WO2019013147A1 - 水性樹脂組成物及び成形体 - Google Patents
水性樹脂組成物及び成形体 Download PDFInfo
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- WO2019013147A1 WO2019013147A1 PCT/JP2018/025816 JP2018025816W WO2019013147A1 WO 2019013147 A1 WO2019013147 A1 WO 2019013147A1 JP 2018025816 W JP2018025816 W JP 2018025816W WO 2019013147 A1 WO2019013147 A1 WO 2019013147A1
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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
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
Definitions
- the present invention relates to an aqueous resin composition and a molded body containing nanofibers.
- Patent No. 5976249 gazette Patent No. 5733761 gazette
- An object of the present invention is to provide an aqueous resin composition containing nanofibers which can obtain a molded article having excellent transparency and a low linear expansion coefficient.
- the present invention provides the following aqueous resin composition and molded article.
- An aqueous resin composition comprising resin particles, nanofibers, and an aqueous medium, The light transmittance of the resin emulsion in which the concentration of the resin particles is 30% by mass is 80% or more at a wavelength of 600 nm and 40% or more at a wavelength of 400 nm, The aqueous nanofiber composition, wherein the nanofibers have an average aspect ratio of 10 or more and an average fiber diameter of 1 nm or more and 500 nm or less.
- the resin particles are selected from the group consisting of polyurethane resins, (meth) acrylic resins, acrylonitrile-styrene copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, epoxy resins, and mixtures thereof
- nanofibers are at least one fiber selected from the group consisting of organic nanofibers, inorganic nanofibers, and a mixture thereof Composition.
- the resin particles have a zeta potential ⁇ particle of a sample for evaluation (S p ) containing the resin particles of ⁇ 20 mV or less, In the nanofibers, the zeta potential ⁇ fiber of the evaluation sample (S f ) including the nanofibers is ⁇ 20 mV or less.
- a molded article comprising resin particles and nanofibers, wherein When an area of 250 ⁇ m 2 is observed with a scanning electron microscope, the number of aggregates of the nanofibers of 1 ⁇ m 2 or more is 1 or less, The molded object whose distance between the said nanofibers is 10 nm or more and 1000 nm or less, when the area
- water-based resin composition containing the nanofiber which can obtain the molded object which is excellent in transparency and whose linear expansion coefficient is low can be provided.
- the aqueous resin composition of the present invention comprises resin particles, nanofibers and an aqueous medium,
- the light transmittance of the resin emulsion in which the concentration of the resin particles is 30% by mass is 80% or more at a wavelength of 600 nm and 40% or more at a wavelength of 400 nm,
- the nanofibers have an average aspect ratio of 10 or more and an average fiber diameter of 1 nm or more and 500 nm or less.
- the aqueous resin composition comprises resin particles, nanofibers and an aqueous medium.
- the amount of resin particles contained in the aqueous resin composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 3 parts by mass or more in 100 parts by mass of the solid content of the aqueous resin composition. More preferably, it is usually 99 parts by mass or less, and preferably 97 parts by mass or less.
- the resin particle has a light transmittance at a wavelength of 600 nm of 80% or more and 83% or more in a resin emulsion (hereinafter sometimes referred to as "resin emulsion (A)") in which the concentration of the resin particle is 30% by mass. Is preferably 85% or more, more preferably 87% or more, and usually less than 100%.
- the resin particle has a light transmittance at a wavelength of 400 nm of 40% or more, preferably 45% or more, more preferably 50% or more, and usually less than 100%. is there.
- the light transmittance of a molded article produced using the aqueous resin composition can be improved, and the linear expansion coefficient can be reduced.
- the light transmittance can be measured by the measurement method described in the examples below.
- the lower limit value of the primary particle diameter (average particle diameter) of the resin particles contained in the aqueous resin composition is 1 nm or more, preferably 5 nm or more, more preferably 8 nm or more, and 10 nm or more. More preferably, the upper limit value is 60 nm or less, preferably 55 nm or less, and more preferably 50 nm or less.
- the primary particle diameter of the resin particles is a value measured for the resin particles in the aqueous resin composition using a dynamic light scattering type particle size distribution measuring device (FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.) .
- the zeta potential -20 particle of the evaluation sample (S p ) containing the resin particles is preferably ⁇ 20 mV or less, more preferably ⁇ 25 mV or less, and further preferably ⁇ 30 mV or less preferable.
- the zeta potential is known as an indicator of dispersion stability, and in general, the larger the absolute value, the better the dispersion stability.
- the value of the ratio of the zeta potential represented by ⁇ particle / ⁇ fiber is preferably 0.930 or more, more preferably 0.950 or more, and more preferably 0.960 or more as shown in the formula (1). Is more preferably 0.970 or more.
- the value of the ratio of the zeta potential is preferably 1.600 or less, more preferably 1.500 or less, and still more preferably 1.400 or less as shown in the formula (1). And still more preferably 1.300 or less.
- the value of the ratio of the zeta potential When the value of the ratio of the zeta potential is in the above range, the light transmittance of a molded article obtained using the aqueous resin composition can be improved, and the coefficient of linear expansion can be easily reduced.
- the reason is considered as follows. That is, when the value of the ratio of the zeta potential described above is within the above range, the charge of the resin particles and the charge of the nanofibers when the resin particles and the nanofibers are dispersed in the aqueous medium are equal to each other. It can be considered that the size of the Thereby, since a suitable repulsive force is generated between the resin particles and the nanofibers, the resin particles and the nanofibers are less likely to aggregate in the aqueous resin composition, and the dispersion stability of both can be improved.
- the method for preparing an evaluation sample (S p ) containing resin particles, and the zeta potential ⁇ particle of the evaluation sample (S p ) can be measured by the measurement method described in the examples below.
- the resin particles preferably have a negative charge.
- a method of imparting a negative charge to the resin particles a method of using a monomer having an anionic substituent as a monomer component forming the resin particles; in the case where the resin particles are dispersed in a dispersion medium such as water, resin emulsion
- a surfactant such as an emulsifying agent
- the surfactant is adsorbed on the surface of the resin particle, and therefore, the resin particle is negatively charged using a surfactant having a negative charge as the surfactant. And the like.
- the resin particles have a negative charge and the nanofibers have a negative charge, a repulsive force is exerted between the resin particles and the nanofibers, so that the nanofibers in the aqueous resin composition are It is believed that the dispersion stability of the resin component can be enhanced.
- the resin particles are at least one selected from the group consisting of polyurethane resins, (meth) acrylic resins, acrylonitrile-styrene copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, epoxy resins, and mixtures thereof. It is preferable that it is the above particle
- the resin particles are more preferably polyurethane resin.
- “(Meth) acrylic” means at least one selected from acrylic and methacrylic. The same applies to the cases of “(meth) acrylate”, “(meth) acryloyloxy group”, “(meth) acryloyl group” and the like.
- the polyurethane-based resin can be obtained by reacting a polyisocyanate compound and a polyol compound with, if necessary, another compound.
- resin particles of a polyurethane resin are obtained as a resin emulsion, they can be obtained by reacting the above-mentioned compounds by a known acetone method, prepolymer mixing method, ketimine method, hot melt dispersion method or the like.
- the organic polyisocyanate compound which has 2 or more of isocyanate groups in a molecule
- numerator used for manufacture of the common polyurethane is mentioned.
- polyol compound the compound which has 2 or more of hydroxyl groups in a molecule
- numerator used for manufacture of the common polyurethane is mentioned.
- polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane and glycerin; polyethylene glycol, polypropylene glycol, polytetramethylene ether Polyether polyols such as glycols; adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, isophthalic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid Etc., ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol
- Polyester polyols such as polycaprolactone polyol, poly ⁇ -methyl- ⁇ -valerolactone; polybutadiene polyol or hydrogenated product thereof, polycarbonate polyol, polythioether polyol, polyacrylic ester polyol etc. .
- the polyurethane resin preferably has a hydrophilic group in the molecule in order to improve the dispersion stability in an aqueous medium.
- the hydrophilic group may be any of an anionic group, a cationic group, and a nonionic group, but as described above, in the case where it is preferable that the resin particle has a negative charge, it is an anionic group Is preferred.
- the anionic group a sulfonyl group, a carboxy group and the like are preferable, and usually, it is preferable to be neutralized by a neutralizing agent.
- the neutralizing agent include tertiary amine compounds such as triethylamine and triethanolamine; inorganic alkali compounds such as sodium hydroxide; and ammonia.
- the (meth) acrylic resin is a resin having a (meth) acrylate monomer having a (meth) acryloyl group as a main constituent monomer.
- the (meth) acrylate monomer a monofunctional (meth) acrylate monomer having one (meth) acryloyloxy group in the molecule, and a bifunctional (meth) acrylate having two (meth) acryloyloxy groups in the molecule
- Monomers and polyfunctional (meth) acrylate monomers having three or more (meth) acryloyloxy groups in the molecule can be mentioned.
- An example of a monofunctional (meth) acrylate monomer is an alkyl (meth) acrylate.
- alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i- Examples include butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like.
- aralkyl (meth) acrylates such as benzyl (meth) acrylate; (meth) acrylates of terpene alcohols such as isobornyl (meth) acrylate; tetrahydrofurfuryl structures such as tetrahydrofurfuryl (meth) acrylate (meth ) Acrylate; alkyl groups such as cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate (Meth) acrylate having a cycloalkyl group at one site; aminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate; 2-phenoxyethyl (meth) acrylate Acrylate,
- monofunctional alkyl (meth) acrylates having a hydroxyl group at the alkyl site and monofunctional alkyl (meth) acrylates having a carboxyl group at the alkyl site can also be used.
- monofunctional alkyl (meth) acrylate having a hydroxyl group at the alkyl site are 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- Hydroxy-3-phenoxypropyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate.
- monofunctional alkyl (meth) acrylates having a carboxyl group at the alkyl site are 2-carboxyethyl (meth) acrylate, ⁇ -carboxy-polycaprolactone (n ⁇ 2) mono (meth) acrylate, 1- [2- (Meth) acryloyloxyethyl] phthalic acid, 1- [2- (meth) acryloyloxyethyl] hexahydrophthalic acid, 1- [2- (meth) acryloyloxyethyl] succinic acid (2-acryloyloxyethyl succinate, A-SA), 4- [2- (meth) acryloyloxyethyl] trimellitic acid, N- (meth) acryloyloxy-N ', N'-dicarboxymethyl-p-phenylenediamine.
- alkylene glycol di (meth) acrylate As a bifunctional (meth) acrylate monomer, alkylene glycol di (meth) acrylate, polyoxyalkylene glycol di (meth) acrylate, halogen substituted alkylene glycol di (meth) acrylate, di (meth) acrylate of aliphatic polyol, hydrogenated Di (meth) acrylate of dicyclopentadiene or tricyclodecanedialkanol, di (meth) acrylate of dioxane glycol or dioxane dialkanol, di (meth) acrylate of alkylene oxide adduct of bisphenol A or bisphenol F, bisphenol A or bisphenol The epoxy di (meth) acrylate of F etc. are mentioned.
- difunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 , 6-Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, ditrile Methylolpropane di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyester Glycol di (meth) acrylate, polypropylene glycol di (
- glycerin tri (meth) acrylate alkoxylated glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.
- the (meth) acrylamide monomer is preferably a (meth) acrylamide having a substituent at the N-position, a typical example of a substituent at the N-position being an alkyl group, but a nitrogen atom of (meth) acrylamide
- the ring may have an oxygen atom as a ring member.
- N-substituted (meth) acrylamides include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-i-propyl (meth) acrylamide, N- N-alkyl (meth) acrylamides such as n-butyl (meth) acrylamide, N-i-butyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-hexyl (meth) acrylamide; N, N- And N, N-dialkyl (meth) acrylamides such as dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide.
- the substituent at the N-position may be an alkyl group having a hydroxyl group, and examples thereof include N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (2) -Hydroxypropyl) (meth) acrylamide and the like.
- N-substituted (meth) acrylamide which forms a 5- or 6-membered ring
- specific examples thereof include N-acryloyl
- pyrrolidine 3- (meth) acryloyl-2-oxazolidinone
- 4- (meth) acryloyl morpholine N- (meth) acryloyl piperidine and the like.
- An acrylonitrile-styrene copolymer resin is a resin having acrylonitrile and a styrenic monomer as constituent monomers.
- the acrylonitrile-styrene copolymer resin preferably contains 25 to 75 parts by mass of acrylonitrile and 75 to 25 parts by mass of a styrene-based monomer with respect to 100 parts by mass of all the monomers constituting the copolymer.
- styrene-based monomer examples include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, methoxystyrene, chloro Styrene, bromostyrene, fluorostyrene, nitrostyrene, chloromethylstyrene, vinyltoluene, acetoxystyrene, p-dimethylaminomethylstyrene and the like.
- the acrylonitrile-butadiene-styrene copolymer resin is a resin having acrylonitrile, butadiene and a styrenic monomer as constituent monomers.
- the acrylonitrile-butadiene-styrene copolymer resin has 20 to 40 parts by mass of acrylonitrile, 25 to 50 parts by mass of butadiene, and 25 to 50 parts by mass of styrene-based monomer, based on 100 parts by mass of all monomers constituting the copolymer. Is preferred.
- As a styrene-type monomer what was mentioned to the above-mentioned specific example can be used.
- the epoxy resin is not particularly limited as long as it is a compound having two or more glycidyl groups per molecule.
- bisphenol A bisphenol F, 1,1'-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, tetramethylbiphenol, naphthalenediol, etc.
- Ether compounds derived from dihydric phenols glycidyl ester compounds derived from aromatic carboxylic acids such as p-hydroxybenzoic acid, m-hydroxybenzoic acid, terephthalic acid and isophthalic acid, or triglycidyl An isocyanurate etc. can be mentioned.
- novolac epoxy resin derived from novolac resin which is a reaction product of phenols such as phenol, o-cresol, m-cresol, p-cresol and formaldehyde, fluoroglycine And glycidyl ether compounds derived from trivalent or higher phenols such as tris- (4-hydroxyphenyl) -methane and 1,1,2,2-tetrakis (4-hydroxyphenyl).
- phenols such as phenol, o-cresol, m-cresol, p-cresol and formaldehyde
- fluoroglycine And glycidyl ether compounds derived from trivalent or higher phenols such as tris- (4-hydroxyphenyl) -methane and 1,1,2,2-tetrakis (4-hydroxyphenyl).
- the resin emulsion can be produced by a known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, emulsion polymerization and the like.
- the nanofibers have an average aspect ratio (average fiber length / average fiber diameter) of 10 or more, and usually 10000 or less.
- the lower limit of the average fiber diameter of the nanofibers is 1 nm or more, preferably 2 nm or more, and the upper limit is 500 nm or less, preferably 200 nm or less, 50 nm or less More preferable.
- the average fiber length of the nanofibers is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, still more preferably 0.2 ⁇ m or more, and preferably 100 ⁇ m or less.
- the thickness is more preferably 20 ⁇ m or less, and still more preferably 4 ⁇ m or less.
- the average aspect ratio is calculated based on the obtained average fiber length and average fiber diameter.
- the average fiber length of nanofibers can be calculated as follows. Nanofibers are fixed on mica sections, and the length of 200 fibers fixed on mica sections is measured using an atomic force microscope (AFM), and the length (weighted) average fiber length is calculated. In addition, measurement of fiber length is performed in the range of arbitrary length using image analysis software WinROOF (made by Mitani Corporation).
- the average fiber diameter of the nanofibers can be calculated as follows.
- a nanofiber dispersion is prepared by diluting the concentration of nanofibers to 0.001% by mass. This diluted dispersion is thinly spread on a mica sample base and dried by heating to prepare a sample for observation. The observation sample is observed by an atomic force microscope (AFM) to measure the cross-sectional height of the shape image, and the weighted average fiber diameter can be calculated.
- a nanofiber dispersion is prepared by diluting the concentration of nanofibers to 0.001% by mass. This diluted dispersion is thinly spread on a mica sample base and dried by heating to prepare a sample for observation. The observation sample is observed by an atomic force microscope (AFM) to measure the cross-sectional height of the shape image, and the weighted average fiber diameter can be calculated.
- AFM atomic force microscope
- nanofibers include: natural polymer nanofibers such as cellulose nanofibers; organic nanofibers such as synthetic polymer nanofibers such as polyamide resin nanofibers; aluminum hydroxide nanofibers, alumina nanofibers, silica nanofibers, silica Inorganic nanofibers such as acid aluminum nanofibers, titania nanofibers, zirconia nanofibers, carbon nanofibers, etc .; and at least one fiber selected from the group consisting of mixtures thereof are preferable. More preferably, the nanofibers include at least one of cellulose nanofibers and aluminum hydroxide nanofibers.
- Cellulose forming cellulose nanofibers has a ⁇ glucose unit in which a hydroxyl group at the 1-position and a hydroxyl group at the 4-position of ⁇ -glucose are linked by condensation polymerization of a large number of ⁇ -glucose.
- a cellulose nanofiber the cellulose nanofiber which has a carboxylate group, the cellulose nanofiber which does not have a carboxylate group, and these mixtures can be mentioned.
- a carboxylate group-containing cellulose nanofiber As a carboxylate group-containing cellulose nanofiber, the microfibril surface of cellulose is subjected to an oxidation reaction catalyzed by a nitroxy radical species such as TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl radical).
- TEMPO 2,2,6,6-tetramethylpiperidinyl-1-oxyl radical
- oxidized cellulose nanofibers carboxymethyl cellulose (CMC), etc. Can be mentioned.
- the hydroxyl group at the position 2, 3 or 6 of the ⁇ -glucose unit on the surface of the microfibrils of cellulose is a carboxymethyl group (-CH 2 -COOH) or a carboxymethyl sodium group (-CH) 2- COONa) is substituted.
- the cellulose nanofiber which does not have a carboxylate group can be obtained by refine
- the cellulose nanofibers may be reduced oxidized cellulose nanofibers.
- the reduced type oxidized cellulose nanofibers can be obtained, for example, by subjecting the above-mentioned oxidized cellulose nanofibers to reduction treatment.
- reduction treatment oxidized cellulose nanofibers having a ketone group at the 2- and 3-positions of the ⁇ -glucose unit and oxidized cellulose nanofibers having an aldehyde group at the 6-position of the ⁇ -glucose unit in addition to the ketone group
- a reduced oxidized cellulose nanofiber is obtained in which at least a part of the ketone group and / or the aldehyde group is converted to an alcoholic hydroxyl group.
- said ketone group is produced
- said aldehyde group is produced
- the amount of ketone group or the amount of ketone group and aldehyde group in the reduced type oxidized cellulose nanofiber is smaller than the above amount in the oxidized cellulose nanofiber before the reduction step.
- the reduced type oxidized cellulose nanofibers can be produced, for example, by the method described in JP-A-2017-2135.
- polyamide resin nanofibers aluminum hydroxide nanofibers, alumina nanofibers, silica nanofibers, aluminum silicate nanofibers, titania nanofibers, zirconia nanofibers, for example, those produced by a known electrospinning method can be used.
- carbon nanofibers can be used, for example, those manufactured by a known method such as a method of manufacturing from hydrocarbons by a CVD method using transition metal nanoparticles as a catalyst.
- the nanofibers preferably have a negative charge.
- negatively charged nanofibers include carboxylate groups-containing cellulose nanofibers and nanofibers into which a negative charge is introduced by a known method. Since the nanofibers have a negative charge and the resin particles have a negative charge, a repulsive force is exerted between the nanofibers and the resin particles, thereby enhancing the dispersion stability of the nanofibers and the resin component in the aqueous resin composition. It is thought that can be done.
- the zeta potential ⁇ fiber of the evaluation sample (S f ) containing nanofibers is preferably ⁇ 20 mV or less, more preferably ⁇ 23 mV or less, still more preferably ⁇ 25 mV or less, and ⁇ 30 mV or less It is even more preferred that And zeta potential zeta fiber of the evaluation sample (S f) containing nanofibers, and the zeta potential zeta particle of the evaluation sample containing resin particles (S p), is preferably in the relationship of the above formula (1) .
- the pH of the aqueous dispersion of nanofibers can be adjusted with an aqueous sodium hydroxide solution or the like.
- the evaluation sample (S f ) containing nanofibers and the evaluation sample (S f ) zeta potential ⁇ fiber can be measured by the measurement method described in the examples below.
- the aqueous medium is water alone or a mixed solvent containing water as a main component and a component miscible with water.
- miscible components include organic solvents such as alcohol solvents.
- a "main component” means the component with most content (mass%) among the components which make a solvent.
- Additives include, for example, antioxidants, metal deactivators, flame retardants, plasticizers, flame retardant aids, light resistance improvers, slip agents, inorganic fillers, organic fillers, reinforcing agents, pigments and dyes, etc.
- the coloring agent, the mold release agent, the antibacterial agent, the antifungal agent, the viscosity modifier, the ultraviolet absorber, the antistatic agent, etc. may be added singly or in combination of two or more.
- the aqueous resin composition can be obtained by mixing resin particles, nanofibers and an aqueous medium.
- the resin particles may be in the form of a resin emulsion dispersed in an aqueous medium
- the nanofibers may be in the form of a nanofiber dispersion dispersed in an aqueous medium.
- the aqueous medium used for the resin emulsion and the aqueous medium used for the nanofiber dispersion may be the same or different.
- aqueous resin composition examples include a method of adding a resin emulsion or resin particles to a nanofiber dispersion, a method of adding a nanofiber or nanofiber dispersion to a resin emulsion, etc. It is preferred to add a resin emulsion to the dispersion.
- the mixing of the resin particles, the nanofibers and the aqueous medium can be performed using a known stirrer, and can be performed by, for example, a homomixer, a homogenizer, a refiner, a beater, a grinder, an ultrasonic device or the like.
- the temperature at which the resin particles, nanofibers and aqueous medium are stirred is preferably 10 ° C. or more, more preferably 30 ° C. or more, still more preferably 50 ° C. or more, and 60 ° C. or more Most preferably, it is 90 ° C. or less, more preferably 85 ° C. or less.
- the stirring of the above three components is usually 100 rpm or more, preferably 300 rpm or more, more preferably 500 rpm or more, still more preferably 1000 rpm or more, and usually 10000 rpm or less. It is preferably 7,000 rpm or less, more preferably 5,000 rpm or less, and still more preferably 4,000 rpm or less.
- a molded object can be produced using an aqueous resin composition.
- the molded body can be obtained, for example, by drying the aqueous resin composition and removing the aqueous medium.
- the molded body contains resin particles and nanofibers
- the light transmittance of the resin emulsion in which the concentration of the resin particles is 30% by mass is 80% or more at a wavelength of 600 nm and 40% or more at a wavelength of 400 nm
- the nanofibers may have an average aspect ratio of 10 or more and an average fiber diameter of 1 nm or more and 50 nm or less.
- the resin particles preferably have a primary particle diameter of 1 nm or more and 60 nm or less. The description of the resin particles and the nanofibers is the same as that described above.
- the molded body can be a molded body molded into a desired shape such as particulate, granular, pellet, film, plate, spherical, cylindrical, prismatic, conical, pyramidal and the like.
- the formed body is, for example, a method of applying an aqueous resin composition to a substrate surface by a spray or the like and drying to form a film-like formed body, the aqueous resin composition is put into a forming die and dried to have a predetermined shape. It can be produced by a method of forming a molded product, a method of forming a film by injecting the aqueous resin composition into a devolatilizing extruder, and forming a film-shaped molded product.
- the molded body may have a single layer structure or a multilayer structure.
- a plurality of layers produced using the aqueous resin composition may be laminated, and the layer produced using the aqueous resin composition and other than the aqueous resin composition What laminated
- stacked the layer which used the resin composition may be used.
- another layer may be formed by dipping, spraying, spin coating, bar coating or the like, and a molded article having a multilayer structure is produced by coextrusion. It is also good.
- the light transmittance at a wavelength of 400 nm is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more when the molded product is formed into a film having a thickness of 300 ⁇ m.
- the light transmittance at a wavelength of 600 nm is preferably 85% or more, more preferably 87% or more, and still more preferably 90% or more when the molded product is formed into a film shape having a thickness of 300 ⁇ m. .
- the light transmittance of the molded product can be measured by using a spectrophotometer for the light transmittance of the molded product in the thickness direction.
- the above-mentioned molded product has a small linear expansion coefficient measured in the range of room temperature to 200 ° C., it is possible to suppress the shape change and the dimensional change even when used under an environment accompanied by a temperature change.
- an aqueous resin composition in which the light transmittance of the resin emulsion (A) is 80% or more at a wavelength of 600 nm and 40% or more at a wavelength of 400 nm a molded article having excellent light transmittance and linear expansion coefficient You can get Further, by using a resin particle having a primary particle diameter of 1 nm or more and 60 nm or less, it is easy to manufacture a molded article having a high light transmittance and a small linear expansion coefficient.
- the zeta potential zeta particle of the evaluation sample containing resin particles (S p), and, along with the zeta potential zeta fiber samples for evaluation containing nanofibers (S f) is less than -20 mV, the above-mentioned equation (1
- the aqueous resin composition satisfying the above relationship facilitates production of a molded article having a high light transmittance and a small linear expansion coefficient.
- the molded body has one or less aggregate of nanofibers of 1 ⁇ m 2 or more when the region of 250 ⁇ m 2 is observed with a scanning electron microscope.
- the upper limit of the size of the aggregate of nanofibers is, for example, 100 ⁇ m 2 or less, preferably 50 ⁇ m 2 or less. The presence of aggregates larger than this may lead to loss of transparency. Therefore, it is preferable that the number of aggregates over 100 ⁇ m 2 be zero, and it is more preferable that the number of aggregates over 50 ⁇ m 2 be zero.
- the aggregate of nanofibers preferably has one or less aggregate of 0.75 ⁇ m 2 or more, and one aggregate of 0.50 ⁇ m 2 or more
- the number of aggregates of nanofibers of 0.40 ⁇ m 2 or more is more preferably 1 or less.
- the upper limit of the size of the aggregate in this case is also, for example, 100 ⁇ m 2 or less, preferably 50 ⁇ m 2 or less, as described above.
- the distance between nanofibers is preferably 10 nm or more, more preferably 20 nm or more, and 1000 nm or less Is more preferably 800 nm or less, still more preferably 600 nm or less, still more preferably 500 nm or less, and may be 400 nm or less or 300 nm or less.
- the distance between the nanofibers becomes large, it is difficult to reduce the linear expansion coefficient, and when the distance between the nanofibers is too small, the formed body may become brittle.
- the molded product contains resin particles and nanofibers, and the linear expansion coefficient of the molded product is 50 ppm / K or less in the temperature range of 90 ° C. to 100 ° C., and in the temperature range of 190 ° C. to 200 ° C. It may be 70 ppm / K or less.
- the linear expansion coefficient of the molded body is preferably 45 ppm / K or less in a temperature range of 90 ° C. to 100 ° C., more preferably 40 ppm / K or less, and a temperature range of 190 ° C. to 200 ° C. Is preferably 60 ppm / K or less, more preferably 50 ppm / K or less.
- the linear expansion coefficient of a molded object can be measured by the measurement method demonstrated by the Example mentioned later.
- a resin emulsion dispersed in water was prepared so that the concentration of the resin particles was 30% by mass.
- the prepared resin emulsion was placed in a quartz cell with an optical path length of 1 cm, and the light transmittance at a wavelength of 300 nm to 800 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corp.).
- aqueous dispersion of cellulose nanofibers was prepared by diluting the concentration of cellulose nanofibers to 0.001% by mass. This diluted dispersion was thinly spread on a mica sample base, and dried by heating at 50 ° C. to prepare a sample for observation. The observation sample was observed with an atomic force microscope (AFM) to measure the cross-sectional height of the shape image, and the weighted average fiber diameter (nm) was calculated.
- AFM atomic force microscope
- the average fiber length (nm) of the nanofibers was measured as follows. Cellulose nanofibers were fixed on mica sections, and the length of 200 fibers fixed on the sections of mica was measured using an atomic force microscope (AFM) to calculate the length (weighted) average fiber length. The measurement of the fiber length was performed using an image analysis software WinROOF (manufactured by Mitani Corporation). The average aspect ratio (average fiber length / average fiber diameter) of the nanofibers was calculated from the average fiber length (nm) of the obtained nanofibers and the average fiber diameter (nm) of the nanofibers measured above.
- AFM atomic force microscope
- zeta potential ⁇ particle The zeta potential ⁇ particle was measured using the sample for evaluation (S p ) under the following measurement conditions.
- -Measuring device Nano Particle Analyzer SZ-100 (manufactured by HORIBA) ⁇ Measurement cell: Flow cell unit ⁇ Measurement method: Laser Doppler method ⁇ Average electric field: About 16 V / cm Mobility measurement: Measurement at five points of 0.15 mm, 0.325 mm, 0.5 mm, 0.675 mm, and 0.85 mm from the lower end of the measurement cell Integration: Three times at each mobility measurement point Mobility: Calculated from Mori-Okamoto equation ⁇ Zeta potential calculation: Smoluchowski method ⁇ Measurement temperature: about 25 ° C.
- Light transmittance of molded body The prepared 300 ⁇ m thick molded body is cut into a size of 50 mm long and 50 mm wide, and a wavelength of 600 nm in the thickness direction of the cut molded body using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corp.) The light transmittance of 400 nm was measured.
- a section obtained by cutting a prepared 300- ⁇ m-thick molded body into a suitable size is immersed in a 0.5% aqueous solution of ruthenium tetraoxide at room temperature for 12 hours to stain nanofibers in the molded body, and then using a microtome.
- a thin section for transmission electron microscope observation of the molded body was produced so as to have a thickness of about 100 nm, to obtain a sample for observation.
- Samples for observation were observed for 10 fields of view under conditions of an acceleration voltage of 30 kV and magnifications of 5000 times and 50000 times using a field emission scanning electron microscope (FE-SEM) (S-4800, manufactured by Hitachi High-Technologies Corporation) The image was taken to obtain an electron microscope image. The number of aggregates of nanofibers was calculated by the following procedure using the obtained electron microscope image, and the distance between the nanofibers was measured.
- FE-SEM field emission scanning electron microscope
- the number of aggregates of nanofibers having an area of 1 ⁇ m 2 or more was counted in an electron microscope image of 10 fields of view in which an area of 250 ⁇ m 2 was observed at a magnification of 5000 ⁇ .
- the area of the aggregate is the area of the portion appearing black in the electron microscope image, and in calculating the area, it is assumed that the portion appearing black is circular, and the largest portion of the image appears black.
- the diameter and the length of the portion having the minimum diameter were measured, and the area was calculated on the assumption that the sum of the lengths of both and dividing by 2 is the diameter.
- a binarization process is performed so that the ratio of the portion appearing as nanofibers in the image is equal to the addition ratio for each of the electron microscope images of 10 fields of observation of the area of 4 ⁇ m 2 at a magnification of 50000 ⁇ did.
- a line perpendicular to the direction in which the nanofibers are most oriented (hereinafter referred to as “orthogonal line”) is drawn to an arbitrary position by an arbitrary number, The distance between nanofibers adjacent to each other on each orthogonal line was calculated using the image analysis software WinROOF (manufactured by Mitani Corp.).
- the distance between adjacent nanofibers was calculated as the distance between the middle points of the length in the direction of the orthogonal line of the nanofibers (the width of the nanofibers).
- the distance between adjacent nanofibers was calculated at a total of 100 locations so as to include at least 10 arbitrary locations on one orthogonal line, and the average value was defined as the distance between the nanofibers.
- Example 1 Manufacture of nanofibers
- Softwood unbleached kraft pulp (whiteness 85%) 500 g (absolutely dry) is added to 500 ml of an aqueous solution of 780 mg of TEMPO (Sigma Aldrich) and 75.5 g of sodium bromide, and the pulp is uniformly dispersed. Stir until.
- an aqueous solution of sodium hypochlorite was added to 6.0 mmol / g to start the oxidation reaction.
- the pH in the system decreased, but 3M aqueous sodium hydroxide solution was sequentially added to adjust to pH 10. The reaction was terminated when sodium hypochlorite was consumed and the pH in the system did not change.
- the mixture after reaction was filtered through a glass filter for pulp separation, and the pulp was thoroughly washed with water to obtain oxidized pulp (carboxylated cellulose).
- the pulp yield at this time was 90%, the time required for the oxidation reaction was 90 minutes, and the amount of carboxyl groups was 1.6 mmol / g.
- the oxidized pulp obtained in the above step is adjusted to 1.0% (w / v) with water and treated three times with an ultrahigh pressure homogenizer (20 ° C., 150 MPa) to obtain water of carboxylate group-containing cellulose nanofibers Dispersion 1 (hereinafter sometimes referred to as “nanofiber aqueous dispersion 1”) was obtained.
- the average fiber diameter, the average aspect ratio, and the zeta potential ⁇ ⁇ ⁇ ⁇ fiber were measured for the obtained fibers by the above-described procedure. As a result, the average fiber diameter was 4 nm, the average fiber length was 500 nm, the average aspect ratio was 125, and ⁇ fiber was ⁇ 36.3 mV.
- the aqueous dispersion 1 of nanofibers and the resin emulsion were used such that the amount of the nanofibers was 5 parts by mass and the amount of the resin particles was 95 parts by mass with respect to 100 parts by mass of the solid content of the aqueous resin composition.
- the primary particle diameter, light transmittance, and zeta potential ⁇ particle of the resin emulsion (a) used were measured according to the above-mentioned procedure to calculate ⁇ particle / ⁇ fiber . The results are shown in Tables 1 and 2.
- the obtained aqueous resin composition was charged into a petri dish, the aqueous medium was removed at a temperature of 50 ° C., and a film-like molded product having a thickness of 300 ⁇ m was obtained.
- the light transmittance and the coefficient of linear expansion of the obtained molded product were measured by the above-described procedure. The results are shown in Table 2.
- Example 2 The aqueous dispersion 1 of the nanofibers and the resin latex (a) were used such that the nanofibers were 10 parts by mass and the resin particles were 90 parts by mass with respect to 100 parts by mass of the solid content of the aqueous resin composition
- An aqueous resin composition and a molded body were obtained in the same manner as in Example 1 except for the above.
- the primary particle diameter, light transmittance, zeta potential ⁇ particle and light transmittance and linear expansion coefficient of the molded product of the resin emulsion used were measured by the above-mentioned procedure to calculate ⁇ particle / ⁇ fiber . The results are shown in Tables 1 and 2.
- Example 2 an electron microscope image was taken according to the procedure of the above-mentioned [observation of nanofibers in the molded body]. It was confirmed that the electron microscope images obtained from 10 fields of view were all substantially the same. Representative images of the obtained electron microscope images are shown in FIGS. 1 (a) and (b) (magnifications are 5000 ⁇ and 50000 ⁇ , respectively). In addition, the number of aggregates of nanofibers having a diameter of 1 ⁇ m 2 or more calculated according to the above-described procedure was 0, and the distance between the nanofibers was 140 nm.
- Example 3 Manufacture of nanofibers
- the pH of the “water dispersion 1 of nanofibers” obtained in Example 1 is adjusted to pH 10 using a 0.5 M aqueous solution of sodium hydroxide, and then the solid content of cellulose nanofibers is 100% by mass. 5% by mass of sodium borohydride was added, and the reaction was carried out for 24 hours with stirring at room temperature (20 to 25 ° C.) to obtain a reduced cellulose nanofiber dispersion.
- the reduced cellulose nanofiber dispersion was dried in a constant temperature drier at 105 ° C. for 3 to 4 hours to obtain a dried solid of reduced cellulose nanofibers.
- the dried solid of the reduced cellulose nanofibers was suspended in water to prepare a slurry having a solid content of 1% by mass.
- the obtained slurry was stirred at 6,000 rpm for 10 minutes using a homomixer to obtain a reduced dispersion type cellulose nanofiber dispersion (water dispersion 2 of nanofibers) having a solid content of 1% by mass after redispersion.
- the average fiber diameter, the average aspect ratio, and the zeta potential ⁇ ⁇ ⁇ ⁇ fiber were measured for the obtained fibers by the above-described procedure. As a result, the average fiber diameter was 4 nm, the average fiber length was 500 nm, the aspect ratio was 125, and ⁇ fiber was -42.7 mV.
- aqueous resin composition (Production of aqueous resin composition) An aqueous resin composition and a molded body were obtained in the same manner as in Example 2 except that the aqueous dispersion of reduced cellulose nanofibers obtained above was used as the aqueous dispersion of nanofibers.
- the primary particle diameter, light transmittance, zeta potential ⁇ particle and light transmittance and linear expansion coefficient of the molded product of the resin emulsion used were measured by the above-mentioned procedure to calculate ⁇ particle / ⁇ fiber . The results are shown in Tables 1 and 2.
- Comparative Example 5 An aqueous resin composition was prepared in the same manner as in Example 1, except that the aqueous dispersion of reduced cellulose nanofibers obtained in Example 3 was used and the resin latex (b) shown in Table 2 was used as the resin latex. An object and a molded body were obtained. The primary particle diameter, light transmittance, zeta potential ⁇ particle and light transmittance and linear expansion coefficient of the molded product of the resin emulsion used were measured by the above-mentioned procedure to calculate ⁇ particle / ⁇ fiber . The results are shown in Tables 1 and 2.
- the resin emulsions (a) to (e) in Tables 1 and 2 are all resin emulsions containing a urethane resin, and Resin emulsion (a): U-coat UWS-145, Sanyo Chemical Industries, Ltd., anionic resin emulsion (b): Superflex 460, Dai-ichi Kogyo Seiyaku Co., Ltd., anionic resin emulsion (c): Permarin UA-150, Sanyo Chemical Industries, Ltd.
- Example 2 As shown in Table 2, in Examples 1 to 3, a molded article excellent in light transmittance at 600 nm and 400 nm and excellent in linear expansion coefficient in the range of 90 to 100 ° C. and in the range of 190 to 200 ° C. can be obtained. I understand. Further, from the results of observation of the formed body using an electron microscope image (see FIGS. 1 (a) and 1 (b)), the formed body obtained in Example 2 is a dispersion of nanofibers in the formed body. It turns out that it is excellent in sex.
Abstract
Description
〔1〕 樹脂粒子とナノファイバーと水性媒体とを含む水性樹脂組成物であって、
前記樹脂粒子の濃度が30質量%である樹脂エマルションの光線透過率が、波長600nmにおいて80%以上であるとともに、波長400nmにおいて40%以上であり、
前記ナノファイバーは、平均アスペクト比が10以上であるとともに、平均繊維径が1nm以上500nm以下である、水性樹脂組成物。
前記ナノファイバーは、前記ナノファイバーを含む評価用試料(Sf)のゼータ電位ζfiberが、-20mV以下であり、
前記ゼータ電位ζparticle及び前記ゼータ電位ζfiberは、下記式(1)の関係を満たす、〔1〕~〔6〕のいずれかに記載の水性樹脂組成物。
〔8〕 〔1〕~〔7〕のいずれかに記載の水性樹脂組成物を用いて作製された成形体。
250μm2の領域を走査型電子顕微鏡で観察したときに、1μm2以上の前記ナノファイバーの凝集体が1個以下であり、
4μm2の領域を走査型電子顕微鏡で観察したときに、前記ナノファイバー間の距離が10nm以上1000nm以下である、成形体。
樹脂粒子の濃度が30質量%である樹脂エマルションの光線透過率は、波長600nmにおいて80%以上であるとともに、波長400nmにおいて40%以上であり、
ナノファイバーは、平均アスペクト比が10以上であるとともに、平均繊維径が1nm以上500nm以下である。
水性樹脂組成物は、樹脂粒子とナノファイバーと水性媒体とを含む。水性樹脂組成物に含まれる樹脂粒子は、水性樹脂組成物の固形分100質量部中、1質量部以上であることが好ましく、2質量部以上であることがより好ましく、3質量部以上であることがより好ましく、また、通常99質量部以下であり、97質量部以下であることが好ましい。
樹脂粒子は、樹脂粒子の濃度が30質量%である樹脂エマルション(以下、「樹脂エマルション(A)」ということがある。)において、波長600nmにおける光線透過率が80%以上であり、83%以上であることが好ましく、85%以上であることがより好ましく、87%以上であることがさらに好ましく、通常100%未満である。また、樹脂粒子は、樹脂エマルション(A)において、波長400nmにおける光線透過率が40%以上であり、45%以上であることが好ましく、50%以上であることがさらに好ましく、通常100%未満である。樹脂エマルション(A)が上記範囲であることにより、水性樹脂組成物を用いて作製された成形体の光線透過率を向上することができ、線膨張率を低減することができる。光線透過率は、後述の実施例で説明する測定方法によって測定することができる。
0.930≦ζparticle/ζfiber≦1.600 (1)
の関係にあることが好ましい。ζparticle/ζfiberで表されるゼータ電位の比の値は、式(1)に示すように0.930以上であることが好ましく、0.950以上であることがより好ましく、0.960以上であることがさらに好ましく、0.970以上であることがさらにより好ましい。また、上記ゼータ電位の比の値は、式(1)に示すように1.600以下であることが好ましく、1.500以下であることがより好ましく、1.400以下であることがさらに好ましく、1.300以下であることがさらにより好ましい。
ナノファイバーは、平均アスペクト比(平均繊維長/平均繊維径)が10以上であり、通常10000以下である。また、ナノファイバーは、平均繊維径の下限値が1nm以上であり、2nm以上であることが好ましく、また、上限値が500nm以下であり、200nm以下であることが好ましく、50nm以下であることがより好ましい。ナノファイバーの平均繊維長は、0.01μm以上であることが好ましく、0.1μm以上であることがより好ましく、0.2μm以上であることがさらに好ましく、また、100μm以下であることが好ましく、20μm以下であることがより好ましく、4μm以下であることがさらに好ましい。平均アスペクト比は、得られた平均繊維長及び平均繊維径に基づいて算出する。
水性媒体は、水単独、又は、水を主成分とし水と混和性のある成分を含む混合溶媒である。混和性のある成分としては、アルコール系溶媒等の有機溶媒を挙げることができる。なお、「主成分」とは、溶媒をなす成分のうち最も含有量(質量%)の多い成分をいう。
水性樹脂組成物には、必要に応じて一般的な添加剤を添加することができる。添加剤としては、例えば、酸化防止剤、金属不活性剤、難燃剤、可塑剤、難燃助剤、耐光性改良剤、スリップ剤、無機充填剤、有機充填剤、強化材、顔料や染料等の着色剤、離型剤、抗菌剤、抗かび剤、粘度調整剤、紫外線吸収剤、帯電防止剤等を、単独で又は2種以上を混合して添加することができる。
水性樹脂組成物は、樹脂粒子とナノファイバーと水性媒体とを混合することによって得ることができる。樹脂粒子は、水性媒体に分散した樹脂エマルションの形態であってもよく、ナノファイバーは、水性媒体に分散したナノファイバー分散体の形態であってもよい。この場合、樹脂エマルションに用いる水性媒体と、ナノファイバー分散体に用いる水性媒体とは、同じであってもよく異なっていてもよい。水性樹脂組成物は、例えば、ナノファイバー分散体に、樹脂エマルション又は樹脂粒子を添加する方法、樹脂エマルションにナノファイバー又はナノファイバー分散体を添加する方法等を挙げることができるが、ナノファイバーの水分散体に樹脂エマルジョンを添加することが好ましい。樹脂粒子とナノファイバーと水性媒体との混合は、公知の撹拌機を使用して行うことができ、例えば、ホモミキサー、ホモジナイザー、リファイナー、ビーター、グラインダー、超音波装置等によって行うことができる。
成形体は、水性樹脂組成物を用いて作製することができる。成形体は、例えば、水性樹脂組成物を乾燥し、水性媒体を除去して得ることができる。
樹脂粒子の濃度が30質量%である樹脂エマルションの光線透過率は、波長600nmにおいて80%以上であるとともに、波長400nmにおいて40%以上であり、
ナノファイバーは、平均アスペクト比が10以上であるとともに、平均繊維径が1nm以上50nm以下であるものであってもよい。樹脂粒子は、1次粒子径が1nm以上60nm以下であることが好ましい。樹脂粒子及びナノファイバーの説明については、上記した説明と同様である。
樹脂粒子の濃度が30質量%となるように水に分散した樹脂エマルションを用意した。用意した樹脂エマルションを光路長1cmの石英セルに入れ、波長300nm~800nmにおける光線透過率を分光光度計U-4100((株)日立ハイテクノロジーズ製)を用いて測定した。
動的光散乱式粒径分布測定装置(「FPAR-1000」大塚電子(株)製)を用い、水性樹脂組成物中の粒子の1次粒子径が測定できるように水性樹脂組成物を水で希釈して、水性樹脂組成物中の粒子の1次粒子径(平均粒子径)を測定した。
セルロースナノファイバーの濃度が0.001質量%となるように希釈したセルロースナノファイバー水分散液を調製した。この希釈分散液をマイカ製試料台に薄く延ばし、50℃で加熱乾燥させて観察用試料を作製した。この観察用試料を原子間力顕微鏡(AFM)で観察して形状像の断面高さを計測し、加重平均繊維径(nm)を算出した。
ナノファイバーの平均繊維長(nm)は、次のようにして測定した。セルロースナノファイバーをマイカ切片上に固定し、原子間力顕微鏡(AFM)を用いて、マイカ切片上に固定された200本の繊維長を測定し、長さ(加重)平均繊維長を算出した。なお、繊維長の測定は、画像解析ソフトWinROOF(三谷商事社製)を用いて行った。得られたナノファイバーの平均繊維長(nm)と上記で測定したナノファイバーの平均繊維径(nm)とから、ナノファイバーの平均アスペクト比(平均繊維長/平均繊維径)を算出した。
(評価用試料(Sp)の準備)
約pH6の超純水に塩化ナトリウムを加えて10mMの塩化ナトリウム水溶液を調製した。この塩化ナトリウム水溶液に、0.1N又は0.01Nの水酸化ナトリウム水溶液を添加して、pHを7に調整したpH調整液を得た。このpH調整液10mLに対し、樹脂粒子の濃度が0.12質量%となるように樹脂エマルションを混合して調製した電気泳動液を作製し評価用試料(Sp)とした。
評価用試料(Sp)を用いて、下記の測定条件でゼータ電位ζparticleを測定した。
・測定装置:Nano Particle Analyzer SZ-100(HORIBA製)
・測定セル:フローセルユニット
・測定法:レーザードップラー法
・平均電場:約16V/cm
・移動度測定:測定セルの下端から、0.15mm、0.325mm、0.5mm、0.675mm、0.85mmの5ポイントにおいて測定
・積算:移動度測定の各ポイントで3回
・真の移動度:森・岡本の式より計算
・ゼータ電位計算:Smoluchowski法
・測定温度:約25℃。
pH調整液に添加する成分を、樹脂エマルションに代えて、ナノファイバーの濃度が1質量%であるナノファイバーの水分散体として、ナノファイバーの濃度が0.12質量%となるように調製した電気泳動液を作製したこと以外は、上記(評価用試料(Sp)の準備)と同様の手順で評価用試料(Sf)を得た。得られた評価用試料(Sf)を用いて、上記(ゼータ電位ζparticleの測定)に記載した測定条件でゼータ電位ζfiberを測定した。
作製した厚み300μmの成形体を縦50mm、横50mmの大きさにカットし、分光光度計U-4100((株)日立ハイテクノロジーズ製)を用いて、カットした成形体の厚み方向における波長600nm及び400nmの光線透過率を測定した。
作製した厚み300μmの成形体を縦20mm、横5mmの大きさにカットし、70℃の真空乾燥オーブンにて24時間以上真空乾燥した。真空乾燥した成形体について、セイコーインスツル(株)社製 TMA6100型を用い、引張モードにて、90~100℃(90℃以上100℃以下)及び190~200℃(190℃以上200℃以下)の範囲における線膨張率を測定した。この際、昇温速度を5℃/minとし、50mL/minの流量で窒素を供給しながら窒素雰囲気下で測定を行った。
作製した厚み300μmの成形体を適当な大きさに切り出した切片を、0.5%四酸化ルテニウム水溶液に室温で12時間浸漬して、成形体中のナノファイバーを染色した後、ミクロトームを用いて厚み約100nmとなるように成形体の透過電子顕微鏡観察用薄片を作製して、観察用サンプルを得た。観察用サンプルを、電界放出型走査電子顕微鏡(FE-SEM)(S-4800、株式会社日立ハイテクノロジーズ製)を用いて、加速電圧30kV、倍率5000倍及び50000倍の条件で、それぞれ10視野について撮影を行い、電子顕微鏡画像を得た。得られた電子顕微鏡画像を用いて、次の手順でナノファイバーの凝集体の個数を算出し、ナノファイバー間の距離を測定した。
倍率5000倍で、250μm2の領域を観察した10視野の電子顕微鏡画像において、面積1μm2以上のナノファイバーの凝集体の個数を数えた。なお、凝集体の面積は、電子顕微鏡画像において黒く表れた部分の面積であり、面積の算出にあたっては、この黒く表れた部分が円形状であると仮定し、画像中の黒く表れた部分において最大径及び最小径となる部分の長さを測定し、両者の長さを足し合わせて2で除したものが直径であると仮定して、面積を算出した。
倍率50000倍で、4μm2の領域を観察した10視野の電子顕微鏡画像のそれぞれに対し、画像中のナノファイバーとして現れた部分の割合が、その添加割合に等しくなるように二値化処理を施した。次いで、二値化処理を施した画像において、ナノファイバーが最も配向している方向に対して直交する線(以下、「直交線」という。)を任意の箇所に、任意の本数引き、それぞれの直交線と交わるナノファイバーについて、各直交線上で隣り合うナノファイバー同士の間の距離を、画像解析ソフトWinROOF(三谷商事社製)を用いて算出した。このとき、隣り合うナノファイバー同士の間の距離は、ナノファイバーの直交線の方向の長さ(ナノファイバーの幅)の中点間の距離として算出した。1つの直交線上において少なくとも任意の10箇所を含むようにして、合計100箇所について隣り合うナノファイバー同士の間の距離を算出し、その平均値をナノファイバー間の距離とした。
(ナノファイバーの製造)
針葉樹由来の漂白済み未叩解クラフトパルプ(白色度85%)500g(絶乾)をTEMPO(Sigma Aldrich社)780mgと臭化ナトリウム75.5gとを溶解した水溶液500mlに加え、パルプが均一に分散するまで撹拌した。次いで次亜塩素酸ナトリウム水溶液を6.0mmol/gになるように添加し、酸化反応を開始した。反応中は系内のpHが低下するが、3M水酸化ナトリウム水溶液を逐次添加し、pH10に調整した。次亜塩素酸ナトリウムが消費され、系内のpHが変化しなくなった時点で反応を終了した。反応後の混合物をガラスフィルターで濾過してパルプ分離し、パルプを十分に水洗することで酸化されたパルプ(カルボキシル化セルロース)を得た。この時のパルプ収率は90%であり、酸化反応に要した時間は90分、カルボキシル基量は1.6mmol/gであった。
上記で得られたナノファイバーの水分散体1を温度80℃で1時間撹拌した後、ナノファイバーの水分散体1の撹拌を行いながら、ウレタン系樹脂の樹脂粒子を含む樹脂エマルション(a)(ユーコートUWS-145、三洋化成社製)を滴下した。その後、さらに温度80℃で1時間撹拌して、室温に冷却して水性樹脂組成物を得た。上記ナノファイバーの水分散体1及び上記樹脂エマルションは、水性樹脂組成物の固形分100質量部に対して、ナノファイバーが5質量部、樹脂粒子が95質量部となるように用いた。用いた樹脂エマルション(a)の1次粒子径、光線透過率、及びゼータ電位ζparticleを、上記した手順で測定し、ζparticle/ζfiberを算出した。その結果を表1及び表2に示す。
得られた水性樹脂組成物をシャーレに投入し、温度50℃で水性媒体を除去し、厚み300μmのフィルム状の成形体を得た。得られた成形体について、上記した手順で、光線透過率及び線膨張率を測定した。その結果を表2に示す。
水性樹脂組成物の固形分100質量部に対して、ナノファイバーが10質量部、樹脂粒子が90質量部となるように、上記ナノファイバーの水分散体1及び上記樹脂ラテックス(a)を用いたこと以外は、実施例1と同様にして水性樹脂組成物及び成形体を得た。用いた樹脂エマルションの1次粒子径、光線透過率、及びゼータ電位ζparticle、成形体の光線透過率及び線膨張率を、上記した手順で測定し、ζparticle/ζfiberを算出した。その結果を表1及び表2に示す。
樹脂ラテックスとして表2に示す樹脂ラテックス(b)~(e)を用いたこと以外は、実施例1と同様にして、水性樹脂組成物及び成形体を得た。用いた樹脂エマルションの1次粒子径、光線透過率、及びゼータ電位ζparticle、成形体の光線透過率及び線膨張率を、上記した手順で測定し、ζparticle/ζfiberを算出した。その結果を表1及び表2に示す。
(ナノファイバーの製造)
実施例1で得た「ナノファイバーの水分散体1」のpHを、0.5Mの水酸化ナトリウム水溶液を用いてpH10に調整した後、セルロースナノファイバーの固形分100質量%に対して2.5質量%の水素化ホウ素ナトリウムを加え、室温(20~25℃)で撹拌しながら反応を24時間行い、還元型セルロースナノファイバー分散体を得た。この還元型セルロースナノファイバー分散体を、105℃の恒温乾燥機中で3~4時間乾燥させ、還元型セルロースナノファイバーの乾燥固形物を得た。さらにこの還元型セルロースナノファイバーの乾燥固形物を水に懸濁して、固形分含量が1質量%のスラリーを調製した。得られたスラリーを、ホモミキサーを用いて6000rpmで10分間撹拌し、固形分含量が1質量%の再分散後の還元型セルロースナノファイバー分散体(ナノファイバーの水分散体2)を得た。得られた繊維について、上記した手順で、平均繊維径、平均アスペクト比、ゼータ電位ζfiberを測定した。その結果、平均繊維径が4nm、平均繊維長が500nm、アスペクト比が125、ζfiberが-42.7mVであった。
ナノファイバーの水分散体として、上記で得られた還元されたセルロースナノファイバーの水分散体を用いこと以外は実施例2と同様にして水性樹脂組成物及び成形体を得た。用いた樹脂エマルションの1次粒子径、光線透過率、及びゼータ電位ζparticle、成形体の光線透過率及び線膨張率を、上記した手順で測定し、ζparticle/ζfiberを算出した。その結果を表1及び表2に示す。
実施例3で得られた還元されたセルロースナノファイバーの水分散体を用い、樹脂ラテックスとして表2に示す樹脂ラテックス(b)を用いたこと以外は、実施例1と同様にして、水性樹脂組成物及び成形体を得た。用いた樹脂エマルションの1次粒子径、光線透過率、及びゼータ電位ζparticle、成形体の光線透過率及び線膨張率を、上記した手順で測定し、ζparticle/ζfiberを算出した。その結果を表1及び表2に示す。
樹脂エマルション(a):ユーコートUWS-145、三洋化成社製、アニオン性
樹脂エマルション(b):スーパーフレックス460、第一工業製薬社製、アニオン性
樹脂エマルション(c):パーマリンUA-150、三洋化成社製、アニオン性
樹脂エマルション(d):スーパーフレックス420NS、第一工業製薬社製、アニオン性
樹脂エマルション(e):スーパーフレックス300、第一工業製薬社製、アニオン性を表す。
Claims (10)
- 樹脂粒子とナノファイバーと水性媒体とを含む水性樹脂組成物であって、
前記樹脂粒子の濃度が30質量%である樹脂エマルションの光線透過率が、波長600nmにおいて80%以上であるとともに、波長400nmにおいて40%以上であり、
前記ナノファイバーは、平均アスペクト比が10以上であるとともに、平均繊維径が1nm以上500nm以下である、水性樹脂組成物。 - 前記樹脂粒子は、1次粒子径が1nm以上60nm以下である、請求項1に記載の水性樹脂組成物。
- 前記樹脂粒子は、ポリウレタン系樹脂、(メタ)アクリル系樹脂、アクリロニトリル-スチレン共重合体系樹脂、アクリロニトリル-ブタジエン-スチレン共重合体系樹脂、エポキシ系樹脂、及びこれらの混合物からなる群より選ばれる少なくとも1種以上の粒子である、請求項1又は2に記載の水性樹脂組成物。
- 前記ナノファイバーは、有機ナノファイバー、無機ナノファイバー、及びこれらの混合物からなる群より選ばれる少なくとも1種以上のファイバーである、請求項1~3のいずれか1項に記載の水性樹脂組成物。
- 前記ナノファイバーは、セルロースナノファイバーを含む、請求項1~4のいずれか1項に記載の水性樹脂組成物。
- 前記樹脂粒子及び前記ナノファイバーは、負電荷を有する、請求項1~5のいずれか1項に記載の水性樹脂組成物。
- 前記樹脂粒子は、前記樹脂粒子を含む評価用試料(Sp)のゼータ電位ζparticleが、-20mV以下であり、
前記ナノファイバーは、前記ナノファイバーを含む評価用試料(Sf)のゼータ電位ζfiberが、-20mV以下であり、
前記ゼータ電位ζparticle及び前記ゼータ電位ζfiberは、下記式(1)の関係を満たす、請求項1~6のいずれか1項に記載の水性樹脂組成物。
0.930≦ζparticle/ζfiber≦1.600 (1) - 請求項1~7のいずれか1項に記載の水性樹脂組成物を用いて作製された成形体。
- 厚み300μmのフィルム形状とした場合の光線透過率が、波長400nmにおいて50%以上であるとともに、波長600nmにおいて85%以上である、請求項8に記載の成形体。
- 樹脂粒子とナノファイバーとを含む成形体であって、
250μm2の領域を走査型電子顕微鏡で観察したときに、1μm2以上の前記ナノファイバーの凝集体が1個以下であり、
4μm2の領域を走査型電子顕微鏡で観察したときに、前記ナノファイバー間の距離が10nm以上1000nm以下である、成形体。
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JP2017043647A (ja) * | 2015-08-24 | 2017-03-02 | 第一工業製薬株式会社 | セルロースエステル水性分散体 |
JP2017043648A (ja) * | 2015-08-24 | 2017-03-02 | 第一工業製薬株式会社 | セルロースエステル水性分散体 |
JP2017043571A (ja) * | 2015-08-28 | 2017-03-02 | 四国化成工業株式会社 | 1,3,4,6−テトラキス((メタ)アクリロイルオキシアルキル)グリコールウリル化合物、その合成方法および該グリコールウリル化合物の利用 |
JP2017025283A (ja) * | 2015-11-25 | 2017-02-02 | 第一工業製薬株式会社 | セルロースエステル水性分散体 |
JP2017043750A (ja) * | 2015-11-25 | 2017-03-02 | 第一工業製薬株式会社 | セルロースエステル水性分散体 |
JP2017115047A (ja) * | 2015-12-25 | 2017-06-29 | 第一工業製薬株式会社 | セルロースナノファイバーおよび樹脂組成物 |
JP5976249B1 (ja) * | 2016-03-30 | 2016-08-23 | 第一工業製薬株式会社 | 水分散体およびコーティング材 |
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JP2020152755A (ja) * | 2019-03-18 | 2020-09-24 | 大王製紙株式会社 | スプレー用溶液及びスプレー容器 |
JP2020200436A (ja) * | 2019-10-07 | 2020-12-17 | サイデン化学株式会社 | 複合樹脂組成物 |
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JP7162589B2 (ja) | 2022-10-28 |
JPWO2019013147A1 (ja) | 2020-07-02 |
KR20200028428A (ko) | 2020-03-16 |
KR102537413B1 (ko) | 2023-05-26 |
CN110869448A (zh) | 2020-03-06 |
CN110869448B (zh) | 2022-06-17 |
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