることが好ましく、3.0mmol/g以下であることがより好ましく、2.5mmol/g以下であることがさらに好ましく、2.0mmol/g以下であることが特に好ましい。カルボキシル基の導入量を上記範囲内とすることにより、繊維原料の微細化を容易にすることができ、微細繊維状セルロースの安定性を高めることができる。
本実施形態においては、イオン性官能基としてカチオン性置換基が微細繊維状セルロースに導入されていてもよい。例えば繊維原料にカチオン化剤及びアルカリ化合物を添加して反応させることにより、繊維原料にカチオン性置換基を導入することができる。
カチオン化剤としては、4級アンモニウム基を有し、かつセルロースのヒドロキシル基と反応する基を有するものを用いることができる。セルロースのヒドロキシル基と反応する基としては、エポキシ基、ハロヒドリンの構造を有する官能基、ビニル基、ハロゲン基等が挙げられる。カチオン化剤の具体例としては、グリシジルトリメチルアンモニウムクロリド、3-クロロ-2-ヒドロキシプロピルトリメチルアンモニウムクロリドなどのグリシジルトリアルキルアンモニウムハライド或いはそのハロヒドリン型の化合物が挙げられる。
アルカリ化合物は、カチオン化反応の促進に寄与するものである。アルカリ化合物は、アルカリ金属の水酸化物またはアルカリ土類金属の水酸化物、アルカリ金属の炭酸塩またはアルカリ土類金属の炭酸塩、アルカリ金属のリン酸塩またはアルカリ土類金属のリン酸塩などの無機アルカリ化合物であってもよいし、アンモニア、脂肪族アミン、芳香族アミン、脂肪族アンモニウム、芳香族アンモニウム、複素環式化合物及びその水酸化物、炭酸塩、リン酸塩等の有機アルカリ化合物であってもよい。カチオン性置換基の導入量の測定は、たとえば元素分析等を用いて行うことができる。
微細繊維状セルロースを製造する場合、イオン性官能基導入工程と、後述する解繊処理工程の間にアルカリ処理を行ってもよい。アルカリ処理の方法としては、特に限定されないが、例えば、アルカリ溶液中に、リン酸基導入繊維を浸漬する方法が挙げられる。
アルカリ溶液に含まれるアルカリ化合物は、特に限定されないが、無機アルカリ化合物であってもよいし、有機アルカリ化合物であってもよい。アルカリ溶液における溶媒としては水または有機溶媒のいずれであってもよい。溶媒は、極性溶媒(水、またはアルコール等の極性有機溶媒)が好ましく、少なくとも水を含む水系溶媒がより好ましい。
また、アルカリ溶液のうちでは、汎用性が高いことから、水酸化ナトリウム水溶液、または水酸化カリウム水溶液が特に好ましい。
アルカリ処理工程におけるアルカリ溶液への浸漬時間は特に限定されないが、5分以上30分以下が好ましく、10分以上20分以下がより好ましい。
アルカリ処理におけるアルカリ溶液の使用量は特に限定されないが、リン酸基導入繊維の絶対乾燥質量に対して100質量%以上100000質量%以下であることが好ましく、1000質量%以上10000質量%以下であることがより好ましい。
リン酸基導入繊維は、解繊処理工程で解繊処理される。解繊処理工程では、通常、解繊処理装置を用いて、繊維を解繊処理して、微細繊維状セルロース含有スラリーを得るが、処理装置、処理方法は、特に限定されない。
解繊処理装置としては、高速解繊機、グラインダー(石臼型粉砕機)、高圧ホモジナイザーや超高圧ホモジナイザー、高圧衝突型粉砕機、ボールミル、ビーズミルなどを使用できる。あるいは、解繊処理装置としては、ディスク型リファイナー、コニカルリファイナー、二軸混練機、振動ミル、高速回転下でのホモミキサー、超音波分散機、またはビーターなど、湿式粉砕する装置等を使用することもできる。解繊処理装置は、上記に限定されるものではない。好ましい解繊処理方法としては、粉砕メディアの影響が少なく、コンタミの心配が少ない高速解繊機、高圧ホモジナイザー、超高圧ホモジナイザーが挙げられる。
本発明のシートは、ポリアクリルアミド系樹脂をさらに含むことが好ましい。ポリアクリルアミド系樹脂としては、例えば、アクリルアミドの単独重合体(ポリアクリルアミド)や、アクリルアミドを主成分とする共重合体が挙げられる。中でも、ポリアクリルアミド系樹脂はアクリルアミドを主成分とする共重合体であることが好ましく、共重合体を構成する単位のうち、アクリルアミドに由来する単位が50質量%以上含まれているものであることが好ましい。アクリルアミドと共重合可能なモノマーとしては、例えば、ノニオン性モノマー、アニオン性モノマー、カチオン性モノマーが挙げられる。
なお、ポリアクリルアミド系樹脂の含有量は、例えば、NMR測定やMSのフラグメント解析、UV解析などを用いて分析することができる
本発明のシートは、たとえば上述した樹脂を除くその他の樹脂をさらに含むことができる。
シートには、上述した成分以外の任意成分が含まれていてもよい。任意成分としては、たとえば、消泡剤、潤滑剤、紫外線吸収剤、染料、顔料、安定剤、界面活性剤等を挙げることができる。また、任意成分としては、例えば、親水性高分子や有機イオン等が挙げられる。親水性高分子は、親水性の含酸素有機化合物(但し、上記セルロース繊維は除く)であることが好ましい。含酸素有機化合物は非繊維状であることが好ましく、このような非繊維状の含酸素有機化合物には、微細繊維状セルロースや熱可塑性樹脂繊維は含まれない。
シートの製造工程は、繊維幅が1000nm以下の繊維状セルロースと、カチオン樹脂とを含むスラリーを得る工程と、このスラリーを基材上に塗工する工程、又は、スラリーを抄紙する工程を含む。中でも、シートの製造工程は、微細繊維状セルロースと、カチオン樹脂とを含むスラリー(以下、単にスラリーということもある)を基材上に塗工する工程を含むことが好ましく、微細繊維状セルロースと、ポリアミンポリアミドエピハロヒドリンとを含むスラリーを基材上に塗工する工程を含むことがより好ましい。
塗工工程は、繊維幅が1000nm以下の繊維状セルロースと、カチオン樹脂とを含むスラリーを基材上に塗工し、これを乾燥して形成されたシートを基材から剥離することによりシートを得る工程である。塗工装置と長尺の基材を用いることで、シートを連続的に生産することができる。
本発明のシートの製造工程は、スラリーを抄紙する工程を含んでもよい。抄紙工程で抄紙機としては、長網式、円網式、傾斜式等の連続抄紙機、これらを組み合わせた多層抄き合わせ抄紙機等が挙げられる。抄紙工程では、手抄き等公知の抄紙を行ってもよい。
本発明は、シートにさらに他の層を積層した構造を有する積層体に関するものであってもよい。このような他の層は、シートの両表面上に設けられていてもよいが、シートの一方の面上にのみ設けられていてもよい。シートの少なくとも一方の面上に積層される他の層としては、例えば、樹脂層や無機層を挙げることができる。
樹脂層は、天然樹脂や合成樹脂を主成分とする層である。ここで、主成分とは、樹脂層の全質量に対して、50質量%以上含まれている成分を指す。樹脂の含有量は、樹脂層の全質量に対して、60質量%以上であることが好ましく、70質量%以上であることがより好ましく、80質量%以上であることがさらに好ましく、90質量%以上であることが特に好ましい。なお、樹脂の含有量は、100質量%とすることもでき、95質量%以下であってもよい。
密着助剤としては、例えば、イソシアネート基、カルボジイミド基、エポキシ基、オキサゾリン基、アミノ基及びシラノール基から選択される少なくとも1種を含む化合物や、有機ケイ素化合物が挙げられる。中でも、密着助剤はイソシアネート基を含む化合物(イソシアネート化合物)及び有機ケイ素化合物から選択される少なくとも1種であることが好ましい。有機ケイ素化合物としては、例えば、シランカップリング剤縮合物や、シランカップリング剤を挙げることができる。
表面処理の方法としては、コロナ処理、プラズマ放電処理、UV照射処理、電子線照射処理、火炎処理等を挙げることができる。
無機層を構成する物質としては、特に限定されないが、例えばアルミニウム、ケイ素、マグネシウム、亜鉛、錫、ニッケル、チタン、白金、金、銀;これらの酸化物、炭化物、窒化物、酸化炭化物、酸化窒化物、もしくは酸化炭化窒化物;またはこれらの混合物が挙げられる。高い防湿性が安定に維持できるとの観点からは、酸化ケイ素、窒化ケイ素、酸化炭化ケイ素、酸化窒化ケイ素、酸化炭化窒化ケイ素、酸化アルミニウム、窒化アルミニウム、酸化炭化アルミニウム、酸化窒化アルミニウム、酸化インジウムスズ(ITO)またはこれらの混合物が好ましい。
本発明のシートは、透明性と耐水性に優れたシートである。上記の特性を活かす観点から、各種のディスプレイ装置、各種の太陽電池、等の光透過性基板の用途に適している。また、電子機器の基板、家電の部材、各種の乗り物や建物の窓材、内装材、外装材、包装用資材等の用途にも適している。さらに、糸、フィルタ、織物、緩衝材、スポンジ、研磨材などの他、シートそのものを補強材として使う用途にも適している。
<リン酸基導入セルロース繊維の作製>
針葉樹クラフトパルプとして、王子製紙製のパルプ(固形分93% 坪量208g/m2シート状 離解してJIS P 8121に準じて測定されるカナダ標準濾水度(CSF)700ml)を使用した。上記針葉樹クラフトパルプ(絶乾質量)100質量部に、リン酸二水素アンモニウムと尿素の混合水溶液を含浸し、リン酸二水素アンモニウム49質量部、尿素130質量部となるように圧搾し、薬液含浸パルプを得た。得られた薬液含浸パルプを105℃の乾燥機で乾燥し、水分を蒸発させてプレ乾燥させた。その後、140℃に設定した送風乾燥機で、10分間加熱し、パルプ中のセルロースにリン酸基を導入し、リン酸化パルプを得た。
得られたリン酸化パルプの絶乾質量として100質量部に対して10000質量部のイオン交換水を注ぎ、攪拌して均一に分散させた後、濾過脱水して、脱水シートを得る工程を2回繰り返し、リン酸変性セルロース繊維を得た。次いで、リン酸基を導入したセルロースに5000mlのイオン交換水を加え、撹拌洗浄後、脱水した。脱水後のパルプを5000mlのイオン交換水で希釈し、撹拌しながら、1Nの水酸化ナトリウム水溶液をpHが12~13になるまで少しずつ添加して、パルプ分散液を得た。その後、このパルプ分散液を脱水し、5000mlのイオン交換水を加えて洗浄を行った。この脱水洗浄をさらに1回繰り返した。
得られたリン酸変性セルロース繊維は、リン酸基の導入量が0.98mmol/gであった。
洗浄脱水後に得られたパルプにイオン交換水を添加して、固形分濃度が1.0質量%のパルプ懸濁液にした。このパルプ懸濁液を、湿式微粒化装置(スギノマシン社製:アルティマイザー)を用いて処理し、微細繊維状セルロース分散液を得た。湿式微粒化装置を用いた処理においては、245MPaの圧力にて処理チャンバーを5回通過させた。微細繊維状セルロース分散液に含まれる微細繊維状セルロースの平均繊維幅は3~4nmであった。
微細繊維状セルロース分散液にポリエチレングリコール(和光純薬社製、分子量400万)を微細繊維状セルロース100質量部に対し、20質量部になるように添加した。その後、ポリアミンポリアミドエピクロロヒドリン(星光PMC株式会社製、湿潤紙力剤WS4030)を微細繊維状セルロース100質量部に対し、0.5質量部になるように添加した。その後、固形分濃度が0.6質量%となるよう濃度調整を行った。シートの仕上がり坪量が45g/m2になるように分散液を計量して、市販のアクリル板に塗工し70℃の乾燥機で24時間乾燥した。なお、所定の坪量となるようアクリル板上には堰止用の板を配置した。以上の手順によりシートが得られ、その厚みは30μmであった。
ポリアミンポリアミドエピクロロヒドリンの添加量を2.5質量部とした以外は、実施例1と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンの添加量を5質量部とした以外は、実施例1と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンの添加量を10質量部とした以外は、実施例1と同様にしてシートを得た。
実施例1の微細繊維状セルロース分散液にポリエチレングリコールを20質量部添加した。その後、分散液にアニオン性のポリアクリルアミド(星光PMC株式会社製、紙力剤DA4104)を微細繊維状セルロース100質量部に対し、1.0質量部になるように添加した。ポリアクリルアミドを添加した30秒後に、ポリアミンポリアミドエピクロロヒドリンを微細繊維状セルロース100質量部に対し、0.5質量部になるように添加した。この分散液からシート化した以外は、実施例1と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンの添加量を2.5質量部、ポリアクリルアミドの添加量を5質量部とした以外は、実施例5と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンの添加量を5質量部、ポリアクリルアミドの添加量を10質量部とした以外は、実施例5と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンの添加量を10質量部、ポリアクリルアミドの添加量を20質量部とした以外は、実施例5と同様にしてシートを得た。
ポリアクリルアミドをノニオン性(星光PMC株式会社製、紙力剤DH4162)とした以外は、実施例6と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンの添加量を5質量部、ポリアクリルアミドの添加量を10質量部とした以外は、実施例9と同様にしてシートを得た。
ポリアクリルアミドをカチオン性(星光PMC株式会社製、紙力剤DS4433)とした以外は、実施例9と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンの添加量を5質量部、ポリアクリルアミドの添加量を10質量部とした以外は、実施例11と同様にしてシートを得た。
ポリアクリルアミドの代わりにポリプロピレン樹脂のエマルジョン(東邦化学工業株式会社、HYTEC P-5060P、粒子径30nm)を使用した以外は、実施例6と同様にしてシートを得た。
乾燥質量100質量部相当の未乾燥の針葉樹晒クラフトパルプと、TEMPO(2,2,6,6-テトラメチルピペリジン 1-オキシル)1.6質量部と、臭化ナトリウム10質量部を、水10000質量部に分散させた。次いで、13質量%次亜塩素酸ナトリウム水溶液を、1.0gのパルプに対して次亜塩素酸ナトリウムの量が3.5mmolになるように加えて反応を開始した。反応中は1.0Mの水酸化ナトリウム水溶液を滴下してpHを10以上11以下に保ち、pHに変化が見られなくなった時点で反応終了と見なし、パルプにカルボキシル基を導入した。このパルプスラリーを脱水し、脱水シートを得た後、5000質量部のイオン交換水を注ぎ、攪拌して均一に分散させた。その後、濾過脱水して、脱水シートを得る工程を2回繰り返し、カルボキシル基変性セルロース繊維を得た。得られたカルボキシル基変性セルロース繊維は、カルボキシル基の導入量が1.01mmol/gであった。これを原料として用いた以外は、実施例3と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンを添加しなかった以外は、実施例1と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンを添加しなかった以外は、実施例14と同様にしてシートを得た。
アニオン性ポリアクリルアミドを10質量部添加した以外は、比較例2と同様にしてシートを得た。
ポリアミンポリアミドエピクロロヒドリンの添加量を20質量部とした以外は、実施例14と同様にしてシートを得た。
<方法>
実施例及び比較例で作製したシートについて、以下の評価方法に従って評価を実施した。
リン酸基の導入量は、セルロースをイオン交換水で含有量が0.2質量%となるように希釈した後、イオン交換樹脂による処理、アルカリを用いた滴定によって測定した。イオン交換樹脂による処理では、0.2質量%セルロース含有スラリーに体積で1/10の強酸性イオン交換樹脂(オルガノ株式会社製、アンバージェット1024:コンディショング済)を加え、1時間振とう処理を行った。その後、目開き90μmのメッシュ上に注ぎ、樹脂とスラリーを分離した。アルカリを用いた滴定では、イオン交換後の繊維状セルロース含有スラリーに、0.1Nの水酸化ナトリウム水溶液を加えながら、スラリーが示す電気伝導度の値の変化を計測した。すなわち、図1に示した曲線の第1領域で必要としたアルカリ量(mmol)を、滴定対象スラリー中の固形分(g)で除して、置換基導入量(mmol/g)とした。
なお、カルボキシル基導入量は、図2(カルボキシル基)に示した曲線の第1領域で必要としたアルカリ量(mmol)を、滴定対象スラリー中の固形分(g)で除して、置換基導入量(mmol/g)とした。
JIS K 7361に準拠し、ヘーズメータ(村上色彩技術研究所社製、HM-150)を用いて全光線透過率を測定した。
JIS K 7136に準拠し、ヘーズメータ(村上色彩技術研究所社製、HM-150)を用いてヘーズを測定した。
JIS K 7373に準拠し、Colour Cute i(スガ試験機株式会社)を用いてシート加熱前後の黄色度を測定した。
JIS P 8113に準拠し、引張試験機テンシロン(エー・アンド・デイ社製)を用いて引張強度、引張弾性率および引張伸度を測定した。
なお、測定においては、23℃、相対湿度50%で24時間調湿したものを試験片とした。
50mm角のシートをイオン交換水に24時間浸漬し、23℃、相対湿度50%で24時間調湿したシートの質量をWd(g)、浸漬後のシート質量をW(g)とし、下記の式から吸水率を求めた。
吸水率(%)=(W-Wd)/Wd×100
一方、比較例においては、吸水率の抑制と、低ヘーズは両立されておらず、耐水性と透明性の両方を兼ね備えたシートが得られていない。
Claims (13)
- 繊維幅が1000nm以下の繊維状セルロースと、カチオン樹脂と、を含み、ヘーズが6%以下であるシート。
- 前記カチオン樹脂が、ポリアミンポリアミドエピハロヒドリンを含む請求項1に記載のシート。
- 前記シートをイオン交換水に24時間浸漬した後の質量をWとし、前記シートを23℃、相対湿度50%で24時間調湿した後の質量をWdとした場合、(W-Wd)/Wd×100で表される吸水率が5000%以下である請求項1又は2に記載のシート。
- 全光線透過率が85%以上である請求項1~3のいずれか1項に記載のシート。
- 23℃、相対湿度50%の条件下で24時間調湿した後の引張弾性率が5GPa以上である請求項1~4のいずれか1項に記載のシート。
- 前記繊維状セルロース100質量部に対して、前記ポリアミンポリアミドエピハロヒドリンを0.1質量部以上15質量部以下含む請求項1~5いずれか1項に記載のシート。
- ポリアクリルアミド系樹脂をさらに含む請求項1~6いずれか1項に記載のシート。
- 前記ポリアクリルアミド系樹脂は、イオン性のポリアクリルアミド系樹脂である請求項7に記載のシート。
- 前記ポリアクリルアミド系樹脂は、ノニオン性のポリアクリルアミド系樹脂である請求項7に記載のシート。
- 前記繊維状セルロースは、イオン性官能基を有する請求項1~9のいずれか1項に記載のシート。
- 前記イオン性官能基はリン酸基である請求項10に記載のシート。
- JIS K 7373に準拠して測定した黄色度が1.2以下である請求項1~11のいずれか1項に記載のシート。
- 粒状の樹脂を含む請求項1~12のいずれか1項に記載のシート。
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WO2019059079A1 (ja) * | 2017-09-20 | 2019-03-28 | 日本製紙株式会社 | アニオン変性セルロースナノファイバーの製造方法 |
JP2019094077A (ja) * | 2017-11-20 | 2019-06-20 | 王子ホールディングス株式会社 | 容器 |
WO2020050346A1 (ja) * | 2018-09-06 | 2020-03-12 | 王子ホールディングス株式会社 | 固形状体、シート及び固形状体の製造方法 |
US20210009771A1 (en) * | 2017-12-19 | 2021-01-14 | Oji Holdings Corporation | Sheet |
JP2021167431A (ja) * | 2018-07-11 | 2021-10-21 | 旭化成株式会社 | セルロース含有樹脂組成物 |
CN113717539A (zh) * | 2021-08-26 | 2021-11-30 | 东莞市凯成环保科技有限公司 | 一种疏水秸秆纤维模塑包装盒材料及包装盒的制备方法 |
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CN105247136B (zh) * | 2013-06-03 | 2019-06-14 | 王子控股株式会社 | 含微细纤维的片材的制造方法 |
CN107923126A (zh) * | 2015-08-05 | 2018-04-17 | 王子控股株式会社 | 片材、片材的制造方法及叠层体 |
KR20200047758A (ko) * | 2015-09-17 | 2020-05-07 | 오지 홀딩스 가부시키가이샤 | 미세 섬유상 셀룰로오스 함유물 |
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JP7258839B2 (ja) * | 2020-12-24 | 2023-04-17 | パナソニックホールディングス株式会社 | 複合樹脂のセルロース複合判別方法及び装置 |
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EP3415553A1 (en) | 2018-12-19 |
JPWO2017138589A1 (ja) | 2018-12-06 |
EP3415553B1 (en) | 2022-01-05 |
US20190055697A1 (en) | 2019-02-21 |
EP3415553A4 (en) | 2019-10-23 |
JP7006278B2 (ja) | 2022-01-24 |
CN108602971A (zh) | 2018-09-28 |
KR102235209B1 (ko) | 2021-04-01 |
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KR20180109083A (ko) | 2018-10-05 |
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