阅读说明：本技术 纤维状纤维素、含纤维状纤维素之组合物、含纤维状纤维素之分散液及纤维状纤维素的制造方法 (The manufacturing method of fibrous cellulose, the composition of fibrousness cellulose, the dispersion liquid of fibrousness cellulose and fibrous cellulose ) 是由 赵孟晨 轰雄右 野口裕一 杉山郁绘 于 2018-03-01 设计创作，主要内容包括：本发明之课题在于提供一种于有机溶剂中亦可发挥良好之分散性之微细纤维状纤维素。本发明系关于一种纤维状纤维素,该纤维状纤维素之纤维宽为1000nm以下,且具有磷酸基或来源于磷酸基之取代基,并且磷酸基或来源于磷酸基之取代基之含量为0.5mmol/g以上,利用测定方法(a)所测定之上清产率为70％以下。(The project of the present invention is to provide a kind of microfibre shape cellulose that can also play good dispersibility in organic solvent.The present disclosure generally relates to a kind of fibrous celluloses, the fiber width of the fibrous cellulose is 1000nm or less, and with phosphate or from the substituent group of phosphate, and the content of phosphate or the substituent group from phosphate is 0.5mmol/g or more, is 70% or less using the supernatant yield that measuring method (a) measures.)

1. a kind of fibrous cellulose, fiber width is 1000nm hereinafter, and with phosphate or from the substitution of phosphate Base；

The content of aforementioned phosphate base or the substituent group from phosphate is 0.5mmol/g or more；

Aforementioned fibrous cellulose is 70% or less using the supernatant yield that following measuring methods (a) measure；

Measuring method (a):

The aqueous dispersions A for preparing the aforementioned fibrous cellulose that solid component concentration is 0.5 mass %, uses defibrating processing device 30 minutes defibrating processings are carried out with 21500 revs/min of condition, obtain aqueous dispersions B；Then, aforementioned aqueous dispersions B is made solid Body constituent concentration is the aqueous dispersions C of 0.2 mass %, carries out 10 minutes centrifuging treatments with 12000G, 15 DEG C of condition, returns Receive supernatant；The solid component concentration for measuring the supernatant recycled calculates supernatant yield according to following formula；

Supernatant yield (%)=supernatant solid component concentration (quality %)/0.2 (quality %) × 100.

2. fibrous cellulose according to claim 1, wherein aforementioned fibrous fiber prime system includes to be selected to contain carbon number At least one of the organic ion for being 17 or more for the organic ion of 5 or more alkyl and total carbon number is used as aforementioned phosphorus The counter ion counterionsl gegenions of acidic group or the substituent group from phosphate.

3. fibrous cellulose according to claim 2, wherein aforementioned organic ion is organic ammonium.

It is containing 85 mass % or more according to claim 1 to any in 3 4. a kind of composition of fibrousness cellulose Fibrous cellulose described in.

5. a kind of dispersion liquid of fibrousness cellulose, is containing threadiness according to any one of claim 1 to 3 Cellulose and organic solvent.

6. the dispersion liquid of fibrousness cellulose according to claim 5, wherein aforementioned organic solvents are opposite in 25 DEG C Dielectric constant is 60 or less.

7. a kind of manufacturing method of fibrous cellulose, comprising the following steps:

There to be the phosphate of 0.5mmol/g or more or derive from the fibrous cellulose of the substituent group of phosphate in water solvent The step of middle carry out defibrating processing, acquisition includes the aqueous dispersions for the fibrous cellulose that fiber width is 1000nm or less；And

By selected from the alkyl for being 5 or more containing carbon number organic ion and total carbon number be 17 or more organic ion in At least one is added to the step in aforementioned aqueous dispersions.

Technical field

The present disclosure generally relates to a kind of fibrous cellulose, the composition of fibrousness cellulose, fibrous cellulose dispersions The manufacturing method of liquid and fibrous cellulose.Specifically, the present disclosure generally relates to the fibers that a kind of fiber width is 1000nm or less Shape cellulose, the composition of fibrousness cellulose, fibrous cellulose dispersion liquid and fiber width are the fiber of 1000nm or less The manufacturing method of shape cellulose.

Background technique

Previously, cellulose fibre was widely used in clothing or absorbent commodity, paper products etc..As cellulose fibre, Other than fiber footpath is 10 μm or more 50 μm or less of fibrous cellulose, also known fiber diameter is 1 μm or less of fine fibre Fibrous cellulose.Microfibre shape cellulose attracts attention as new material, and the purposes of the microfibre shape cellulose is spread It is many-sided.For example, the positive exploitation for promoting sheet material or resin composite body, tackifier containing microfibre shape cellulose.

It is steadily scattered in water solvent in general, microfibre shape is cellulose-based, therefore in most cases with moisture The state of dispersion liquid provides and is used for various uses.On the other hand, it is made in mixing microfibre shape cellulose with resin component Whens making complex etc., also expectation is intended to mix microfibre shape cellulose with organic solvent and use.As such expectation of reply Technology, positive research is scattered in microfibre shape cellulose in the decentralized medium comprising organic solvent and manufacture and contain fine fibre The technology (patent document 1 to patent document 3) of the dispersion liquid of fibrous cellulose.

For example, disclosing in patent document 1 has one kind that interfacial agent is made to be adsorbed in the microfibre shape fibre with carboxyl Microfibre shape cellulose complex made of dimension element.Herein, disclosing has following methods: by cellulose fibre in water solvent After being miniaturize, make method of the microfibre shape cellulose gel coalescence and re dispersion in organic solvent；Or in organic solvent Cellulose fibre is miniaturize, thus to obtain the method for microfibre shape cellulose.In addition, being disclosed in patent document 2 There is a kind of dispersion, which includes the microfibre shape cellulose and organic solvent for being imported with carboxyl, and includes organic Ion is as counter ion counterionsl gegenions.The manufacturing method for having a kind of microfibre shape cellulose dispersion liquid, the party are disclosed in patent document 3 Method is the following steps are included: preparation has the step of aqueous dispersions of the microfibre shape cellulose of the base of carboxylic acid type；By carboxylic acid The base of salt form is substituted by the step of base of amine carboxylic acid salt form of the amine containing organic group；And make the base with amine carboxylic acid salt form Microfibre shape cellulose is scattered in the step in organic solvent.

[prior art document]

[patent document]

Patent document 1: Japanese Patent Laid-Open 2011-140738 bulletin.

Patent document 2: Japanese Patent Laid-Open 2015-101694 bulletin.

Patent document 3: Japanese Patent Laid-Open 2012-021081 bulletin.

Summary of the invention

[invention is intended to the project solved]

In general, it is known to which the relative dielectric constant of solvent is lower than water, therefore being difficult to obtain makes microfibre shape fiber The required electrostatic repulsion of element dispersion when institute.Therefore, in organic solvent, it is seen that the dispersibility of microfibre shape cellulose becomes not Abundant tendency.

Therefore, inventor et al. is in order to solve the project of such prior art, to be provided in also may be used in organic solvent It is studied for the purpose of the microfibre shape cellulose of the good dispersibility of performance.

[to solve the means of project]

Inventor et al. is concentrated on studies in order to solve the above problems, as a result, it has been found that, by with phosphorus Acidic group or in the microfibre shape cellulose of the substituent group of phosphate by phosphate or derive from phosphate substituent group Content be set as 0.5mmol/g or more, and then the supernatant yield of the aqueous dispersions of microfibre shape cellulose is set as predetermined model In enclosing, the microfibre shape cellulose that good dispersibility can be also played in organic solvent can get.

Specifically, the present invention has following composition.

[1] a kind of fibrous cellulose, series fiber width be 1000nm hereinafter, and have phosphate or from phosphate it Substituent group, and the content of phosphate or the substituent group from phosphate is 0.5mmol/g or more, by following measuring methods (a) the supernatant yield measured is 70% or less.

Measuring method (a): the aqueous dispersions A for the fibrous cellulose that solid component concentration is 0.5 mass % is prepared, is used Defibrating processing device carries out 30 minutes defibrating processings with 21500 revs/min of condition, obtains aqueous dispersions B；Then, by water dispersion The aqueous dispersions C that solid component concentration is 0.2 mass % is made in liquid B, carries out centrifugation point in 10 minutes with 12000G, 15 DEG C of condition From processing, supernatant is recycled；The solid component concentration for measuring the supernatant recycled calculates supernatant yield according to following formula.

Supernatant yield (%)=supernatant solid component concentration (quality %)/0.2 (quality %) × 100

[2] fibrous cellulose as recorded such as [1] is comprising selected from the organic of the alkyl for being 5 or more containing carbon number At least one of organic ion that ion and total carbon number are 17 or more is as phosphate or from the substituent group of phosphate Counter ion counterionsl gegenions.

[3] fibrous cellulose as recorded such as [2], wherein organic ion is organic ammonium.

[4] a kind of composition of fibrousness cellulose is comprising 85 mass % or more such as any one of [1] to [3] Recorded fibrous cellulose.

[5] a kind of dispersion liquid of fibrousness cellulose is comprising the threadiness as recorded in any one of [1] to [3] Cellulose and organic solvent.

[6] such as the dispersion liquid of [5] recorded fibrousness cellulose, wherein organic solvent is normal in 25 DEG C of opposite dielectric Number is 60 or less.

[7] a kind of manufacturing method of fibrous cellulose is the following steps are included: will contain the phosphorus of 0.5mmol/g or more The fibrous cellulose of acidic group or the substituent group from phosphate carries out defibrating processing in water solvent, and obtaining includes fiber The step of width is the aqueous dispersions of the fibrous cellulose of 1000nm or less；And it will be selected from the alkyl for being 5 or more containing carbon number Organic ion and total carbon number be 17 or more at least one of organic ion be added to the step in aqueous dispersions.

[invention effect]

According to the present invention, can get one kind can also play the microfibre shape fiber of good dispersibility in organic solvent Element.

Detailed description of the invention

Fig. 1 system indicates the chart of the relationship to the NaOH dripping quantity and electrical conductivity of the fibrous raw material with phosphate.

Fig. 2 system indicates the chart of the relationship to the NaOH dripping quantity and electrical conductivity of the fibrous raw material with carboxyl.

Specific embodiment

Hereinafter, the present invention is described in detail.The explanation of recorded constitutive requirements is based on representativeness sometimes below Embodiment or specific example and carry out, but the present invention is not limited thereto kind embodiment.

(fibrous cellulose)

It is 1000nm or less present invention is directed to a kind of fiber width and there is phosphate or derive from the substitution of phosphate The fibrous cellulose of base.Herein, the content of phosphate or the substituent group from phosphate is 0.5mmol/g or more.In addition, It is 70% or less using the supernatant yield that following measuring methods (a) measure.

Measuring method (a): the aqueous dispersions A for the fibrous cellulose that solid component concentration is 0.5 mass % is prepared, is used Defibrating processing device carries out 30 minutes defibrating processings with 21500 revs/min of condition, obtains aqueous dispersions B.Then, by water dispersion The aqueous dispersions C that solid component concentration is 0.2 mass % is made in liquid B, carries out centrifugation point in 10 minutes with 12000G, 15 DEG C of condition From processing, supernatant is recycled.The solid component concentration for measuring the supernatant recycled calculates supernatant yield according to following formula.

Supernatant yield (%)=supernatant solid component concentration (quality %)/0.2 (quality %) × 100

The fibrous cellulose of the present invention has above-mentioned composition, therefore good dispersibility can be also played in organic solvent. Specifically, the viscosity for making the fibrous cellulose of the present invention be scattered in point dispersion liquid in organic solvent is high.In this explanation In book, the dispersibility for making fibrous cellulose be scattered in point dispersion liquid in organic solvent can be sentenced according to the viscosity of dispersion liquid It is fixed.

Furthermore the fibrous cellulose that fiber width is 1000nm or less in this manual, is also known as microfibre shape Cellulose.

The supernatant yield measured using said determination method (a) is 70% or less the microfibre shape for meaning the present invention Cellulose has the hydrophobicity of certain degree., it can be said that there is hydrophobicity, and Yu Youji by fibrous cellulose in the present invention Good dispersibility can be played in solvent.As long as the supernatant yield measured using said determination method (a) is 70% or less i.e. Can, preferably 50% hereinafter, more preferably 30% hereinafter, good in turn is 25% or less.

In measuring method (a), the water for the microfibre shape cellulose that solid component concentration is 0.5 mass % is prepared first Dispersion liquid A.So-called solid component concentration herein is the concentration of microfibre shape cellulose, includes 0.5 matter in aqueous dispersions A Measure the microfibre shape cellulose of %.Then, 30 minutes defiberings are carried out with 21500 revs/min of condition using defibrating processing device Processing obtains aqueous dispersions B.At this point, as defibrating processing device, such as preferably use high speed rotation defibrating processing device. The Clearmix 2.2S of M-Technique company manufacture specifically can be used.Then, ion is added in aqueous dispersions B to hand over Water is changed, the aqueous dispersions C that solid component concentration is 0.2 mass % is made, be centrifuged within 10 minutes with 12000G, 15 DEG C of condition Separating treatment recycles supernatant.Furthermore in centrifuging treatment step, preferably using cooling high-speed centrifuge.Tool The H-2000B of Kokusan company can be used for body.Then, the solid component concentration for the supernatant that measurement is recycled, according to upper It states formula and calculates supernatant yield.

Sufficiently, such dispersibility is in opposite Jie for the cellulose-based dispersibility in organic solvent of the microfibre shape of the present invention It is also played in the low organic solvent of electric constant.The organic solvent for being used as decentralized medium is not particularly limited, such as can be enumerated: first Alcohol (relative dielectric constant 32.6), ethyl alcohol (relative dielectric constant 24.3), normal propyl alcohol (relative dielectric constant 20.1), isopropanol (IPA) (relative dielectric constant 18.62), n-butyl alcohol (relative dielectric constant 18), methyl ether (relative dielectric constant 11.8), glycerol (relative dielectric constant 42.5), acetic acid (relative dielectric constant 6.15), pyridine (relative dielectric constant 12.3), tetrahydrofuran (THF) (relative dielectric constant 7.5), acetone (relative dielectric constant 20.7), methyl ethyl ketone (MEK) (relative dielectric constant 15.45), ethyl acetate (relative dielectric constant 6.4), aniline (relative dielectric constant 6.89), N- methyl -2- Pyrrolizidine ketone (NMP) (relative dielectric constant 32.2), dimethyl sulfoxide (DMSO) (relative dielectric constant 45), N,N-dimethylformamide (DMF) (relative dielectric constant 38), hexane (relative dielectric constant 1.8), hexamethylene (relative dielectric constant 2.0), benzene are (opposite to be situated between Electric constant 2.3), toluene (relative dielectric constant 2.4), paraxylene (relative dielectric constant 2.3), (opposite dielectric is normal for diethyl ether Number 4.3), chloroform (relative dielectric constant 4.8), 2-Pyrrolidone (relative dielectric constant 28.2) etc..It wherein, can be preferably with N- methyl -2- Pyrrolizidine ketone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), toluene, paraxylene, Methanol, 2-Pyrrolidone.

The viscosity system for making microfibre shape cellulose be scattered in point dispersion liquid in organic solvent depends on as dispersion The concentration of the type of the organic solvent of medium and the microfibre shape cellulose in dispersion liquid.Such as the fine fibre in dispersion liquid When the concentration of fibrous cellulose is 2.0 mass %, when organic solvent is the situation of dimethyl sulfoxide (DMSO), dispersion liquid is glutinous Degree is preferably 8000mPas or more, more preferably 10000mPas or more, and then good is 30000mPas or more, further good For 50000mPas or more.In addition, when organic solvent is the situation of n,N-Dimethylformamide (DMF), the viscosity of dispersion liquid Preferably 500mPas or more, more preferably 1000mPas or more.In organic solvent be N- methyl -2- Pyrrolizidine ketone (NMP) it When situation, the viscosity of dispersion liquid is preferably 1500mPas or more, more preferably 2000mPas or more.In organic solvent be toluene Situation when, the viscosity of dispersion liquid is preferably 50mPas or more, more preferably 53mPas or more.In turn, it is in organic solvent When the situation of paraxylene, the viscosity of dispersion liquid is preferably 100mPas or more, more preferably 200mPas or more.In organic molten When agent is the situation of methanol, the viscosity of dispersion liquid is preferably 8000mPas or more, more preferably 10000mPas or more, in turn Good is 20000mPas or more.When organic solvent is the situation of 2-Pyrrolidone, the viscosity of dispersion liquid is preferably 10000mPas or more, more preferably 30000mPas or more, and then good is 50000mPas or more.

It, will when to making microfibre shape cellulose be scattered in the viscosity of point dispersion liquid in organic solvent to be measured Be scattered in microfibre shape cellulose obtained in organic solvent containing micro- in a manner of solid component concentration becomes 2.0 mass % The slurry of fine-fibrous cellulose is measured after 25 DEG C stand 24 hours using Type B viscosmeter.As Type B viscosmeter, example The Analogue viscosmeter T-LVT of BLOOKFIELD company manufacture such as can be used.Determination condition system is set as 25 DEG C of condition, measurement Viscosity when with 6rpm rotation 3 minutes.

The cellulose-based favorable dispersibility in organic solvent of the microfibre shape of the present invention, therefore do not given birth in dispersion liquid There is feature at the aspect of sediment.Therefore, microfibre shape cellulose can will be made to be scattered in point in organic solvent to dissipate The viscosity of liquid is set as in above range.In addition, favorable dispersibility of the microfibre shape cellulose of the present invention to organic solvent, therefore The energy for consuming microfibre shape cellulose when being scattered in organic solvent can be reduced.

About the total light transmittance for making microfibre shape cellulose be scattered in point dispersion liquid in organic solvent, in point When the concentration of microfibre shape cellulose in dispersion liquid is 2.0 mass %, above-mentioned total light transmittance is preferably 50% or more, more Good is 55% or more, and then good is 65% or more, and further good is 70% or more, further more preferably 80% or more, it is further preferred that being 85% or more.

It is carried out in the total light transmittance for making microfibre shape cellulose be scattered in point dispersion liquid in organic solvent When measurement, to by solid component concentration become 2.0 mass % in a manner of be scattered in microfibre shape cellulose in organic solvent The total light transmittance of the slurry of the resulting cellulose of shape containing microfibre is measured.The measurement of total light transmittance is to use With aquarium, (rattan original makes the liquid of haze meter (HM-150 of company, color technical research institute manufacture in village) and optical path length 1cm Manufactured MG-40, backlight road), according to JIS (Japanese Industrial Standard；Japanese Industrial Standards) K 7361 and carry out.Furthermore Measurement Zero Point system is carried out using the ion exchange water being added into the aquarium.

Solid component concentration before dispersing from the microfibre shape cellulose of the present invention to organic solvent is preferably 70 matter % or more, more preferably 80 mass % or more are measured, and then good is 85 mass % or more.The microfibre shape cellulose of the present invention is in water The low aspect of/content has feature, and can inhibit makes the microfibre shape cellulose of the present invention be scattered in gained in organic solvent Dispersion liquid in the amount of moisture brought into.

The microfibre shape celluloses of the present invention such as comprising selected from containing carbon number be 5 or more alkyl it is organic from At least one of organic ion that son and total carbon number are 17 or more as phosphate or from phosphate substituent group it Counter ion counterionsl gegenions.

The alkyl of stretching that the alkyl that carbon number is 5 or more is preferably the alkyl that carbon number is 5 or more or carbon number is 5 or more, more preferably The alkyl of stretching that the alkyl or carbon number that carbon number is 7 or more are 7 or more, so it is good be alkyl that carbon number is 10 or more or carbon number be 10 with Upper stretches alkyl.Wherein, organic ion be preferably contains carbon number be 5 or more alkyl, more preferably containing carbon number be 5 or more it The organic ion that alkyl and total carbon number are 17 or more.

Containing carbon number be 5 or more alkyl organic ion and total carbon number be 17 or more organic ion be preferably The represented organic ion of the following general formula (A).

[chemical formula 1]

In above-mentioned general formula (A), M is nitrogen-atoms or phosphorus atoms, R₁To R₄Separately indicate hydrogen atom or organic group.Its In, R₁To R₄At least one be the organic group or R that carbon number is 5 or more₁To R₄Carbon number add up to 17 or more.

Wherein, M is preferably nitrogen-atoms.Also that is, organic ion is preferably organic ammonium.In addition, preferably R₁To R₄At least One is alkyl that carbon number is 5 or more, and R₁To R₄Carbon number add up to 17 or more.Furthermore the alkyl that carbon number is 5 or more also may be used With substituent group.

It as such organic ion, such as can enumerate: four pentyl ammonium, tetrahexyl ammonium, four heptyl ammoniums, lauryl trimethyl Ammonium, cetyltrimethylammonium ammonium, stearyl trimethyl ammonium, octyldimethyl ethyl ammonium, lauryl dimethyl ethyl ammonium, didecyl two Methyl ammonium, lauryl dimethyl benzyl ammonium, tributyl hexadecyldimethyl benzyl ammonium, three n-octyl ammonium of methyl, hexyl ammonium, n-octyl ammonium, dodecane Base ammonium, myristyl ammonium, cetyltrimethyl ammonium, stearyl ammonium, N, N- dimethyl dodecyl base ammonium, N, N- dimethyl tetradecyl base Ammonium, N, N- dimethyl hexadecyl base ammonium, N, N- dimethyl-n-octadecane base ammonium, dihexyl ammonium, two (2- ethylhexyl) ammoniums, two N-octyl ammonium, didecyl ammonium, two-dodecyl ammoniums, didecyl methyl ammonium, N, bis--dodecyl methyl of N- ammonium, polyoxyethylene Dodecyl ammonium, alkyl dimethyl benzyl ammonium, two-n alkyl dimethyl ammoniums, behenyl ammonium, tetraphenylphosphoniphenolate, four Xin Ji Phosphonium, acetonyl triphenyl phosphonium, allyl triphenyl phosphonium, amyl triphenyl phosphonium, Bian base triphenyl phosphonium, Yi base triphenyl phosphonium Deng.

Furthermore as shown in general formula (A), the central element of organic ion is bonded with total 4 bases or hydrogen.In above-mentioned organic When the base being bonded in the title of ion is less than 4 situations, remaining forms organic ion through bonded hydrogen atoms.Such as If N, N- bis--dodecyl methyl ammonium then can determine whether to be bonded with 2 dodecyls and 1 methyl according to title.In the situation When, remaining one is bonded through hydrogen and forms organic ion.

The molecular weight of organic ion is preferably 2000 hereinafter, more preferably 1800 or less.By dividing organic ion Son amount is set as in above range, and the operability of microfibre shape cellulose can be improved.In addition, generally can inhibit containing for cellulose There is rate reduction.

Relative to phosphoric acid base unit weight contained in microfibre shape cellulose, having in the microfibre shape cellulose of the present invention The content of machine ion is preferably equimolar amounts to 2 times of moles, is not particularly limited.The content of organic ion can be by chasing after The typical contained atom of track organic ion and measure.Specifically, measuring nitrogen when organic ion is the situation of ammonium ion The amount of atom measures the amount of phosphorus atoms when the situation of organic ion Wei phosphonium ion.Furthermore it is removed in microfibre shape cellulose When containing the situation of nitrogen-atoms or phosphorus atoms other than organic ion, only the method for organic ion is extracted i.e. as long as taking Can, as long as such as carrying out the amounts of measurement target atoms after extraction operation using acid.

The microfibre shape cellulose of the present invention also may include metal ion as counter ion counterionsl gegenions.In addition, the present invention's is micro- Fine-fibrous cellulose also can be free of metal ion as counter ion counterionsl gegenions.Include metal ion conduct in microfibre shape cellulose When the situation of counter ion counterionsl gegenions, as metal ion, such as sodium ion, potassium ion, calcium ion, magnesium ion and aluminium ion can be enumerated.

In the total charge dosage of the represented phosphate of following formula (a) is set as Ea, and by the represented sodium of following formula (b) from Total charge dosage when being set as the situation of Eb of son, potassium ion, calcium ion, magnesium ion and aluminium ion, preferably meet sometimes Eb < Ea × 0.1 condition.It on the other hand, also can be Eb≤Ea × 0.1.

Formula (a):

Amount (mmol/g) × phosphate valence mumber of Ea=phosphate

Formula (b):

Eb=(content (mmol/g) × sodium ion valence mumber (monovalence) of the sodium ion)+(content (mmol/g) of potassium ion The valence mumber (monovalence) of × potassium ion)+(content (mmol/g) × calcium ion valence mumber (divalent) of calcium ion)+(magnesium ion contains Measure the valence mumber (divalent) of (mmol/g) × magnesium ion)+(content (mmol/g) × aluminium ion valence mumber (trivalent) of aluminium ion)

It as the fibrous cellulose raw material to obtain microfibre shape cellulose, is not particularly limited, is easy for obtaining It takes and for inexpensive aspect, preferably uses paper pulp.As paper pulp, wood pulp, non-wood pulp, deinking paper can be enumerated Slurry.It as wood pulp, such as can enumerate: broad leaf tree kraft pulp (LBKP), softwood kraft pulp (NBKP), sulphite Paper pulp (SP), dissolving pulp (DP), soda pulps (AP), UKP unbleached kraft pulp (UKP), oxygen bleaching kraft pulp (OKP) etc. are changed Learn paper pulp etc..In addition it can enumerate: the semichemical wood pulps such as semi-chemical pulp (SCP), chemistry mill wet pulp (CGP), ground wood pulp (GP), heat engine Tool starches (TMP (Thermo Mechanical Pulp；Thermomechanical pulp), BCTMP (BleachedChemi-Thermo Mechanical Pul；Bleached chemical thermomechanical pulp)) etc. mechanical pulps etc., be not particularly limited.As non-wood pulp, Can enumerate: cottons system paper pulp, fiber crops, straw, the bagasse etc. such as velveteen (cotton linter) or cotton-wool (cotton lint) are non-wood Material system paper pulp is not particularly limited from the cellulose, chitin, chitosan etc. of the separation such as ascidian or sea grass.As deinking paper Slurry, can enumerate the de inked pulp using waste paper as raw material, be not particularly limited.The paper pulp of present embodiment can be used alone above-mentioned one Kind, or two or more mixing can also be used.In above-mentioned paper pulp, for obtaining the aspect of easiness, preferably containing fibre Tie up wood pulp, the de inked pulp of element.In wood pulp, chemical pulp is preferable for following aspect: cellulose ratio is big, therefore And the yield of microfibre shape cellulose when fiber miniaturization (defibering) is high, in addition the decomposition of the cellulose in paper pulp is small, can Obtain microfibre shape cellulose of the axis than big long fibre.Wherein, kraft pulp, sulfite pulp can most preferably be selected.

The average fiber of microfibre shape cellulose is wide to be 1000nm or less with electron microscope observation.Average fiber is wide Preferably 2nm or more 1000nm hereinafter, more preferably 2nm or more 100nm hereinafter, in turn it is good be 2nm or more 50nm hereinafter, in turn compared with Good is 2nm or more 10nm hereinafter, being not particularly limited.If the average fiber of microfibre shape cellulose is wide to be less than 2nm, with fibre It ties up the form of plain molecule and is dissolved in the water, therefore have the physical property (intensity or just for being difficult to show as microfibre shape cellulose Property, dimensional stability) tendency.Furthermore the single fiber shape that microfibre shape celluloses such as series fiber width are 1000nm or less Cellulose.

The wide measurement of the fiber using electron microscope observation of microfibre shape cellulose is the progress as following.Preparation The water system suspension of the microfibre shape cellulose of 0.05 mass % of concentration or more, 0.1 mass % or less, which is poured Carbon film to hydrophilized processing is coated on grid and TEM (Transmission Electron Microscopy is made；Transmission Electron microscope) it observes and uses sample.When comprising the situation of the wide fiber of width, also can to the surface being poured on glass it SEM(Scanning ElectronMicroscope；Scanning electron microscope) as being observed.According to the width for constituting fiber Spend and carry out with 1000 times, 5000 times, 10000 times or 50000 times of any multiplying power the observation of electron microscope image.Wherein, Sample, observation condition or multiplying power system are adjusted in a manner of following conditions by meeting.

(1) straight line X is drawn in any place in observation image, 20 or more fibers intersect with straight line X.

(2) in drawing the straight line Y vertically intersected with the straight line in identical image, 20 or more fibers and straight line Y Intersect.

For the observation image for meeting above-mentioned condition, the width with straight line X, straight line the Y fiber to interlock is read by range estimation Degree.The image that 3 groups or more of the surface element not overlapped point is at least observed as so is read and straight line X, straight line Y for each image The width of fiber staggeredly.The fiber that 20 × 2 × 3=120 item is at least read as so is wide.Microfibre shape cellulose is flat Equal fiber width be so as reading the wide average value of fiber.

The fiber length of microfibre shape cellulose is not particularly limited, and preferably 0.1 μm or more 1000 μm hereinafter, good in turn For 0.1 μm or more 800 μm hereinafter, it is further preferred that being 0.1 μm or more 600 μm or less.It is set as in above range, can press down by by fiber length In addition the slurry viscosity of microfibre shape cellulose can be set as appropriate by the destruction of the crystal region of microfibre shape cellulose processed Range.Furthermore the fiber of microfibre shape cellulose grows system by utilization TEM, SEM, AFM (Atomic Force Microscop；Atomic force microscope) image analysis and find out.

Microfibre shape cellulose preferably has I type crystal structure.Herein, microfibre shape cellulose is crystallized in I type Construction can identify that the Diffraction fringe distribution is by using through graphite and the CuK α of monochromatization in following Diffraction fringe distributionWide angle X-ray diffraction photo obtained by.Specifically, can be according near 17 ° of 2 θ=14 ° or more or less With 23 ° or less of 2 θ=22 ° or more nearby two at position there is the wave crest of typical case and identify.

I type crystal structure ratio shared in microfibre shape cellulose is preferably 30% or more, more preferably 50% with On, and then good is 70% or more.When the situation, in showing the aspect of heat resistance and low coefficient of linear thermal expansion it can be expected that more excellent Different performance.About crystallinity, can measure X-ray diffraction distribution and according to the pattern of the X-ray diffraction distribution by well-established law and It finds out (Seagal et al., Textile Research Journal, volume 29, page 786, nineteen fifty-nine).

Microfibre shape cellulose has phosphate or derives from the substituent group (being also referred to simply as phosphate sometimes) of phosphate. Also that is, the microfibre shape cellulose of the present invention is phosphorylated cellulose.Phosphate be equivalent to remove from phosphoric acid hydroxyl it Divalent functional group.Specifically-PO₃H₂Represented base.Substituent group from phosphate includes that phosphate polycondensation forms it Base, the salt of phosphate, the substituent groups such as phosphate-based, can be ionic substituent group, also can be nonionic substituent group.

In the present invention, phosphate or substituent group that also can be represented for following formula (1) from the substituent group of phosphate.

[chemical formula 2]

In formula (1), a, b and n are natural number (wherein, a=b × m).α¹、α²、……、αⁿAnd a is a for O in α '^-, remaining is R, any one of OR.Furthermore each αⁿAnd α ' also can all O^-.R is respectively hydrogen atom, saturation-straight-chain alkyl, saturation-branch Chain alkyl, saturation-cyclic hydrocarbon group, unsaturation-straight-chain alkyl, unsaturation-branch's chain state alkyl, unsaturation-cyclic hydrocarbon group, Aromatic series base or this etc. derivative base.

As saturation-straight-chain alkyl, methyl, ethyl, n-propyl or normal-butyl etc. can be enumerated, is not particularly limited.Make For saturation-branch's chain state alkyl, isopropyl or third butyl etc. can be enumerated, is not particularly limited.As saturation-cyclic hydrocarbon group, Cyclopenta or cyclohexyl etc. can be enumerated, is not particularly limited.As unsaturation-straight-chain alkyl, vinyl or allyl can be enumerated Base etc., is not particularly limited.As unsaturation-branch's chain state alkyl, isopropenyl or 3- cyclobutenyl etc. can be enumerated, is had no especially It limits.As unsaturation-cyclic hydrocarbon group, cyclopentenyl, cyclohexenyl group etc. can be enumerated, is not particularly limited.As aromatic series base, Phenyl or naphthyl etc. can be enumerated, is not particularly limited.

In addition, can be enumerated as the derivative base in R: main chain or side chain and addition carboxyl, hydroxyl for above-mentioned various alkyl At least one in the functional groups such as base or amido or the shape through at least one substitution in the functional groups such as carboxyl, hydroxyl or amido The functional group of state, is not particularly limited.In addition, the carbon atom number of main chain for constituting R is not particularly limited, preferably 20 hereinafter, More preferably 10 or less.It is set as above range by the carbon atom number for the main chain that will constitute R, the molecular weight of phosphate can be set as suitable Work as range, is also easy to permeate and can be improved the yield of fine cellulose fiber to fibrous raw material.

β^b+By the cation more than monovalence that is made of organic matter or inorganic matter.As the monovalence being made of organic matter Above cation, can enumerate aliphatic ammonium or aromatic series ammonium can as the cation more than monovalence being made of inorganic matter Enumerate: the ion of the alkali metal such as sodium, potassium or lithium perhaps cation of the divalent metals such as calcium or magnesium or hydrogen ion etc. have no spy It does not limit.This etc. can be applied using one kind or by two or more combinations.As the monovalence being made of organic matter or inorganic matter Above cation, is preferably not easy xanthochromia when heating to the fibrous raw material comprising β, is in addition easy to utilize in industrial Sodium or potassium ion, be not particularly limited.

<phosphate steps for importing>

Phosphate steps for importing can by make in compound and its salt with phosphate it is it is at least one (hereinafter referred to as For " phosphorylation agent " or " compound A ") it reacts and carries out with the fibrous raw material comprising cellulose.Such phosphorylation agent also can It is mixed with the state of powder or aqueous solution into the fibrous raw material of drying regime or moisture state.In addition, as other examples, also The powder or aqueous solution of phosphorylation agent can be added in the slurry of fibrous raw material.

Phosphate steps for importing can by make in by compound and its salt with phosphate it is at least one (phosphoric acid Change reagent or compound A) it reacts and carries out with the fibrous raw material comprising cellulose.Furthermore the reaction also can in selected from urea and its It is carried out in the presence of at least one (hereinafter referred to as " compound B ") in derivative.

As making compound A act on an example of the method for fibrous raw material in coexisting down for compound B, can enumerate: Yu Gan The powder or aqueous solution of mixed compound A and compound B in the fibrous raw material of dry state or moisture state.In addition, as other Example can be recited in the method that the powder or aqueous solution of compound A and compound B are added in the slurry of fibrous raw material.Among this is equal, In reaction uniformity height aspect for, preferably in the fibrous raw material of drying regime add compound A and compound B it The method of aqueous solution adds the powder of compound A and compound B or the side of aqueous solution in the fibrous raw material of moisture state Method.In addition, compound A and compound B can be added simultaneously, can also add respectively.In addition, also can first will be for the compound A of reaction It is added in the form of the aqueous solution with compound B, and removes extra chemical liquids by squeezing.The form of fibrous raw material is preferably Cotton like or thin sheet, are not particularly limited.

The compound A used in present embodiment is at least one in compound and its salt with phosphate.

As the compound with phosphate, phosphoric acid, the lithium salts of phosphoric acid, the sodium salt of phosphoric acid, the sylvite of phosphoric acid, phosphorus can be enumerated The ammonium salt etc. of acid, is not particularly limited.As the lithium salts of phosphoric acid, can enumerate lithium dihydrogen phosphate, two lithium of phosphoric acid hydrogen, tricresyl phosphate lithium, Pyrophosphoric acid lithium or polyphosphoric acid lithium etc..As the sodium salt of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate, burnt phosphorus can be enumerated Sour sodium or polyphosphate sodium etc..As the sylvite of phosphoric acid, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate can be enumerated Or PA 800K etc..As the ammonium salt of phosphoric acid, ammonium dihydrogen phosphate can be enumerated, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, gathered Ammonium phosphate etc..

Among this is equal, the importing with regard to phosphate is high-efficient, and defibering efficiency is easy to further increase in aftermentioned defibering step, at This is low, and for the industrial viewpoint for being easy to apply, preferably the ammonium salt of phosphoric acid, the sylvite of the sodium salt of phosphoric acid or phosphoric acid, phosphoric acid. More preferably sodium dihydrogen phosphate or disodium hydrogen phosphate.

In addition, improving with regard to the uniformity of reaction and for the aspect of the efficiency raising of phosphate importing, compound A is preferably It is used in the form of the aqueous solution.The pH value of the aqueous solution of compound A is not particularly limited, and improves it with regard to the importing efficiency of phosphate For aspect, for preferably 7 hereinafter, may refrain from the viewpoint of the hydrolysis of paper pulp fiber, and then it is good for 3 or more pH value 7 of pH value with Under.The pH value of aqueous solution about compound A, such as can also would indicate that the chemical combination of acidity in the compound with phosphate Object is used in combination with the compound for showing alkalinity, and changes the amount ratio of the grade compounds and adjust pH value.The aqueous solution of compound A it PH value also can by the compound for showing acidity in the compound with phosphate add inorganic base or organic base etc. and Adjustment.

Compound A is not particularly limited relative to the additive amount of fibrous raw material, in the additive amount of compound A is converted into phosphorus When the situation of atomic weight, phosphorus atoms are preferably 0.5 mass % or more relative to the additive amount of fibrous raw material (adiabatic drying quality) 100 mass % hereinafter, more preferably 1 mass % or more, 50 mass % hereinafter, most preferably 2 mass % or more, 30 mass % or less.If Phosphorus atoms are that then can further improve the production of microfibre shape cellulose in above range relative to the additive amount of fibrous raw material Rate.If phosphorus atoms are more than 100 mass % relative to the additive amount of fibrous raw material, the effect of yield raising culminates, is made With compound A cost increase.On the other hand, above-mentioned lower limit is set as relative to the additive amount of fibrous raw material by by phosphorus atoms More than value, yield can be improved.

As compound B used in present embodiment, urea, biuret, 1- phenylurea, 1- benzylurea, 1- can be enumerated Methylurea, 1- ethyl carbamide etc..

Compound B is preferably used in the form of the aqueous solution in the same manner as compound A.In addition, just the uniformity of reaction mentions For the aspect of height, the aqueous solution of both compound A and compound B dissolution is preferably used.Compound B is relative to fibrous raw material The additive amount of (adiabatic drying quality) is preferably 1 mass % or more, 500 mass % hereinafter, more preferably 10 mass % or more, 400 matter % is measured hereinafter, good in turn is 100 mass % or more, 350 mass % hereinafter, it is further preferred that being 150 mass % or more, 300 mass % or less.

Other than compound A and compound B, amides or amine can be also contained in reaction system contains.As amides, Formamide, dimethylformamide, acetamide, dimethyl acetamide etc. can be enumerated.As amine, methylamine, ethamine, front three can be enumerated Amine, triethylamine, monoethanolamine, diethanol amine, triethanolamine, pyridine, ethylenediamine, hexamethylene diamine etc..Among this is equal, especially Known triethylamine plays a role as good reaction catalyst.

In phosphate steps for importing, preferably implement heat treatment.Heat treatment temperature preferably selects to inhibit fiber Thermal decomposition or hydrolysis and the temperature that can efficiently import phosphate.Specifically, preferably 50 DEG C or more 300 DEG C Hereinafter, more preferably 100 DEG C or more 250 DEG C hereinafter, good in turn is 150 DEG C or more 200 DEG C or less.Subtract in addition, heating also can be used Press drying machine, infrared heating device, microwave heating equipment.

When heat treatment, if containing in when water in the fibrous raw material slurry added with compound A, fiber is stood The time of raw material is elongated, then hydrone and the molten compound A deposited are moved to fibrous raw material surface along with dry.Therefore, have The concentration of compound A in possible fibrous raw material generates unevenness, there is the anxiety for not importing phosphate equably to fiber surface.For Inhibit the density unevenness that the compound A in fibrous raw material is generated because dry, as long as using the fiber of very thin sheet former Material, or using on one side being kneaded fibrous raw material and compound A using kneader etc. or while stirring heats drying or is dried under reduced pressure Method.

It, preferably can be by moisture that slurry is kept and phosphate etc. to fiber as the heating device for being used for heat treatment Hydroxyl addition reaction in the moisture that generates be expelled to the device outside device system, such as the baking oven of preferably air supply mode always Deng.If the moisture in device system is discharged always, the hydrolysis that can inhibit the phosphoric acid ester bond of the back reaction as Phosphation is anti- It answers, furthermore also can inhibit the sour water solution of the sugar chain in fiber, can get axis than high microfibre.

The time of heat treatment is also influenced by heating temperature, preferably substantially removes moisture removal from fibrous raw material slurry Afterwards for 1 second or more 300 points hereinafter, more preferably 1000 seconds 1 second or more hereinafter, good in turn is 800 seconds 10 seconds or more or less.The present invention In, it is set as appropriate range by by heating temperature and heating time, the import volume of phosphate can be set as in preferred range.

The content (import volume of phosphate) of phosphate as long as be relative to microfibre shape cellulose 1g (quality) 0.50mmol/g or more, preferably 0.70mmol/g or more, more preferably 0.90mmol/g or more.In addition, phosphate contains As long as amount relative to microfibre shape cellulose 1g (quality) is 4.00mmol/g or less, preferably 3.65mmol/g with Under, more preferably 3.50mmol/g is hereinafter, good in turn is 3.00mmol/g or less.Above range is set as by by the content of phosphate It is interior, the miniaturization of fibrous raw material is easily implemented, improves the stability of microfibre shape cellulose.In addition, by by phosphoric acid The content of base is set as in above range, and the content of the above-mentioned organic ion of the counter ion counterionsl gegenions as phosphate can be improved, therefore can Microfibre shape cellulose is more effectively improved to the dispersibility of organic solvent.Furthermore in this specification, microfibre shape fiber The phosphoric acid having as the content (import volume of phosphate) for the phosphate that element has is as be described hereinafter with microfibre shape cellulose The highly acid base unit weight of base is equal.

Phosphate can measure the import volume of fibrous raw material by electric conductivity titration.Specifically, at by defibering It manages step and is miniaturize, handled using slurry of the ion exchange resin to the cellulose of shape containing microfibre of gained Afterwards, the variation of electrical conductivity is found out while adding sodium hydrate aqueous solution, can measure import volume whereby.

In electrical conductivity titration, curve shown in Fig. 1 is obtained if gradually adding alkali.Initially, electrical conductivity drastically reduces (following It is denoted as " first area ").Then, electrical conductivity slightly begins to ramp up (hereinafter referred to as " second area ").Subsequently, the increasing of electrical conductivity Width increases (hereinafter referred to as " third region ").Also that is, there are 3 regions.Furthermore the point of interface system of second area and third region Reach the point of maximum with the variable quantity of the second differential value of electrical conductivity, that is, the amplification (slope) of electrical conductivity to define.Wherein, Alkali number required for one region is equal with for the highly acid base unit weight in the slurry of titration, alkali number required for second area and use Faintly acid base unit weight in the slurry of titration is equal.When the situation of condensation occurs for phosphate, faintly acid base is apparently lost, with Alkali number required for first area compares and the alkali number required for second area is reduced.On the other hand, highly acid base unit weight with have It is consistent without amount unrelated and with phosphorus atoms is condensed, therefore in only referring to phosphate import volume (or phosphoric acid base unit weight) or substituent group importing When the situation of amount (or replacing base unit weight), highly acid base unit weight is indicated.Also that is, by required for the first area of curve shown in Fig. 1 it Alkali number (mmol) is divided by the solid component (g) in titration object slurry, as substituent group import volume (mmol/g).

As long as phosphate steps for importing at least once, can also carry out repeatedly.Imported when the situation it is more it Phosphate, so preferably.

<defibrating processing step>

The fiber for being imported with phosphate, which is lain in, carries out defibrating processing in defibrating processing step.In defibrating processing step, lead to Be often used defibrating processing device to fiber carry out defibrating processing, obtain contain microfibre shape cellulose slurry, processing unit, Processing method is not particularly limited.

As defibrating processing device, high speed fiber uncoiling machine, grinder (stone mortar formula pulverizer), high pressure homogenizer or super can be used High pressure homogenizer, high-pressure impingement formula pulverizer, ball mill, ball mill etc..Alternatively, disk also can be used as defibrating processing device Homogeneous blender, ultrasonic dispersion machine or beater under grinding machine, type taper grinder, twin shaft muller, vibrating mill, high speed rotation (beater) etc. the device etc. of case of wet attrition is carried out.Defibrating processing device is not limited to above-mentioned apparatus.At preferably defibering Reason method can enumerate the influence of crushing medium less and the few high speed fiber uncoiling machine of worry, the high pressure homogenizer, super-high-pressure homogenization of pollution Machine.

When defibrating processing, fibrous raw material and water and organic solvent are diluted alone or in combination preferably and slurry is made Expect shape, is not particularly limited.As decentralized medium, in addition to water, polar organic solvent can be used.Have as preferably polarity Solvent can enumerate alcohols, ketone, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF) or dimethyl acetamide (DMAc) etc., it is not particularly limited.As alcohols, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol or third butanol can be enumerated Deng.As ketone, acetone or methyl ethyl ketone (MEK) etc. can be enumerated.As ethers, diethyl ether or tetrahydrofuran can be enumerated (THF) etc..Decentralized medium can be one kind, also can be two or more.In addition, also can be in decentralized medium containing other than fibrous raw material Solid component, such as the urea with hydrogen bond.

In the present invention, also defibrating processing can be carried out after making the concentration of microfibre shape cellulose, drying.In the situation When, it is concentrated, the method for drying is not particularly limited, such as can enumerate: being added in the slurry of Yu Hanyou microfibre shape cellulose The method of concentrating agents；Use conventionally used dewaterer, press, method of drying machine etc..In addition, known method example can be used The method as recorded in WO2014/024876, WO2012/107642 and WO2013/121086.In addition, also can by it is concentrated it Sheet material is made in microfibre shape cellulose.Also the sheet material can be crushed and carries out defibrating processing.

As the device for being used for crushing when microfibre shape cellulose crushes, high speed fiber uncoiling machine, grinder also can be used (stone mortar formula pulverizer), high pressure homogenizer, superhigh-voltage homogenizing machine, high-pressure impingement formula pulverizer, ball mill, ball mill, disc mill, Homogeneous blender, ultrasonic dispersion machine, beater under type taper grinder, twin shaft muller, vibrating mill, high speed rotation etc. carry out wet The device etc. of formula crushing, is not particularly limited.

<agglomeration step>

In agglomeration step, in the slurry by the cellulose of shape containing microfibre of defibrating processing step gained, addition Above-mentioned organic ion or the compound that organic ion is formed by neutralization.At this point, organic ion is preferably to contain The form of the aqueous solution of organic ion is added.

Aqueous solution containing organic ion usually contains organic ion and counter ion counterionsl gegenions (anion).It is organic in preparing When the aqueous solution of ion, when organic ion is with the corresponding counter ion counterionsl gegenions situation of forming salt, as long as keeping the salt direct It is dissolved in the water.It is given birth to just now in addition, organic ion is for example also neutralized such as lauryl amine etc. by acid sometimes At.Also that is, organic ion is obtained using the compound of organic ion and reacting for acid is formed by neutralization.In this When situation, as the acid for being used for neutralization, can enumerate the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid or lactic acid, acetic acid, formic acid, oxalic acid etc. has Machine acid.In agglomeration step, the compound that organic ion is formed by neutralization can be also added directly to containing fine fibre In the slurry of fibrous cellulose, formed using phosphate contained by microfibre shape cellulose as counter ion counterionsl gegenions it is organic from Son.

Relative to the gross mass of microfibre shape cellulose, the additive amount of organic ion is preferably 2 mass % or more, more Good is 10 mass % or more, and then good is 50 mass % or more, it is further preferred that being 100 mass % or more.Furthermore relative to microfibre The gross mass of shape cellulose, the additive amount of organic ion are preferably 1000 mass % or less.

In addition, the molal quantity of the organic ion added is preferably the amount of the contained substituent group of microfibre shape cellulose (molal quantity) is multiplied by 0.2 times or more of the resulting value of valence mumber, more preferably 1.0 times or more, and then good is 2.0 times or more.Furthermore institute The molal quantity of the organic ion of addition is preferably the amount (molal quantity) of the contained substituent group of microfibre shape cellulose multiplied by valence 10 times or less of the resulting value of number.

If addition organic ion is stirred, condensation product is generated in the slurry of the cellulose of shape containing microfibre.It should There is condensed system organic ion to agglomerate as the microfibre shape cellulose of counter ion counterionsl gegenions.By cohesion will be produced The slurry containing microfibre shape cellulose of object is filtered under diminished pressure, and can recycle microfibre shape cellulose gel polymers.

The microfibre shape cellulose gel polymers of gained also carries out using ion exchange water clean.It is handed over by using ion It changes water and cleans microfibre shape cellulose gel polymers repeatedly, it can will be extra organic contained by microfibre shape cellulose gel polymers The removal such as ion.

<alkali process>

It, also can be in phosphate steps for importing and aftermentioned defibrating processing step when manufacturing the situation of microfibre shape cellulose Between carry out alkali process.As the method for alkali process, be not particularly limited, for example, can enumerate will be imported with phosphate fiber leaching Method of the stain in aqueous slkali.

The contained alkali cpd of aqueous slkali is not particularly limited, and can be inorganic alkali compound, or also can be organic base chemical combination Object.As the solvent in aqueous slkali, water or organic solvent.Preferred solvents are that (water or alcohol isopolarity are organic molten for polar solvent Agent), more preferably at least contain the water solvent of water.

In addition, in aqueous slkali, for the aspect of versatility height, it is further preferred that water-soluble for sodium hydrate aqueous solution or potassium hydroxide Liquid.

The temperature of aqueous slkali in alkali treatment is not particularly limited, and preferably 5 DEG C or more 80 DEG C hereinafter, more preferably 10 DEG C or more 60 DEG C or less.

The dip time into aqueous slkali in alkali treatment is not particularly limited, preferably 5 points or more 30 points hereinafter, More preferably 10 points or more 20 points or less.

The usage amount of aqueous slkali in alkali process is not particularly limited, relative to the absolute dry of the fiber for being imported with phosphate Drying quality, preferably 100 mass % or more, 100000 mass % hereinafter, more preferably 1000 mass % or more, 10000 mass % with Under.

It, also can be before the alkali treatment by water or organic molten in order to reduce the aqueous slkali usage amount in alkali treatment The fiber that agent will be imported with phosphate is cleaned.After alkali process, in order to improve operability, preferably in defibrating processing step it Before, it will be cleaned through the fiber for being imported with phosphate of alkali process by water or organic solvent.

(composition of fibrousness cellulose)

The present disclosure generally relates to a kind of fibrousness fibers that microfibre shape cellulose is stated containing 85 mass % on more than The composition of element.Herein, the content system of the microfibre shape cellulose in the composition of fibrousness cellulose is by following formula And it calculates.

The content (quality %) of microfibre shape cellulose=microfibre shape cellulose adiabatic drying quality/(fine Quality+solvent quality of fibrous cellulose) × 100

The form of the composition of the fibrousness cellulose of the present invention is not particularly limited, and may be, for example, solid-like or gel Shape.However, the composition of fibrousness cellulose can be free of water, it can also contain water.In by the composition of fibrousness cellulose It is preferably not aqueous when the situation of the purposes for deterrent water.When the composition of fibrousness cellulose contains the situation of water, Moisture content is not particularly limited, the gross mass of the composition relative to the cellulose of shape containing microfibre, moisture content for example compared with Good is 15 mass % hereinafter, more preferably 12 mass % or less.In addition, moisture content also can be 0.1 mass % or more, also can be 0.3 mass % or more also can be 0.5 mass % or more.

(dispersion liquid of fibrousness cellulose)

The present disclosure generally relates to a kind of fibrousness cellulose containing above-mentioned microfibre shape cellulose and organic solvent it Dispersion liquid.The dispersion liquid of the fibrousness cellulose of the present invention, which is fastened, states microfibre shape cellulose or the fiber of shape containing microfibre The dispersion liquid of fibrousness cellulose made of the composition of element is scattered in the decentralized medium comprising organic solvent.Furthermore this The dispersion liquid of the fibrousness cellulose of invention also other than organic solvent and then can contain water as decentralized medium.

In the present invention fibrousness cellulose composition include organic solvent situation when, organic solvent in 25 DEG C it Relative dielectric constant is preferably 60 hereinafter, more preferably 50 or less.The microfibre shape cellulose of the present invention is in relative dielectric constant Also can play excellent dispersibility in low organic solvent, thus organic solvent in 25 DEG C relative dielectric constant also can for 45 with Under, it also can be for 40 hereinafter, also can be 35 or less.

The δ p of the Hansen Solubility Parameter (Hansen solubility parameter, HSP) of organic solvent is preferably 5MPa^1/2The above 20MPa^1/2Hereinafter, more preferably 10MPa^1/2The above 19MPa^1/2Hereinafter, good in turn is 12MPa^1/2The above 18MPa^1/2 Below.In addition, δ h is preferably 5MPa^1/2The above 40MPa^1/2Hereinafter, more preferably 5MPa^1/2The above 30MPa^1/2Hereinafter, good in turn be 5MPa^1/2The above 20MPa^1/2Below.In addition, also preferably while meeting δ p for 0MPa^1/2The above 4MPa^1/2Range below, and δ H is 0MPa^1/2The above 6MPa^1/2Range below.

In the dispersion liquid of the fibrousness cellulose of the present invention, the content of water to be preferred less.Relative to fibrousness fibre The gross mass of the dispersion liquid of element is tieed up, the content of the water in the dispersion liquid of fibrousness cellulose is preferably 5 mass % hereinafter, more preferably For 1 mass % or less.Furthermore the content of the water in the dispersion liquid of fibrousness cellulose is also preferably 0 mass %.

The gross mass of dispersion liquid relative to fibrousness cellulose, the fine fibre in the dispersion liquid of fibrousness cellulose The content of fibrous cellulose is preferably 0.1 mass % or more, more preferably 1 mass % or more, and then good is 2 mass % or more.Separately Outside, the gross mass relative to the dispersion liquid of fibrousness cellulose, the content of microfibre shape cellulose are preferably 30 mass % Hereinafter, more preferably 20 mass % or less.

The method of dispersion liquid as the fibrousness cellulose for obtaining the present invention, such as can enumerate: (1) in water solvent After middle carry out defibrating processing, the method for redisperse in organic solvent；(2) the side of defibrating processing is carried out in organic solvent Method.

In the method for (1), will have first phosphate or from phosphate substituent group fibrous cellulose in Defibrating processing is carried out in water solvent and obtains the slurry of the cellulose of shape containing microfibre.Then, in the shape containing microfibre fibre It ties up and adds above-mentioned organic ion in the slurry of element, obtain the condensation product or the fiber of shape containing microfibre of microfibre shape cellulose The composition of element.Then, make the condensation product of the microfibre shape cellulose of gained or the composition of the cellulose of shape containing microfibre It is scattered in organic solvent, and is stirred, thus can get the dispersion liquid of fibrousness cellulose.

In the method for (2), first using with obtain the fibrous cellulose stock dispersion of microfibre shape cellulose in In water solvent, above-mentioned organic ion is added in point dispersion liquid, obtains the condensation product of fibrous cellulose raw material.Make The condensation product is scattered in organic solvent and carries out defibrating processing (miniaturization processing), thus can get fibrousness cellulose it Dispersion liquid.

Furthermore in the present invention, the method for the dispersion liquid of the fibrousness cellulose more excellent as acquisition dispersibility, compared with The good method to use (1).

In the method for above-mentioned (1), preferably in by the group of microfibre shape cellulose or the cellulose of shape containing microfibre When conjunction object is scattered in organic solvent, it is sufficiently stirred.It as stirring means, is not particularly limited, can enumerate using following The stirring of device etc.: high speed fiber uncoiling machine, grinder (stone mortar formula pulverizer), low pressure homogenizer, high pressure homogenizer, super-high-pressure homogenization Machine, high-pressure impingement type pulverizer, ball mill, ball mill, disc mill, type taper grinder, twin shaft muller, vibrating mill, high speed rotation Homogeneous blender down, magnetic stirring apparatus, ultrasonic dispersion machine, beater etc. carry out the device of case of wet attrition.

As making microfibre shape cellulose or the composition of the cellulose of shape containing microfibre be scattered in it in organic solvent Condition is not particularly limited, such as can suitably adjust microfibre shape cellulose concentration.At this point, also can periodically be had Microfibre shape cellulose concentration is adjusted to required dispersion concentration by the addition of solvent.In addition, dispersion solvent is also adjusted Temperature, any ingredient other than microfibre shape cellulose and organic solvent can be also added in dispersion solvent.

(aqueous dispersions of fibrousness cellulose)

Also it by the microfibre shape cellulose dispersion for making the present invention or can suspend in water, and fibrousness fiber is made The aqueous dispersions (water slurry of fibrousness cellulose) of element.Furthermore in this manual, the moisture of fibrousness cellulose Dispersion liquid is the dispersion liquid without organic solvent as solvent, therefore is distinguished with the dispersion phase of above-mentioned fibrousness cellulose.

(manufacturing method of fibrous cellulose)

The present disclosure generally relates to a kind of manufacturing methods of fibrous cellulose.Specifically, the fibrous cellulose of the present invention Manufacturing method be preferably the following steps are included: will have 0.5mmol/g or more phosphate or derive from phosphate substitution The fibrous cellulose of base carries out defibrating processing in water solvent, obtains fine containing the threadiness that fiber width is 1000nm or less The step of tieing up the aqueous dispersions of element；It and will be 17 selected from the organic ion for containing the alkyl that carbon number is 5 or more and total carbon number Above at least one of the organic ion is added to the step in aqueous dispersions.

In obtain containing fiber width be 1000nm or less fibrous cellulose aqueous dispersions the step of in, preferably into Row above-mentioned<phosphate steps for importing>and<defibrating processing step>.In addition, in having for the alkyl for being 5 or more containing carbon number will be selected from At least one of the organic ion that machine ion and total carbon number are 17 or more is added in the step in aqueous dispersions, compared with Good is to carry out above-mentioned<agglomeration step>.

In the organic ion that will be selected from the alkyl for being 5 or more containing carbon number and total carbon number be 17 or more it is organic from At least one of son is added in the step in aqueous dispersions, relative to the gross mass of microfibre shape cellulose, preferably By become 2 mass % or more in a manner of add organic ion, more preferably by become 10 mass % or more in a manner of add, in turn It is good for by become 50 mass % or more in a manner of add, it is further preferred that for by become 100 mass % or more in a manner of add.In addition, this When preferably with the molal quantity of the organic ion added become microfibre shape cellulose contained by substituent group amount (mole Count) organic ion is added multiplied by 0.2 times or more of mode of the resulting value of valence mumber, more preferably to become 1.0 times or more sides Formula add organic ion, and then it is good for by become 2.0 times or more in a manner of add organic ion.

In the organic ion that will be selected from the alkyl for being 5 or more containing carbon number and total carbon number be 17 or more it is organic from At least one of son is added in the step in aqueous dispersions, can get the condensation product of microfibre shape cellulose.Yu Benfa In the manufacturing method of bright fibrous cellulose, also can in will be selected from containing carbon number be 5 or more alkyl organic ion and At least one of the organic ion that total carbon number is 17 or more is added to after the step in aqueous dispersions, and further setting will The step of condensation product separation and the step for cleaning condensation product.The microfibre shape of such gained is cellulose-based to organic solvent In dispersibility it is excellent.

(purposes)

The microfibre shape of the present invention it is cellulose-based by resin mix use or organic solvent mixing it in the form of and preferably It uses.Resin, which mixes bonding composition, can be used as the reinforcing material of resin.It mixes in bonding composition by resin by the micro- of the present invention Fine-fibrous cellulose is directly mixed with resin, can form the resin composite body that microfibre shape cellulose is uniformly dispersed.Separately Outside, organic solvent, which mixes bonding composition, can be used as the tackifier or particle dispersion stabilizer of the system comprising organic solvent.Especially It can be preferably used for mixing with organic solvent comprising resin component.By by the microfibre shape cellulose of the present invention and packet It is resinous to be mixed at the organic solvent divided, the resin composite body that microfibre shape cellulose is uniformly dispersed can be formed.It can be same Ground is filmed using microfibre shape cellulose redisperse slurry, is used as various films.