JP2019094391A - Resin composition and molding - Google Patents

Abstract

To provide a resin composition that can be made into a dispersion liquid having excellent thickening properties even when there is a low content of fine fibrous cellulose, and a molding having excellent tensile characteristics.SOLUTION: The present invention provides a resin composition containing fine fibrous cellulose with a fiber width of 1000 nm or less, a resin having at least one functional group selected from a hydroxy group and an oxo acid group, an amphoteric metal, and an organic solvent, with the water content of less than 10 mass%. There is also provided a molding.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a molded body.

Wood-derived fibrous cellulose is widely used as a natural fiber that can be regenerated from environmental awareness. It is known that fine fibrous cellulose obtained by refining fibrous cellulose into nanosize has characteristics such as excellent strength and thickening property.
In order to make fibrous cellulose fine, it is known to perform pretreatment by chemical treatment and biological treatment in combination with mechanical treatment. In particular, when a hydrophilic functional group (for example, a carboxyl group, a cationic group, a phosphoric acid group, etc.) is introduced to the hydroxy group of the cellulose surface by chemical treatment, the electric repulsion between the ions and the hydration of the ions In particular, the dispersibility in an aqueous solvent can be remarkably improved, and it is useful for the refinement of fibrous cellulose.

Moreover, fine fibrous cellulose is suitably used as a material such as a film in addition to a thickener because of its properties such as environmental friendliness, strength, thickening property and light weight.
Then, the technical improvement for the improvement of the further physical property is performed as a film containing fine fiber-like cellulose, and a composition which has thickening property (for example, refer patent documents 1-4).
In patent document 1, containing a fine fibrous cellulose, an acrylic acid type polymer, and water as a thickener composition used for paints etc. is described. Patent Document 2 describes a method of producing a film using fine fibrous cellulose and polyvinyl alcohol. Patent Document 3 describes a dispersion containing fine fibrous cellulose, a compound containing an amphoteric metal ion, and tetraalkylonium hydroxide. Patent Document 4 describes that resins such as polyvinyl alcohol, fine fibrous cellulose, and polyvalent ions such as aluminum ions are contained as a resin composite having excellent water resistance and sufficient strength.

Patent No. 5795094 gazette Patent No. 5901815 gazette Unexamined-Japanese-Patent No. 2017-52943 International Publication No. 2017/135413

However, in Patent Document 1, the thickening effect is not sufficiently satisfactory. Moreover, in patent document 2, although content of a fine fibrous cellulose is 30-55 mass parts with respect to 100 mass parts of polyvinyl alcohols, since fine fibrous cellulose is expensive, it is desired that the content is small In the technique disclosed in Patent Document 2, it is difficult to obtain a film having good tensile properties even when the content of fine fibrous cellulose is small.
Further, Patent Document 3 has a large amount of water and has room for improvement in viscosity and tensile properties, and does not disclose the effect of mixing with a specific resin and resin that can be mixed in a dispersion. Moreover, in patent document 4, the polyvalent ion in a resin complex exists as a cation, and it is not described regarding thickening property or a tensile property.
Therefore, even when the content of the fine fibrous cellulose in the composition is small, there is room for improvement for further improvement of the thickening property and the tensile properties in the case of using a dispersion or a film.

An object of the present invention is to provide a resin composition that can be made into a dispersion having excellent thickening properties even when the content of fine fibrous cellulose is small.
Another object of the present invention is to provide a molded article excellent in tensile properties.

As a result of earnest studies to solve the above problems, the present inventors considered the present invention described below and found that the problems can be solved.
That is, the present invention is as follows.

[1] A fine fibrous cellulose having a fiber width of 1000 nm or less, a resin having one or more functional groups selected from a hydroxyl group and an oxo group, an amphoteric metal, and an organic solvent, and the water content is 10% by mass The resin composition which is less than.
[2] The resin composition according to [1], further containing an organic onium salt.
[3] The resin composition according to [2], wherein the organic onium salt is a quaternary ammonium salt.
[4] The resin composition according to any one of [1] to [3], wherein a hydroxyl value or an acid value of the resin measured according to JIS K 0070: 1992 is 1 to 10000 mg KOH / g.
[5] The resin composition according to any one of [1] to [4], wherein the amphoteric metal is aluminum.
[6] The resin composition according to any one of [1] to [5], wherein the amphoteric metal is an anion.
[7] The resin composition according to any one of [1] to [6], wherein the fine fibrous cellulose has an anionic group.
[8] The resin composition according to any one of [1] to [7], wherein the resin composition is a dispersion.
[9] A molded article comprising a fine fibrous cellulose having a fiber width of 1000 nm or less, a resin having one or more functional groups selected from a hydroxyl group and an oxo acid group, and an amphoteric metal.
[10] The molded article according to [9], further containing an organic onium salt.
[11] The molded article according to [10], wherein the organic onium salt is a quaternary ammonium salt.
[12] The molded article according to any one of [9] to [11], wherein a hydroxyl value or an acid value of the resin measured according to JIS K 0070: 1992 is 1 to 10000 mg KOH / g.
[13] The molded article according to any one of [9] to [12], wherein the amphoteric metal is aluminum.
[14] The molded article according to any one of [9] to [13], wherein the amphoteric metal is an anion.
[15] The molded article according to any one of [9] to [14], wherein the fine fibrous cellulose has an anionic group.

According to the present invention, it is possible to provide a resin composition that can be made into a dispersion having excellent thickening properties even when the content of fine fibrous cellulose is small.
Further, according to the present invention, a molded article excellent in tensile properties can be provided.

FIG. 1 is a schematic view showing an example of the bonding form of the resin composition of the present invention. FIG. 2 is a graph showing the relationship between the amount of dropped NaOH and the conductivity of the fiber material having a phosphate group. FIG. 3 is a graph showing the relationship between the amount of dropped NaOH and the electrical conductivity for a fiber material having a carboxyl group.

<Resin composition>
The resin composition of the present invention is a resin having at least one kind of functional group selected from fine fibrous cellulose (sometimes referred to simply as "fine fibrous cellulose") having a fiber width of 1000 nm or less, a hydroxyl group and an oxo acid group. It is characterized by containing an amphoteric metal (sometimes simply referred to as "resin"), and an organic solvent, and having a water content of less than 10% by mass.

In the resin composition of the present invention, it is considered that the fine fibrous cellulose and the resin are crosslinked via an amphoteric metal.
Specifically, it will be described with reference to a schematic view which is an example of the bonding form of the resin composition of the present invention shown in FIG. The fine fibrous cellulose 1 has a hydroxyl group a, and the resin 2 has at least one functional group b selected from a hydroxyl group and an oxo acid group. That is, both the fine fibrous cellulose and the resin have functional groups capable of hydrogen bonding. In the resin composition, the amphoteric metal M has a functional group capable of hydrogen bonding as a hydroxide ion c such as an aluminate ion and is anionized.
Then, in the resin composition, the fine fibrous cellulose 1, the resin 2 and the amphoteric metal M respectively have the above-mentioned functional groups so that hydrogen bonding becomes possible, and the fine fibrous cellulose 1 and the resin 2 can be intervened through the amphoteric metal M. Are believed to form a cross-linked linkage form.

Furthermore, it is thought that, when the content of water is less than 10% by mass, the resin composition of the present invention can make the above-mentioned hydrogen bond stronger and can exhibit excellent thickening property.
Therefore, the resin composition of the present invention can give a dispersion having excellent thickening property which can not be obtained with a dispersion containing only one of the fine fibrous cellulose and the resin by having the above-mentioned bonding form. .
When the solid content is 1.1% by mass, the viscosity of the resin composition of the present invention is 5 mPa · s or more, preferably 10 mPa · s or more, more preferably 100 mPa or more, still more preferably 1000 mPa · s or more can do.
In the present invention, the viscosity can be measured by a B-type viscometer, and specifically, it can be measured by the method described in the examples described later.
In addition, by using the resin composition of the present invention, it is also possible to mold a molded article having a large specific energy absorption amount and excellent tensile properties. The reason is not clear, but when the content of water in the resin composition is less than 10% by mass, it is possible to improve the tensile properties.

[Fine fibrous cellulose]
(Fine fibrous cellulose)
The fine fibrous cellulose used in the present invention can be produced from a fiber material containing cellulose.
The fiber raw material containing cellulose is not particularly limited, but it is preferable to use pulp in terms of availability and low cost. Pulp includes, for example, wood pulp, non-wood pulp and deinked pulp. The wood pulp is not particularly limited. For example, hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), sulfite pulp (SP), dissolving pulp (DP), soda pulp (AP), unbleached kraft pulp (UKP ) And chemical pulp such as oxygen bleached kraft pulp (OKP), semichemical pulp such as semichemical pulp (SCP) and chemigroundwood pulp (CGP), ground pulp (GP) and thermomechanical pulp (TMP, BCTMP) Mechanical pulp etc. are mentioned. The non-wood pulp is not particularly limited, and examples thereof include cotton-based pulps such as cotton linters and cotton lint, and non-wood-based pulps such as hemp, straw and bagasse. The deinked pulp is not particularly limited, and examples thereof include deinked pulp made from used paper as a raw material. The pulp of this embodiment may be used singly or in combination of two or more.
Among the above-mentioned pulps, wood pulp and deinked pulp are preferable, for example, from the viewpoint of easy availability. Further, among the wood pulps, in view of a high ratio of cellulose and a high yield of fine fibrous cellulose at the time of fibrillation treatment, the decomposition of cellulose in the pulp is small, and a fine fibrous cellulose of long fibers having a large axial ratio can be obtained. From the viewpoint, for example, chemical pulp is more preferable, and kraft pulp and sulfite pulp are more preferable. In addition, when the fine fibrous cellulose of the long fiber with a large axial ratio is used, there exists a tendency for a viscosity to become high.

As a fiber material containing cellulose, for example, cellulose contained in ascidians and bacterial cellulose produced by acetic acid bacteria can also be used.
Moreover, it can replace with the fiber raw material containing a cellulose, and can also use the fiber which linear nitrogen-containing polysaccharide polymers, such as chitin and chitosan, form.

(Fiber width)
The fiber width of the fine fibrous cellulose used in the present invention is 1000 nm or less. When the fiber width exceeds 1000 nm, the thickening property is lowered, and the effect of the present invention can not be exhibited.
The fiber width of the fine fibrous cellulose is preferably 2 nm to 1000 nm, more preferably 2 nm to 100 nm, still more preferably 2 nm to 50 nm, and particularly preferably 2 nm to 10 nm. preferable. By setting the fiber width of the fine fibrous cellulose to 2 nm or more, it is possible to suppress dissolution in water as cellulose molecules and to more easily express the effect of improving the strength, rigidity, and dimensional stability by the fine fibrous cellulose. Can. The fine fibrous cellulose is, for example, monofibrillar cellulose.

The average fiber width of the fine fibrous cellulose is measured, for example, using an electron microscope as follows. First, an aqueous suspension of fine fibrous cellulose with a concentration of 0.05% by mass or more and 0.1% by mass or less is prepared, and this suspension is cast on a hydrophilized carbon film-coated grid for TEM observation Let it be a sample. If wide fibers are included, an SEM image of the surface cast on glass may be observed. Next, observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times or 50000 times depending on the width of the fiber to be observed. However, the sample, observation conditions and magnification are adjusted to satisfy the following conditions.
(1) One straight line X is drawn at an arbitrary position in the observation image, and 20 or more fibers cross the straight line X.
(2) Draw a straight line Y intersecting perpendicularly with the straight line in the same image, and 20 or more fibers cross the straight line Y.

  With respect to the observation image satisfying the above conditions, the width of the fiber intersecting with the straight line X and the straight line Y is visually read. In this way, three or more sets of observation images of surface portions not overlapping each other at least are obtained. Then, for each image, the width of the fiber intersecting the straight line X and the straight line Y is read. Thereby, a fiber width of at least 20 × 2 × 3 = 120 is read. And let the average value of the read fiber width be an average fiber width of fine fibrous cellulose.

  The fiber length of the fine fibrous cellulose is not particularly limited, but is preferably 0.1 μm to 1000 μm, for example, and more preferably 0.1 μm to 800 μm, and preferably 0.1 μm to 600 μm. More preferable. By setting the fiber length within the above range, it is possible to suppress the destruction of the crystalline region of the fine fibrous cellulose. It also becomes possible to make the slurry viscosity of fibrous cellulose into a suitable range. In addition, the fiber length of fine fibrous cellulose can be calculated | required from the image analysis by TEM, SEM, and AFM, for example.

The fine fibrous cellulose preferably has a type I crystal structure. Here, the fact that the fine fibrous cellulose has a type I crystal structure can be identified in a diffraction profile obtained from a wide angle X-ray diffraction photograph using CuKα (λ = 1.5418 Å) monochromatized with graphite. Specifically, it can be identified from having typical peaks at two positions of 2θ = 14 ° or more and 17 ° or less and 2θ = 22 ° or more and 23 ° or less.
The proportion of the type I crystal structure in the fine fibrous cellulose is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. Thereby, it can be expected to be excellent in heat resistance and low linear thermal expansion coefficient. With regard to the degree of crystallinity, the X-ray diffraction profile is measured, and the pattern is determined by a conventional method (Seagal et al., Textile Research Journal, 29: 786, 1959).
The fibrous cellulose in the present embodiment has, for example, both a crystalline region and a noncrystalline region. In particular, fine fibrous cellulose having both crystalline regions and noncrystalline regions and having a high axial ratio is realized by the method of producing fine fibrous cellulose described later.

(Anionic group)
The fine fibrous cellulose preferably has an anionic group. From the viewpoint of enhancing the disintegration efficiency in the disintegration treatment of fibrous cellulose, an anionic group is introduced to the fibrous cellulose by reacting the fiber raw material with the compound having an anionic group.
As the anionic group, for example, a phosphate group or a substituent derived from a phosphate group (sometimes simply referred to as “phosphate group”), a carboxyl group or a substituent derived from a carboxyl group (simply “carboxyl group” And at least one selected from a sulfone group or a substituent derived from a sulfone group (sometimes referred to simply as “sulfone group”), and is selected from a phosphate group and a carboxyl group It is more preferable that it is at least one selected from the group consisting of: phosphoric acid group.

A phosphoric acid group is a group which functions as a dibasic acid which corresponds to what removed the hydroxy group from phosphoric acid. Groups derived from phosphate groups include salts of phosphate groups, phosphate ester groups and the like. In addition, the group originating in a phosphoric acid group may be contained in the fine cellulose fiber as a group which the phosphoric acid group condensed.
The phosphate group or the group derived from the phosphate group is, for example, a group represented by the following formula (1).

In formula (1), a, b and n are natural numbers (however, a = b × m). At least one of α ¹ , α ² ,..., α ⁿ and α ′ is O ⁻ , and the remainder is either R or OR. All of each α ⁿ and α ′ may be O ⁻ . When n is 2 or more and α ′ is R or OR, at least one of each α ⁿ is O ⁻ and the remainder is R or OR. n is equal to or greater than 2, alpha 'is O ^- when it is may be a respective alpha ⁿ are all R, may be all OR, at least one O ^- remaining in the R or It may be OR. R each independently represents a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched chain Hydrocarbon groups, aromatic groups, and derivatives thereof.
Although a methyl group, an ethyl group, n-propyl group, or n-butyl group etc. are mentioned as a saturated-linear hydrocarbon group, It does not specifically limit. Examples of the saturated-branched hydrocarbon group include i-propyl group and t-butyl group, but are not particularly limited. Although a cyclopentyl group, a cyclohexyl group, etc. are mentioned as a saturated cyclic hydrocarbon group, It does not specifically limit. Examples of the unsaturated-linear hydrocarbon group include, but are not particularly limited to, a vinyl group, an allyl group and the like. Examples of unsaturated-branched hydrocarbon groups include i-propenyl group and 3-butenyl group, but are not particularly limited. Although a cyclopentenyl group, a cyclohexenyl group, etc. are mentioned as unsaturated-cyclic hydrocarbon group, It does not specifically limit. Examples of the aromatic group include, but are not particularly limited to, a phenyl group or a naphthalene group.
In addition, as the derivative in R, at least one of functional groups such as a carboxyl group, a hydroxyl group, or an amino group is added or substituted to the main chain or side chain of the various hydrocarbon groups. Although a group is mentioned, it is not limited in particular. The number of carbon atoms constituting the main chain of R is not particularly limited, but is preferably 20 or less, and more preferably 10 or less. By setting the number of carbon atoms constituting the main chain of R to 20 or less, it is possible to prevent the molecule of the phosphorus oxo acid group containing R from becoming too large and maintain good permeability to the fiber material, It can contribute to the improvement of the yield of fine cellulose fiber.
β ^{b +} is a monovalent or more cation composed of an organic substance or an inorganic substance. The monovalent or more monovalent cations of organic substances include aliphatic ammonium or aromatic ammonium, and the monovalent or more monovalent cations of inorganic substances include ions of alkali metals such as sodium, potassium or lithium, Examples thereof include cations of divalent metals such as calcium or magnesium, or hydrogen ions, but not particularly limited. These can also be applied combining 1 type or 2 or more types. The monovalent or more monovalent cation composed of an organic substance or an inorganic substance is preferably an ion of sodium or potassium which is not easily yellowed when the fiber material containing β is heated and which is industrially easy to use, but is not particularly limited.

The amount of the anionic group introduced into the fine fibrous cellulose is, for example, preferably 0.10 mmol / g or more, more preferably 0.20 mmol / g or more, per 1 g (mass) of the fine fibrous cellulose, and 0. It is more preferably 50 mmol / g or more, particularly preferably 1.00 mmol / g or more.
When the anionic group is a phosphate group, the amount of phosphate group introduced into the fine fibrous cellulose is, for example, preferably 3.65 mmol / g or less per 1 g (mass) of fine fibrous cellulose, and 3. It is more preferably 50 mmol / g or less, and still more preferably 3.00 mmol / g or less.
By making the introduction amount of the anionic group within the above range, it is possible to facilitate the miniaturization of the fiber raw material, and it is possible to enhance the stability of the fine fibrous cellulose. Further, by setting the introduction amount of the anionic group in the above range, good properties can be exhibited in various uses as a thickener and the like of the resin composition containing fine fibrous cellulose.
The introduction amount of the anionic group to the fine fibrous cellulose can be measured, for example, by the conductivity titration method. In the measurement by the conductivity titration method, the introduced amount is measured by determining the change in conductivity while adding an alkali such as an aqueous solution of sodium hydroxide to the obtained slurry containing fine fibrous cellulose.

FIG. 2 is a graph showing the relationship between the amount of dropped NaOH and the electrical conductivity with respect to fine fibrous cellulose having a phosphate group.
The introduction amount of the phosphate group to the fine fibrous cellulose can be measured as follows.
First, a slurry containing fine fibrous cellulose is treated with a strongly acidic ion exchange resin. In addition, you may implement the disintegration processing similar to the below-mentioned disintegration processing process with respect to a measuring object before the processing by strongly acidic ion exchange resin as needed. Then, while the aqueous sodium hydroxide solution is added, the change in electrical conductivity is observed to obtain a titration curve as shown in FIG. As shown in FIG. 2, the electric conductivity drops rapidly at first (hereinafter, referred to as “first region”). Thereafter, the conductivity starts to rise slightly (hereinafter referred to as "the second region"). After that, the increment of conductivity increases (hereinafter, referred to as "third region"). The boundary point between the second area and the third area is defined as a point at which the second derivative value of the conductivity, that is, the change amount of the increment (inclination) of the conductivity is maximum. Thus, three regions appear in the titration curve. Among them, the amount of alkali required in the first region is equal to the amount of strongly acidic groups in the slurry used for titration, and the amount of alkali required in the second region is the amount of weakly acidic groups in the slurry used for titration Become equal. When the phosphoric acid group causes condensation, the weakly acidic group is apparently lost, and the amount of alkali required for the second region is smaller than the amount of alkali required for the first region. On the other hand, the amount of strongly acidic groups is the same as the amount of phosphorus atoms regardless of the presence or absence of condensation. For this reason, when it is simply referred to as a phosphate group introduction amount (or a phosphate group amount) or a substituent introduction amount (or a substituent amount), it means the amount of strongly acidic group. Therefore, the value obtained by dividing the amount of alkali (mmol) required in the first region of the titration curve obtained above by the solid content (g) in the slurry to be titrated is the amount of phosphate group introduced (mmol / g).

In addition, since the above-mentioned phosphate group introduction amount (mmol / g) indicates that “g” of the denominator represents the mass of acid type fine fibrous cellulose, the amount of phosphate groups possessed by acid type fine fibrous cellulose (“ (It may be called "phosphate amount (acid type)"). On the other hand, when the counter ion of the phosphate group is substituted by an arbitrary cation C so as to be a charge equivalent, the denominator is converted to the mass of fine fibrous cellulose when the cation C is a counter ion By doing this, it is possible to determine the amount of phosphoric acid groups (sometimes referred to as “the amount of phosphoric acid groups (C type)”) possessed by the fine fibrous cellulose in which the cation C is a counter ion.
That is, it calculates with the following formula.
Amount of phosphoric acid group (C type) = amount of phosphoric acid group (acid type) / {1 + (W-1) x A / 1000}
A [mmol / g]: Total amount of anion derived from phosphoric acid group possessed by fine fibrous cellulose (value obtained by adding the amount of strongly acidic group of phosphoric acid group and the amount of weakly acidic group)
W: Formula weight per monovalent C cation (for example, 23 for Na, 9 for Al)

Moreover, FIG. 3 is a graph which shows the relationship of the amount of NaOH dripping with respect to the fine fibrous cellulose which has a carboxyl group, and electrical conductivity.
The introduction amount of carboxyl group to the fine fibrous cellulose is measured, for example, as follows.
First, a slurry containing fine fibrous cellulose is treated with a strongly acidic ion exchange resin. In addition, you may implement the disintegration processing similar to the below-mentioned disintegration processing process with respect to a measuring object before the processing by strongly acidic ion exchange resin as needed. Then, while the aqueous sodium hydroxide solution is added, the change in electrical conductivity is observed to obtain a titration curve as shown in FIG. In addition, you may implement the disintegration processing similar to the below-mentioned disintegration processing process with respect to a measuring object as needed. The titration curve, as shown in FIG. 3, shows that after the conductivity decreases, the first region until the conductivity increment (slope) becomes almost constant, and then the conductivity increment (slope) increases. It is divided into the second area. The boundary point between the first region and the second region is defined as a point at which the second derivative value of the conductivity, that is, the amount of change in the conductivity increment (slope) becomes maximum. And the value obtained by dividing the amount of alkali (mmol) required in the first region of the titration curve by the solid content (g) in the fine fibrous cellulose-containing slurry to be titrated is the amount of carboxyl group introduced ( It becomes mmol / g).

In addition, since the above-mentioned carboxyl group introduction amount (mmol / g) is the mass of the fine fibrous cellulose of the acid type “g” of the denominator, the amount of carboxyl groups possessed by the fine fibrous cellulose of the acid type (“Carboxyl group Amount (sometimes referred to as “acid form”). On the other hand, when the counter ion of the carboxyl group is substituted by an arbitrary cation C so as to have a charge equivalent, the denominator is converted to the mass of fine fibrous cellulose when the cation C is a counter ion Thereby, it is possible to determine the amount of carboxyl groups (sometimes referred to as “amount of carboxyl group (C type)”) possessed by the fine fibrous cellulose in which the cation C is a counter ion.
That is, it calculates with the following formula.
Carboxyl group weight (C type) = Carboxyl group weight (acid type) / {1+ (W-1) × (Carboxyl group weight (acid type)) / 1000}
W: Formula weight per monovalent C cation (for example, 23 for Na, 9 for Al)

  A well-known technique can be used as a method of introduce | transducing an anionic group into fibrous cellulose and refine | miniaturizing, For example, the anionic group introduction process of introduce | transducing an anionic group to a fiber raw material, a washing process, an alkali treatment process ( Neutralization Step) Through the defibration treatment step, it can be obtained as a dispersion liquid containing fine fibrous cellulose into which an anionic group has been introduced. The obtained dispersion liquid containing fine fibrous cellulose can be used as it is for the production of the resin composition of the present invention described later.

In the anionic group introducing step, when the anionic group is a phosphate group, for example, a fiber raw material containing cellulose and a compound capable of introducing a phosphate group are reacted while heating in the presence of urea or a derivative thereof Can be done.
As a compound capable of introducing a phosphate group, the efficiency of introduction of the phosphate group is high, and the disaggregation efficiency can be more easily improved in the defibration step described later, and can be applied at low cost and industrially, Phosphoric acid, sodium salt of phosphoric acid, potassium salt of phosphoric acid, and ammonium salt of phosphoric acid are preferable, and phosphoric acid, sodium dihydrogen phosphate, and disodium hydrogen phosphate, ammonium dihydrogen phosphate are more preferable.
The addition amount of the compound capable of introducing the phosphate group to the fiber raw material may be appropriately determined so as to be the introduction amount of the anionic group to the fine fibrous cellulose described above.

Examples of urea or derivatives thereof include urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea and 1-ethylurea. Urea and its derivative may be used individually by 1 type of the above, and may be used in mixture of 2 or more types.
The amount of urea or its derivative added to the fiber material (absolute dry mass) is not particularly limited, but is preferably 1% by mass to 500% by mass, and more preferably 10% by mass to 400% by mass And 100% by mass or more and 350% by mass or less.
The phosphate group introduction step may be performed at least once, but may be repeated twice or more.

When the anionic group is a carboxyl group, oxidation treatment such as oxidation by ozone oxidation or Fenton method, TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) oxidation treatment, etc., to a fiber raw material containing cellulose Or a compound having a group derived from carboxylic acid or a derivative thereof, or an acid anhydride of a compound having a group derived from carboxylic acid or a derivative thereof.
Examples of the compound having a group derived from carboxylic acid include dicarboxylic acids such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid and itaconic acid; tricarboxylic acids such as citric acid and aconitic acid; maleic anhydride, Acid anhydrides such as succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, itaconic anhydride; compounds having a carboxyl group such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride, etc. The derivative etc. of the acid anhydride in which the hydrogen atom of the at least one part of the acid anhydride was substituted by substituents, such as an alkyl group and a phenyl group, are mentioned.
The addition amount of the compound having a group derived from carboxylic acid to the fiber raw material may be appropriately determined so as to be the introduction amount of the anionic group to the above-mentioned fine fibrous cellulose.

The above-mentioned washing step is carried out, for example, by washing fibrous cellulose introduced with an anionic group with water or an organic solvent, and the number of washings is not particularly limited.
Although it does not specifically limit as said alkali treatment process (neutralization process), For example, the method of immersing the fibrous cellulose which introduce | transduced anionic group in the alkaline solution is mentioned. As the alkaline solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution and the like are preferable because of high versatility.
The fibrillation treatment process can be performed using a fibrillation treatment apparatus. Among the disintegration processing apparatuses, it is preferable to use a high speed disintegration device, a high pressure homogenizer, or an ultra high pressure homogenizer which is less affected by the grinding media and less likely to contaminate. Moreover, in the defibration treatment step, it is preferable to dilute the fibrous cellulose into which an anionic group has been introduced into a dispersion medium to obtain a dispersion. The dispersion medium is selected from water and an organic solvent such as a polar organic solvent, and one of the above may be used alone, or two or more may be mixed and used.

(Content of fine fibrous cellulose)
The content of the fine fibrous cellulose in the resin composition of the present invention is preferably 0.0001 to 50% by mass, more preferably 0.001 to 30% by mass, and still more preferably 0.01 to 10% by mass. The resin composition of the present invention can give a dispersion having excellent thickening properties even when the content of fine fibrous cellulose is small, and the viscosity can be sufficiently expressed within the above range. be able to.
Further, the content ratio [fine fibrous cellulose / resin] in the mass ratio of the fine fibrous cellulose to the resin described later in the resin composition of the present invention is preferably 0.1 / 99.9 to 50/50. 1/99 to 30/70 is more preferable, and 5/95 to 20/80 is further preferable.

[resin]
The resin used in the present invention has at least one functional group selected from a hydroxyl group and an oxo acid group. As described above, by having the above-mentioned functional group, the resin is considered to form a cross-linked structure with the fine fibrous cellulose via the amphoteric metal and to exhibit excellent thickening property and tensile property.
Examples of the oxo acid group include a carboxyl group, a phosphate group, a sulfo group and a sulfate group. Among the above functional groups, from the viewpoint of the ease of hydrogen bonding with an amphoteric metal, preferred are a hydroxyl group and a carboxyl group, and more preferred is a hydroxyl group. The hydroxyl group may be either an alcoholic hydroxyl group or a phenolic hydroxyl group, preferably an alcoholic hydroxyl group.
The resin is a homopolymer of a monomer having one or more functional groups selected from a hydroxyl group and an oxo acid group, a copolymer of a monomer having the functional group and a monomer having no functional group, the functional group It may be a copolymer of a plurality of monomers each having a different type of.

The resin having a hydroxyl group is not particularly limited as long as it has a hydroxyl group, and polyvinyl alcohol resins, polyester resins having hydroxyl groups, urethane resins having hydroxyl groups, phenol resins and the like can be mentioned.
The resin having a carboxyl group is not particularly limited as long as it has a carboxyl group, and acrylic resins having a carboxyl group such as polyacrylic acid and alkyl methacrylate / acrylic acid copolymer, carboxyvinyl resin, polyglycolic acid And polyester resins.
Among the above-described resins, polyvinyl alcohol, poly (meth) acrylic acid and carboxyvinyl resin are preferable from the viewpoint of viscosity and tensile properties, and polyvinyl alcohol is more preferable.
The resin having one or more types of functional groups selected from a hydroxyl group and an oxo acid group may be used alone or in combination of two or more.

  The hydroxyl value or acid value of the above-mentioned resin measured according to JIS K 0070: 1992 is preferably 1 to 10000 mg KOH / g, more preferably 2 to 5000 mg KOH / g, and still more preferably 5 to 2000 mg KOH / g. If it is in the said range, a crosslinking point can fully be formed and the resin composition which was more excellent in viscosity can be obtained.

  The content of the resin in the resin composition of the present invention is preferably 0.0001 to 99.9% by mass, and more preferably 0.001 to 99% by mass, from the viewpoint of thickening property by a sufficient amount of crosslinking points. 0.01-95 mass% is further more preferable.

[Ampholytic metal]
The amphoteric metal contained in the resin composition of the present invention includes aluminum, zinc, tin and lead, and may be used alone or in combination of two or more. Among the amphoteric metals, aluminum and zinc are preferable, and aluminum is more preferable, from the viewpoint of being able to improve the thickening property with a small amount because there are many valences per atomic weight.
The amphoteric metal is present as an anion in the resin composition as described above, and the resin composition of the present invention can be produced by the method described later using a compound containing the amphoteric metal. Examples of the compound containing an amphoteric metal include aluminum sulfate, polyaluminum chloride, aluminum chloride, zinc sulfate, zinc chloride, tin sulfate, tin chloride, lead sulfate, lead chloride and the like. The compound containing an amphoteric metal may be used singly or in combination of two or more.

The content of the amphoteric metal in the resin composition of the present invention is preferably 0.000001 to 5% by mass, more preferably 0.00001 to 3% by mass, from the viewpoint of the thickening property by a sufficient amount of crosslinking points. More preferably, from .0001 to 1% by mass.
In addition, content of the said amphoteric metal can be calculated according to the method as described in the Example mentioned later.

[Organic solvent]
It is preferable that the organic solvent contained in the resin composition of this invention does not have a hydroxyl group and an oxo acid group.
As an organic solvent, for example, dimethylsulfoxide; dimethylformamide; dimethylacetamide; 2-pyrrolidone; N-methyl-2-pyrrolidone; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate: diethyl ether, tetrahydrofuran Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether and ethylene glycol mono t-butyl ether, pyridine, aniline, hexane, cyclohexane, benzene, toluene, p-xylene, dichloromethane, chloroform Carbon tetrachloride etc. are mentioned. Among the above organic solvents, dimethyl sulfoxide is preferable from the viewpoint of the solubility of the resin. The organic solvent may be used alone or in combination of two or more.
The content of the organic solvent in the resin composition of the present invention is preferably 0.01 to 90% by mass, more preferably 0.05 to 50% by mass, from the viewpoint of exhibiting excellent thickening property. More preferably, it can be adjusted to be 0.1 to 5% by mass.

[Water content]
The content of water in the resin composition of the present invention is less than 10% by mass, preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.6% by mass or less. , 0 mass% may be sufficient. When the content of the water is 10% by mass or more, excellent viscosity can not be expressed.

[Organic onium salt]
The resin composition of the present invention preferably contains an organic onium salt.
Examples of onium salts of organic onium salts include ammonium salts, phosphonium salts, oxonium salts, sulfonium salts, fluoronium salts, chloronium salts, bromonium salts, iodonium salts and the like, with preference given to ammonium salts and phosphonium salts, with preference given to Is an ammonium salt.
Among the organic onium salts, from the viewpoint of hydrophobizing fine fibrous cellulose, tetraalkyl onium hydroxide and the like are preferable, particularly tetraalkyl ammonium hydroxide and tetraalkyl phosphonium hydroxide are preferable, and tetraalkyl ammonium hydroxide is more preferable.

Examples of tetraalkylammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylmethylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide and tetraethylammonium hydroxide. Heptyl ammonium hydroxide, lauryl trimethyl ammonium hydroxide, cetyl trimethyl ammonium hydroxide, stearyl trimethyl ammonium hydroxide, octyl dimethyl ethyl ammonium hydroxide, lauryl dimethyl ethyl ammonium hydroxide, didecyl dimethyl ammonium hydroxide, lauryl dimethyl benzyl ammonium Muhidorokishido, tributyl benzyl ammonium hydroxide, methyl tri -n- octyl ammonium hydroxide, alkyl dimethyl benzyl ammonium hydroxide, di -n- alkyldimethyl ammonium hydroxide, behenyl trimethyl ammonium hydroxide, and the like.
Examples of tetraalkyl phosphonium hydroxides include tetramethyl phosphonium hydroxide, tetraethyl phosphonium hydroxide, tetrapropyl phosphonium hydroxide, tetrabutyl phosphonium hydroxide, triethyl methyl phosphonium hydroxide, tetraphenyl phosphonium hydroxide, tetraoctyl phosphonium hydroxide, aceto Nyltriphenylphosphonium hydroxide, allyltriphenylphosphonium hydroxide, amyltriphenylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide and the like. The organic onium salt may be used alone or in combination of two or more.

The content of the organic onium salt in the resin composition of the present invention is preferably 0.001 to 10% by mass, and more preferably 0.005 to 5% by mass, from the viewpoint of thickening property by a sufficient amount of crosslinking points. 0.01 to 1% by mass is more preferable.
Also, from the viewpoint of thickening property by fine dispersion of fine fibrous cellulose, the content of the organic onium salt with respect to the total amount of anions introduced to the fine fibrous cellulose and the total amount of amphoteric metal ions is preferably 0 in molar ratio. 1 to 10, more preferably 0.5 to 5.

[Other ingredients]
In the resin composition of the present invention, other components other than the fine fibrous cellulose, the resin and the amphoteric metal may be added as long as the effects of the present invention are not impaired. Other components include surfactants, organic ions, coupling agents, inorganic layered compounds, inorganic compounds, leveling agents, preservatives, antifoaming agents, organic particles, lubricants, antistatic agents, UV protective agents, dyes. Pigments, stabilizers, magnetic powders, orientation accelerators, plasticizers, dispersants, crosslinking agents, and the like. The other components may be used alone or in combination of two or more.

[Method of producing resin composition]
In the resin composition of the present invention, for example, when the fine fibrous cellulose has an anionic group, a concentration step of obtaining a concentrate of fine fibrous cellulose using the dispersion containing the fine fibrous cellulose described above, the concentrate It can manufacture by passing through the collection process of collecting, the re-dispersion process of re-dispersing fine fibrous cellulose, and the process mixed with resin.
Moreover, the resin composition of this invention can be obtained in the state of a dispersion liquid through the said process.

(Concentration process)
The concentration step is a step of adding a compound containing the above-mentioned amphoteric metal to a dispersion liquid containing the above-described fine fibrous cellulose to obtain a concentrate of the fine fibrous cellulose. By this process, the cation which is a counter ion of the anionic group introduce | transduced into the fine fibrous cellulose is substituted by the cation of an amphoteric metal. By substitution of the cation, the fine fibrous cellulose is aggregated to obtain a concentrate of fine fibrous cellulose.
There is no particular limitation on the method of adding the above-described compound containing an amphoteric metal to the above-described dispersion containing fine fibrous cellulose. For example, a compound containing an amphoteric metal may be added while stirring a dispersion containing fine fibrous cellulose. The compound containing an amphoteric metal may be added as a solid, or may be added as a solution or dispersion using a solvent. The stirring time is not particularly limited as long as the fine fibrous cellulose and the amphoteric metal are mixed, but it is usually about 1 minute to 8 hours, preferably 1 to 8 hours.

(Recovery process)
The recovery step is a step of recovering the concentrate by, for example, filtration, washing and drying. There is no restriction | limiting in particular in the collection | recovery method, What is necessary is just to carry out by a well-known method.
For example, filtration may be performed using filters such as filter paper, non-woven fabric, membrane filter, etc., and filtration may be performed by natural filtration, vacuum filtration, pressure filtration, centrifugal separation or the like.
The washing may be performed using a washing solution such as water or an organic solvent, and the washing may be performed by heating the washing solution to a normal temperature or about 30 to 70 ° C. Drying may be performed by reduced pressure drying, heat drying or the like. When heating is performed, the drying can be performed usually at about 30 to 70 ° C. and usually for about 1 to 60 minutes.
The above washing and drying may or may not be carried out, and may be carried out repeatedly, and there is no restriction on the order.
Further, from the viewpoint of sufficiently advancing the substitution of the counter ion to the amphoteric metal, the conductivity of the filtrate in the above-mentioned filtration is preferably 130 μS / cm or less.

(Redispersion process)
The re-dispersion step is a step of adding the organic onium salt to the recovered concentrate to re-disperse the fine fibrous cellulose in the organic solvent.
By the re-dispersion step, the amphoteric metal of the cation aggregating the fine fibrous cellulose can be separated, and the fine fibrous cellulose can be dispersed again. At this time, the amphoteric metal is anionized by the added organic onium salt. In addition, the fine fibrous cellulose is hydrophobized by the anionic group of the fine fibrous cellulose and the cation of the organic onium, and the compatibility between the resin to be mixed later and the fine fibrous cellulose can be improved.

As an organic onium salt used at this process, what was illustrated as an organic onium salt which may be contained in a resin composition by description of the resin composition of this invention mentioned above is mentioned.
The addition amount of the organic onium salt in this step is a molar ratio with respect to the total amount of anions and amphoteric metal ions introduced to the fine fibrous cellulose from the viewpoint of thickening property by the good dispersion of the fine fibrous cellulose. Preferably it is 0.1-10, More preferably, it is 0.5-5.

Further, as the organic solvent, those exemplified as the organic solvent contained in the resin composition in the description of the resin composition of the present invention described above can be used.
The amount of the organic solvent added in this step is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, of the fine fibrous cellulose in the redispersion solution from the viewpoint of uniformly dispersing It is preferable to adjust so as to be%.

  The dispersing apparatus used for redispersion is not particularly limited. For example, a high-speed fibrillation machine, a grinder (stone mill type crusher), a high pressure homogenizer or an ultrahigh pressure homogenizer, a high pressure collision type crusher, a ball mill, a bead mill, a bead mill, a disc type refiner, a conical refiner A twin-screw kneader, a vibration mill, a homomixer under high speed rotation, an ultrasonic disperser, a beater or the like can be used.

(Step of mixing with resin)
The resin composition of the present invention can be produced through the process of adding the above-mentioned resin to the above redispersion solution and mixing.
The resin may be added after being dissolved or dispersed in an organic solvent in advance. As the organic solvent, those exemplified in the above redispersion step can be used, and it is preferably the same as the organic solvent used in the dispersion step.
In the present step, other components other than the fine fibrous cellulose, the resin and the amphoteric metal may be added to the redispersion solution as long as the effects of the present invention are not impaired. Other components are as described above.

Whether or not the resin composition produced from the above contains an organic onium salt can be determined by ion chromatography, but in the case of tetraalkylammonium hydroxide, a trace nitrogen analysis method in the case of tetraalkylammonium hydroxide, in the case of tetraalkylphosphonium hydroxide And molybdenum blue method and the like.
When the resin composition produced from the above contains tetraalkylammonium hydroxide, the nitrogen content of the resin composition is preferably 1 to 10 in molar ratio with respect to the amount of the amphoteric metal contained in the resin composition. And 2 to 6 are more preferable.
When the resin composition produced from the above contains tetraalkylphosphonium hydroxide, the phosphorus content of the resin composition is preferably 2 to 12 in molar ratio with respect to the amount of the amphoteric metal contained in the resin composition. And 4-8 are more preferable.

<Molded body>
The present invention provides a fine fibrous cellulose having a fiber width of 1000 nm or less, a resin having one or more functional groups selected from a hydroxyl group and an oxo acid group, and a molded article containing an amphoteric metal.
The molded article of the present invention has a characteristic of being excellent in tensile properties such as a large amount of specific tensile energy. The specific tensile energy content of the molded article of the present invention is 0.5 mJ / g or more, preferably 3.5 mJ / g or more, and more preferably 5.0 mJ / g or more.
In the present invention, the specific tensile energy amount can be measured in accordance with JIS P 8113: 2006, and specifically, it is measured by the method described in the examples described later.
Further, the above-mentioned fine fibrous cellulose, resin and amphoteric metal contained in the molded body can be equivalent to the fine fibrous cellulose, resin and amphoteric metal contained in the above-mentioned resin composition, and each content is also It can be equal. Furthermore, the molded object of this invention can contain an organic onium salt, and the organic onium salt which may be contained in the above-mentioned resin composition, and its content can also be made equivalent.

Although it does not specifically limit as a manufacturing method of the said molded object, For example, the said molded object can be manufactured by shape | molding using the above-mentioned resin composition.
There is no restriction | limiting in particular as a molding method at the time of shape | molding the above-mentioned resin composition, and forming it into a molded object According to the desired molded object, compression molding, transfer molding, extrusion molding, injection molding, a cast method, inflation molding etc. A known method of may be adopted. As a film forming method in the case of using a molded object as a sheet, a cast method, an inflation method, etc. are preferable and you may carry out using a drum roll.

<Use>
The resin composition of the present invention can be used as a thickener for additives for various uses such as food, cosmetics, cement, paint, and ink. In addition, the resin composition of the present invention may be molded into a molded article by a known method, or the resin composition may be formed into a film to produce various sheets.
The molded article of the present invention can also be used as a reinforcing material and various sheets. The sheet is suitable for use as a light transmitting substrate such as various display devices and various solar cells. In addition, it is suitable for applications such as substrates of electronic devices, members of household appliances, window materials of various vehicles and buildings, interior materials, exterior materials, packaging materials, and the like. Furthermore, the sheet itself is suitable for use as a reinforcing material.
In addition, the resin composition and the molded article of the present invention are suitable for applications such as yarns, filters, fabrics, cushioning materials, sponges, abrasives and the like.

  Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto.

<Production Example 1-1>
[Production of Fine Fibrous Cellulose Dispersion]
Softwood kraft pulp manufactured by Oji Paper Co., Ltd. (solid content 93% by mass, basis weight 208 g / m ^{2 in} sheet form) as a raw material pulp, Canadian Standard Freeness (CSF) which is disintegrated and measured according to JIS P 8121 Used 700 ml).

  The raw material pulp was subjected to a phosphorylation treatment as follows. First, a mixed aqueous solution of ammonium dihydrogen phosphate and urea is added to 100 parts by mass (dry mass) of the above-mentioned raw material pulp to make 45 parts by mass of ammonium dihydrogen phosphate, 120 parts by mass of urea, 150 parts by mass of water The solution was adjusted to obtain a chemical solution impregnated pulp. Next, the chemical-impregnated pulp obtained was heated for 200 seconds with a hot air drier at 165 ° C. to introduce a phosphoric acid group to the cellulose in the pulp to obtain a phosphorylated pulp.

  Next, the resulting phosphorylated pulp was subjected to a washing treatment. The washing process is performed by repeating the operation of filtering and dewatering the pulp dispersion obtained by pouring 10 L of ion-exchanged water with respect to 100 g (absolute dry mass) of phosphorylated pulp so that the pulp can be uniformly dispersed. went. When the electric conductivity of the filtrate became 100 μS / cm or less, it was regarded as the washing end point.

  The above-described phosphorylation treatment and the above-mentioned washing treatment were further performed once in this order on the phosphorylated pulp after washing.

  Next, neutralization treatment was performed on the washed phosphorylated pulp as follows. First, after diluting the phosphorylated pulp after washing with 10 L of ion exchanged water, a phosphated pulp slurry having a pH of 12 or more and 13 or less was obtained by gradually adding 1N aqueous sodium hydroxide solution while stirring. . Next, the phosphorylated pulp slurry was dewatered to obtain a phosphorylated pulp subjected to neutralization treatment. Next, the above-mentioned washing treatment was performed on the phosphorylated pulp after the neutralization treatment.

The infrared absorption spectrum of the phosphorylated pulp thus obtained was measured using FT-IR. As a result, absorption based on phosphate was observed around 1230 cm ⁻¹ , and it was confirmed that phosphate was added to the pulp. Moreover, the amount of phosphate groups (the amount of strongly acidic groups) measured by the measuring method described later was 2.00 mmol / g.

  Moreover, when the obtained phosphorylated pulp was tested and analyzed by an X-ray diffractometer, it was found at two positions of 2θ = 14 ° or more and 17 ° or less and 2θ = 22 or more and 23 ° or less A typical peak was confirmed and confirmed to have cellulose type I crystals.

  Ion-exchanged water was added to the obtained phosphorylated pulp to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated six times at a pressure of 200 MPa with a wet atomization apparatus (Starburst, manufactured by Sugino Machine Co., Ltd.) to obtain a fine fibrous cellulose dispersion A containing fine fibrous cellulose.

  It was confirmed by X-ray diffraction that this fine fibrous cellulose maintained cellulose type I crystals. Moreover, it was 3-5 nm when the fiber width of the fine fibrous cellulose was measured using the transmission electron microscope.

[Concentration step]
100 g of the fine fibrous cellulose dispersion A obtained above was separated, and 0.39 g of aluminum sulfate was added while stirring. When stirring was further continued for 5 hours, aggregation of fine fibrous cellulose was observed.
[Collection process]
Next, the fine fibrous cellulose dispersion was filtered and then pressed with filter paper to obtain a fine fibrous cellulose concentrate. The obtained fine fibrous cellulose concentrate was resuspended with ion exchange water so that the content of fine fibrous cellulose was 2.0% by mass. Then, it wash | cleaned by repeating operation which performs filtration and expression again, and the fine fibrous cellulose concentrate A was obtained.
The end point of washing was a point at which the conductivity of the filtrate became 100 μS / cm or less. The solid content concentration of the obtained fine fibrous cellulose concentrate A was 17% by mass. When the amount of aluminum contained in the obtained fine fibrous cellulose concentrate A was measured by the method described later, it was 2.9 g per 100 g of solid content.

The measured amount of aluminum C [mmol] contained in the fine fibrous cellulose concentrate A was almost the same as the amount of aluminum C _cal calculated from the formula (1).
C _cal = A × B / X (1)
Here, in the above formula (1), A, B and X represent the following.
A: Anion amount derived from the functional group introduced to the fine fibrous cellulose [mmol / g]
B: Amount of fine fibrous cellulose tested [g]
X: valence of aluminum ion (= 3)
When a metal other than aluminum is used in the following production examples, the amount of aluminum and the valence of the aluminum ion are read as the amount of metal and the valence of the metal ion.

<Production Example 1-2>
250 g of calcium chloride aqueous solution diluted to 0.5 mass% was added with respect to 500 g of fine fibrous cellulose dispersion liquid A obtained by manufacture example 1-1, and it gelatinized. The obtained gel was filtered and then squeezed with filter paper to obtain a fine fibrous cellulose concentrate.
The fine fibrous cellulose concentrate was immersed in 250 g of a 0.1 N aqueous hydrochloric acid solution for 30 minutes, filtered, and then pressed with filter paper. Then, the fine fibrous cellulose concentrate was pulverized using a mixer (Iriya Sangyo Co., Ltd. product, Mircer 800 DG) to obtain a fine fibrous cellulose concentrate B.
The solid content concentration of the fine fibrous cellulose concentrate B was 26% by mass. When the amount of aluminum contained in the obtained fine fibrous cellulose concentrate B was evaluated by the above-mentioned method, it did not reach the detectable amount.

<Production Example 2-1>
[Production of Fine Fibrous Cellulose Dispersion]
Softwood kraft pulp manufactured by Oji Paper Co., Ltd. (solid content 93% by mass, basis weight 208 g / m ^{2 in} sheet form) as a raw material pulp, Canadian Standard Freeness (CSF) which is disintegrated and measured according to JIS P 8121 Used 700 ml). The raw pulp was subjected to TEMPO oxidation as follows.

  First, the above raw material pulp equivalent to a dry mass of 100 parts by mass, 1.6 parts by mass of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl), 10 parts by mass of sodium bromide, 10000 parts of water It was dispersed in the department. Then, 13 mass% sodium hypochlorite aqueous solution was added to 10 mmol per 1.0 g of pulp to start the reaction. During the reaction, 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10 or more and 10.5 or less, and when no change was observed in the pH, the reaction was regarded as complete.

  Next, the obtained TEMPO oxidized pulp was washed. Washing is performed by dewatering the pulp slurry after TEMPO oxidation to obtain a dewatered sheet, pouring 5000 parts by mass of ion-exchanged water, stirring and uniformly dispersing, and then repeating the operation of filtering and dewatering. The When the electric conductivity of the filtrate became 100 μS / cm or less, it was regarded as the washing end point.

  About the TEMPO oxidation pulp obtained by this, the carboxyl group content measured by the measuring method mentioned later was 1.80 mmol / g.

  In addition, when the obtained TEMPO oxidized pulp is tested and analyzed by an X-ray diffractometer, it is found at two positions of 2θ = 14 ° or more and 17 ° or less and 2θ = 22 or more and 23 ° or less A typical peak was confirmed and confirmed to have cellulose type I crystals.

  Ion-exchanged water was added to the obtained TEMPO oxidized pulp to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated six times at a pressure of 200 MPa with a wet atomization device (Starburst, manufactured by Sugino Machine Co., Ltd.) to obtain a fine fibrous cellulose dispersion B containing fine fibrous cellulose.

  It was confirmed by X-ray diffraction that this fine fibrous cellulose maintained cellulose type I crystals. Moreover, it was 3-5 nm when the fiber width of the fine fibrous cellulose was measured using the transmission electron microscope.

[Concentration step] and [recovery step]
The same procedure as in Production Example 1-1 was conducted, except that the fine fibrous cellulose dispersion B obtained above was used instead of the fine fibrous cellulose dispersion A, and the addition amount of aluminum sulfate was 0.22 g. The fine fibrous cellulose concentrate C was obtained.
The solid content concentration of the fine fibrous cellulose concentrate D was 20% by mass. When the amount of aluminum contained in the obtained fine fibrous cellulose concentrate D was measured by the method described later, it was 1.6 g per 100 g of solid content.

Production Example 2-2
A fine fibrous cellulose is prepared in the same manner as in Production Example 1-2, except that the fine fibrous cellulose dispersion B is used instead of the fine fibrous cellulose dispersion A and the amount of the calcium chloride aqueous solution added is 140 g. A concentrate D was obtained.
The solid content concentration of the fine fibrous cellulose concentrate E was 28% by mass. When the amount of aluminum contained in the obtained fine fibrous cellulose concentrate E was measured by the method described later, it did not reach the detectable amount.

Example 1
[Redispersion process]
To 11.2 g of the fine fibrous cellulose concentrate A, 3.96 g of a 55% by mass aqueous solution of tetrabutylammonium hydroxide was added, and dimethyl sulfoxide was added such that the content of the fine fibrous cellulose was 0.5% by mass. Then, it was treated with an ultrasonic homogenizer (manufactured by hielscher, UP400S) for 10 minutes to obtain a fine fibrous cellulose redispersion solution.

The addition amount D [mmol] of tetrabutylammonium hydroxide was a value obtained by the following formula (2).
D = (A + C) x B (2)
Here, in the above-mentioned formula (2), A, B and C show the following.
A: Anion amount derived from the functional group introduced to the fine fibrous cellulose [mmol / g]
B: Amount of fine fibrous cellulose tested [g]
C: Amount of aluminum ion contained in the fine fibrous cellulose concentrate [mmol / g]
When a metal other than aluminum is used instead of aluminum in the following examples, the amount of aluminum and the valence of the aluminum ion are read as the amount of metal and the valence of the metal ion.

[Mixing process of resin]
(Dissolution of resin)
Add dimethyl sulfoxide so that the concentration of polyvinyl alcohol (Kuraray Co., Ltd., Poval 117, degree of polymerization 1700, degree of saponification 98 to 99 mol%) is 20% by mass, stir at 95 ° C for 1 hour, polyvinyl alcohol A solution was obtained.

(Preparation of dispersion)
A polyvinyl alcohol solution is added to the obtained fine fibrous cellulose re-dispersion solution so that polyvinyl alcohol is 90 parts by mass with respect to 10 parts by mass of fine fibrous cellulose, and the solid concentration is further adjusted to 1.1%. A resin-containing fine fibrous cellulose dispersion was obtained by adding a sulfoxide.
The content of fine fibrous cellulose in the obtained dispersion was 0.097% by mass, the content of polyvinyl alcohol was 0.9% by mass, the content of aluminum was 0.003% by mass, and tetrabutylammonium hydroxide was used. The content was 0.11% by mass.
Further, the water content of the obtained dispersion was 0.57 g per 100 g when calculated from the addition amounts of the fine fibrous cellulose concentrate A and the 55% aqueous tetrabutylammonium solution tested.

[Sheeting]
The resin-containing fine fibrous cellulose dispersion obtained above is weighed so that the finished basis weight of the sheet is 40 g / m ² , spread on a stainless steel plate (SUS 304), and heated at 110 ° C. with a hot air dryer. Let dry for 24 hours. In addition, a plate for blocking was arranged on the stainless steel plate so as to obtain a predetermined basis weight. By the above procedure, a 92 μm thick sheet was obtained.

The viscosity of the obtained resin-containing fine fibrous cellulose dispersion and the specific tensile energy absorption amount of the obtained sheet were evaluated by the method described later. Moreover, the hydroxyl value of the used polyvinyl alcohol was measured by the below-mentioned method.
The evaluation and measurement results are shown in Table 1.

Example 2
A resin-containing fine fibrous cellulose dispersion liquid and a sheet were obtained in the same manner as in Example 1 except that the fine fibrous cellulose concentrate C was used instead of the fine fibrous cellulose concentrate A.
The content of fine fibrous cellulose in the obtained dispersion was 0.098% by mass, the content of polyvinyl alcohol was 0.9% by mass, the content of aluminum was 0.002% by mass, and tetrabutylammonium hydroxide was used. The content was 0.06% by mass.
The water content of the obtained dispersion was 0.45 g per 100 g when calculated from the addition amounts of the fine fibrous cellulose concentrate and the 55% aqueous tetrabutylammonium solution.
Furthermore, the viscosity of the obtained dispersion and the specific tensile energy absorption of the obtained sheet were evaluated by the method described later.
The evaluation and measurement results are shown in Table 1.

Example 3
Dimethyl sulfoxide was added to the solution so that the concentration of carbomer (carboxyvinyl resin, Hibiswako 103, Wako Pure Chemical Industries, Ltd.) was 0.6% by mass, and the mixture was stirred for 1 hour to obtain a carbomer solution.
A resin was prepared in the same manner as in Example 1, except that the obtained carbomer solution was used instead of the polyvinyl alcohol solution to dilute the solid content concentration of the resin-containing fine fibrous cellulose dispersion to 0.4% by mass. A fine fibrous cellulose-containing dispersion was obtained. The physical properties could not be measured because no sheet was obtained.
The content of fine fibrous cellulose in the obtained dispersion is 0.049% by mass, the content of carbomer is 0.45% by mass, the content of aluminum is 0.001% by mass, and the content of tetrabutylammonium hydroxide is The amount was 0.06% by mass.
The water content of the obtained dispersion was 0.23 g per 100 g as calculated from the addition amounts of the fine fibrous cellulose concentrate and the 55% aqueous tetrabutylammonium solution.
Furthermore, the viscosity of the obtained dispersion was evaluated by the method described later. Moreover, the acid value of the used polyacrylic acid was measured by the below-mentioned method.
The evaluation and measurement results are shown in Table 1.

Comparative Example 1
A resin-containing fine fibrous cellulose dispersion liquid and a sheet were obtained in the same manner as in Example 1 except that the fine fibrous cellulose concentrate B was used instead of the fine fibrous cellulose concentrate A.
The content of fine fibrous cellulose in the obtained dispersion is 0.1% by mass, the content of polyvinyl alcohol is 0.9% by mass, the content of tetrabutylammonium hydroxide is 0.09% by mass, calcium The content was less than 0.001% by mass, and the counter ion of the phosphate group of fine fibrous cellulose was H ⁺ (hydrogen ion).
Further, the water content of the obtained dispersion was 0.35 g per 100 g when calculated from the addition amounts of the fine fibrous cellulose concentrate and the 55% aqueous tetrabutylammonium solution.
Furthermore, the viscosity of the obtained dispersion and the specific tensile energy absorption of the obtained sheet were evaluated by the method described later.
The evaluation and measurement results are shown in Table 1.

Comparative Example 2
A resin-containing fine fibrous cellulose dispersion liquid and a sheet were obtained in the same manner as in Example 1 except that the fine fibrous cellulose concentrate D was used instead of the fine fibrous cellulose concentrate A.
The content of fine fibrous cellulose in the obtained dispersion is 0.1% by mass, the content of polyvinyl alcohol is 0.9% by mass, the content of tetrabutylammonium hydroxide is 0.05% by mass, calcium The content was less than 0.001% by mass, and the counter ion of the carboxyl group of the fine fibrous cellulose was H ⁺ (hydrogen ion).
The water content of the obtained dispersion was 0.30 g per 100 g when calculated from the addition amounts of the microfibrous cellulose concentrate and the 55% aqueous tetrabutylammonium solution.
Furthermore, the viscosity of the obtained dispersion and the specific tensile energy absorption of the obtained sheet were evaluated by the method described later.
The evaluation and measurement results are shown in Table 1.

Comparative Example 3
3.96 g of tetrabutyl ammonium hydroxide aqueous solution was added to the fine fibrous cellulose concentrate A, and methyl ethyl ketone was added so that the content of the fine fibrous cellulose was 0.5% by mass. Then, it was treated with an ultrasonic homogenizer (manufactured by hielscher, UP400S) for 10 minutes to obtain a fine fibrous cellulose redispersion solution.
Methyl ethyl ketone was added to the solution so that the concentration of polymethyl methacrylate (PMMA, manufactured by DSM, NeoCryl B-811, molecular weight 40000) was 20% by mass, and the mixture was stirred for 1 hour to obtain a polymethyl methacrylate solution.
A polymethyl methacrylate solution is added to the obtained fine fibrous cellulose redispersion solution so that polymethyl methacrylate is 90 parts by mass with respect to 10 parts by mass of the fine fibrous cellulose, and the solid content concentration is 4.5 mass% Further, methyl ethyl ketone was added so as to obtain a resin-containing fine fibrous cellulose dispersion.

The resin-containing fine fibrous cellulose dispersion was weighed so that the finished basis weight of the sheet was 100 g / m ² , spread on a stainless steel plate (SUS 304), and dried with a hot air dryer at 50 ° C. for 24 hours . In addition, a plate for blocking was arranged on the stainless steel plate so as to obtain a predetermined basis weight. By the above procedure, a sheet with a thickness of 164 μm was obtained.
The content of fine fibrous cellulose in the obtained dispersion is 0.39% by mass, the content of polymethyl methacrylate is 3.6% by mass, the content of aluminum is 0.01% by mass, and tetrabutylammonium hydroxy The content of de was 0.46% by mass.
Moreover, the water content of the obtained dispersion liquid was 2.32 g per 100 g when calculated from the addition amount of the fine fibrous cellulose concentrate and the 55% tetrabutylammonium aqueous solution tested.
The viscosity of the obtained resin-containing fine fibrous cellulose dispersion was evaluated by the method described later. Moreover, the specific tensile energy absorption amount of the obtained sheet | seat was evaluated by the below-mentioned method. Furthermore, the acid value and the hydroxyl value of the used poly (methyl methacrylate) were measured by the method described later.
The evaluation and measurement results are shown in Table 1. Table 1 shows the sum of the acid value and the hydroxyl value (the same applies to Reference Example 1).

Reference Example 1
A resin-containing fine fiber was prepared in the same manner as in Comparative Example 3, except that a fine fibrous cellulose concentrate B was used instead of the fine fibrous cellulose concentrate A and the solid content concentration was adjusted to 4.4% by mass. A cellulose dispersion and a sheet were obtained.
The content of fine fibrous cellulose in the obtained dispersion is 0.4% by mass, the content of polymethyl methacrylate is 3.6% by mass, the content of tetrabutylammonium hydroxide is 0.35% by mass, The calcium content was less than 0.001% by mass, and the counter ion of the phosphate group of the fine fibrous cellulose was H ⁺ (hydrogen ion).
Further, the water content of the obtained dispersion was 1.41 g per 100 g when calculated from the addition amounts of the fine fibrous cellulose concentrate and the 55% by mass aqueous tetrabutylammonium solution.
Furthermore, the viscosity of the obtained dispersion and the specific tensile energy absorption of the obtained sheet were evaluated by the method described later.
The evaluation and measurement results are shown in Table 1.

Reference Example 2
A resin-containing fine fibrous cellulose dispersion and sheet are obtained in the same manner as in Example 1 except that ion-exchanged water is added so that the water content of the dispersion becomes 10% by mass in the preparation process of the dispersion. The
The content of fine fibrous cellulose in the obtained dispersion was 0.097% by mass, the content of polyvinyl alcohol was 0.9% by mass, the content of aluminum was 0.003% by mass, and tetrabutylammonium hydroxide was used. The content was 0.11% by mass.
Furthermore, the viscosity of the obtained dispersion and the specific tensile energy absorption of the obtained sheet were evaluated by the method described later.
The evaluation and measurement results are shown in Table 1.

[Measuring method]
Each measuring method of the said Example and comparative example is as follows.
[Measurement of phosphate group amount]
The phosphoric acid group content of the fine fibrous cellulose is prepared by diluting the fine fibrous cellulose dispersion containing the fine fibrous cellulose to be treated with ion exchanged water so that the content is 0.2% by mass. The cellulose-containing slurry was treated with an ion exchange resin and then measured by titration with an alkali.
The treatment with ion exchange resin is carried out by adding 1/10 strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) to the above fibrous cellulose-containing slurry and shaking it for 1 hour It was carried out by pouring on a mesh of 90 μm mesh to separate resin and slurry.
In addition, titration using an alkali is carried out by adding an aqueous solution of 0.1 N sodium hydroxide to the fibrous cellulose-containing slurry after treatment with an ion exchange resin, while adding 50 μL each once for every 30 seconds. This was done by measuring the change in the value of. The amount of phosphate group (mmol / g) is obtained by dividing the amount of alkali (mmol) required in the region corresponding to the first region shown in FIG. 2 among the measurement results by the solid content (g) in the slurry to be titrated. Calculated.

[Measurement of amount of carboxyl group]
The carboxyl group content of the fine fibrous cellulose is prepared by diluting the fine fibrous cellulose dispersion liquid containing the fine fibrous cellulose to be treated with ion exchange water so that the content becomes 0.2% by mass. After the treatment with the ion exchange resin was performed on the contained slurry, it was measured by performing titration using an alkali.
The treatment with ion exchange resin is carried out by adding 1/10 strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) to the above fibrous cellulose-containing slurry and shaking it for 1 hour It was carried out by pouring on a mesh of 90 μm mesh to separate resin and slurry.
In addition, titration using an alkali is carried out by adding an aqueous solution of 0.1 N sodium hydroxide solution once in 30 seconds to the fibrous cellulose-containing slurry treated with the ion exchange resin, while adding 50 μL of the aqueous solution to the slurry. It did by measuring the change of value. The amount of carboxyl groups (mmol / g) is obtained by dividing the amount of alkali (mmol) required in the region corresponding to the first region shown in FIG. 3 among the measurement results by the solid content (g) in the slurry to be titrated. Calculated.

[Measurement of aluminum content]
The amount of aluminum in the fine fibrous cellulose concentrate was measured in accordance with JIS G 1257-10-1: 2013.

[Measurement of hydroxyl value or acid value]
The hydroxyl value or acid value of the used resin was measured in accordance with JIS K 0070: 1992.

[Evaluation method]
Each evaluation method of the said Example, a comparative example, and a reference example is as follows.
[Measurement of viscosity of dispersion]
The viscosity of the fine fibrous cellulose dispersion was measured using a B-type viscometer (analog viscometer T-LVT manufactured by BLOOKFIELD). The measurement conditions were a rotational speed of 12 rpm, and the viscosity value 3 minutes after the start of the measurement was taken as the viscosity of the dispersion. Further, the dispersion to be measured was allowed to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity before measurement. The liquid temperature of the dispersion at the time of measurement was 23 ° C.
The evaluation results are shown in Table 1.

[Measurement of specific tensile energy absorption of sheet]
The specific tensile energy absorption amount of the sheet was measured using a tensile tester Tensilon (manufactured by A & D Co., Ltd.) in accordance with JIS P 8113: 2006. In addition, when measuring specific tensile energy absorption amount, what was conditioned for 24 hours at 23 degreeC and 50% of relative humidity was used as a test piece.
The evaluation results are shown in Table 1.

  The resin composition of the present invention can be made into a dispersion having excellent thickening property even when the content of fine fibrous cellulose is small, and further, molding using the resin composition provides excellent molding properties. Since it is possible to use it as a body, it can be used as a thickener for foods, cosmetics, cements, paints, inks, etc., sheets, threads, filters, fabrics, cushioning materials used for various display devices, various solar cells, etc. , Sponges, abrasives and the like.

1: fine fibrous cellulose 2: resin a: hydroxyl group b: functional group c: hydroxide ion M: amphoteric metal

Claims (15)

  A fine fibrous cellulose having a fiber width of 1000 nm or less, a resin having one or more functional groups selected from a hydroxyl group and an oxo acid group, an amphoteric metal, and an organic solvent, and the water content is less than 10% by mass Resin composition.   The resin composition according to claim 1, further comprising an organic onium salt.   The resin composition according to claim 2, wherein the organic onium salt is a quaternary ammonium salt.   The resin composition according to any one of claims 1 to 3, wherein a hydroxyl value or an acid value of the resin measured according to JIS K 0070: 1992 is 1 to 10000 mg KOH / g.   The resin composition according to any one of claims 1 to 4, wherein the amphoteric metal is aluminum.   The resin composition according to any one of claims 1 to 5, wherein the amphoteric metal is an anion.   The resin composition according to any one of claims 1 to 6, wherein the fine fibrous cellulose has an anionic group.   The resin composition according to any one of claims 1 to 7, wherein the resin composition is a dispersion.   A molded article comprising a fine fibrous cellulose having a fiber width of 1000 nm or less, a resin having one or more functional groups selected from a hydroxyl group and an oxo acid group, and an amphoteric metal.   The molded article according to claim 9, further comprising an organic onium salt.   The molded article according to claim 10, wherein the organic onium salt is a quaternary ammonium salt.   The molded object according to any one of claims 9 to 11 whose hydroxyl value or acid value measured based on JIS K 0070: 1992 of said resin is 1 to 10000 mg KOH / g.   The molded object in any one of Claims 9-12 whose said amphoteric metal is aluminum.   The molded object in any one of Claims 9-13 whose said amphoteric metal is an anion.   The molded object in any one of Claims 9-14 in which the said fine fibrous cellulose has an anionic group.