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  • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
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Definitions

• the present invention relates to a cellulose fiber composite, a dispersion containing the same, a resin composition, a molded product, and a method for producing a cellulose fiber composite.
• the fibers agglomerate due to a huge amount of hydrogen bonds between the cellulose fibers.
• a medium such as water or an organic solvent.
• the dried cellulose fiber is an inconvenient material.
• the surface of the cellulose fibers is hydrophilic, if the dispersion medium or the resin is hydrophobic, the cellulose fibers are likely to aggregate and the dispersibility in the dispersion medium or the resin is lowered. Therefore, in order to blend the cellulose fiber into a resin or the like and enhance its mechanical properties and the like, it is necessary to enhance the dispersibility of the cellulose fiber.
• thickening with an organic medium is often required in some fields such as paints and inks having a low viscosity. Further, it is also important to enhance the compatibility with the resin or impart a specific function by introducing a specific reactive functional group into the cellulose fiber. At the same time, from the viewpoint of application development, there is a demand for cellulose fibers that do not reduce transparency when blended in a dispersion medium or resin.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2010-168572 states that as a gas barrier molded product having high permeation inhibitory properties against oxygen gas, water vapor, etc., it has a reactive functionality with cellulose fibers having an average fiber diameter of 200 nm or less.
• a material for a gas barrier containing a cross-linking agent having a group and having a carboxy group content of cellulose constituting a cellulose fiber of 0.1 to 2 mmol / g is disclosed.
• Patent Document 2 Japanese Patent Application Laid-Open No. 2016-183329 (Patent Document 2), (A) a number average fiber diameter of 0.5 to 200 nm and a carboxy group content of 0.1 mmol / as an aqueous composition having a small decrease in viscosity at high temperatures.
• An aqueous composition containing (A) component and (B) component in a specific ratio and having a specific viscosity is disclosed.
• Patent Document 3 as a gel-like composition having excellent dispersibility and viscosity, (A) cellulose nanofibers having a maximum fiber diameter of 1000 nm or less and a number average fiber diameter of 2 to 150 nm.
• the cellulose has a cellulose type I crystal structure, the hydroxyl group at the C6 position of the glucose unit in the cellulose molecule is selectively oxidatively modified to form a carboxy group or the like, and the carboxy group is an amino group of polyether amine.
• a gel-like composition containing cellulose nanofibers ionically bonded to and (B) an organic solvent is disclosed.
• the present invention is a cellulose fiber composite in which one or more amines selected from polyvalent amines and monoamines having a reactive functional group are bonded to anion-modified cellulose fibers.
• the present invention relates to a cellulose fiber complex that satisfies at least one of the following conditions 1 and 2.
• Condition 1 The introduction rate of the amine represented by the following formula (1) is 60% or less.
• Amine introduction rate (%) [Amine amount bonded to anionic group introduced into cellulose fiber (mmol / g) / Content of anionic group introduced into cellulose fiber (mmol / g)] ⁇ 100 ( 1)
• Condition 2 The average degree of polymerization of the anion-modified cellulose fiber is 300 or less.
• the present invention relates to a cellulose fiber composite having excellent dispersion stability, more specifically, (1) a cellulose fiber composite having excellent dispersion stability and high viscosity, and (2) a dispersion having excellent dispersion stability.
• the present invention relates to a cellulose fiber composite having excellent transparency, and a method for producing a dispersion containing them, a resin composition, a molded product, and a cellulose fiber composite.
• the present inventors have combined (1) an anion-modified cellulose fiber with one or more amines selected from polyvalent amines and monoamines having a reactive functional group bonded at an introduction rate of 60% or less. Further, (2) the above problem is solved by combining and complexing an anion-modified cellulose fiber having an average degree of polymerization of 300 or less and one or more amines selected from polyvalent amines and monoamines having a reactive functional group. I found that it could be done. That is, the present invention relates to the following [1] to [5]. [1] A cellulose fiber composite in which one or more amines selected from polyvalent amines and monoamines having a reactive functional group are bonded to anion-modified cellulose fibers.
• a cellulose fiber complex that satisfies at least one of the following conditions 1 and 2.
• Condition 1 The introduction rate of the amine represented by the following formula (1) is 60% or less.
• Amine introduction rate (%) [Amine amount bonded to anionic group introduced into cellulose fiber (mmol / g) / Content of anionic group introduced into cellulose fiber (mmol / g)] ⁇ 100 ( 1)
• Condition 2 The average degree of polymerization of the anion-modified cellulose fiber is 300 or less.
• [3] A resin composition obtained by blending the cellulose fiber complex according to the above [1] with a resin.
• a cellulose fiber composite having excellent dispersion stability more specifically, (1) a cellulose fiber composite having excellent dispersion stability and high viscosity, and (2) excellent dispersion stability, It is possible to provide a cellulose fiber composite in which the transparency of the dispersion is also excellent, a dispersion containing them, a resin composition, a molded product having excellent mechanical strength, and a method for producing the cellulose fiber composite. ..
• the cellulose fiber composite of the present invention is a cellulose fiber composite in which one or more amines selected from polyvalent amines and monoamines having a reactive functional group are bonded to anion-modified cellulose fibers, and the following condition 1 And at least one of 2 is satisfied.
• Condition 1 The introduction rate of the amine represented by the following formula (1) is 60% or less.
• Amine introduction rate (%) [Amine amount bonded to anionic group introduced into cellulose fiber (mmol / g) / Content of anionic group introduced into cellulose fiber (mmol / g)] ⁇ 100 ( 1)
• Condition 2 The average degree of polymerization of the anion-modified cellulose fiber is 300 or less.
• an invention satisfying condition 1 is referred to as a first invention
• an invention satisfying condition 2 is referred to as a second invention.
• the present invention refers to the first invention and the second invention, and the description without particular description of the first invention and the second invention is a description of matters common to the first invention and the second invention.
• the cellulose fiber composite of the first invention has excellent dispersion stability and high viscosity
• the cellulose fiber composite of the second invention has excellent dispersion stability and excellent transparency of the dispersion.
• the reason is not clear, but it can be considered as follows.
• a reactive functional group has a property of being able to interact with other structures such as high polarity, so that the introduction rate should be 60% or less.
• anion-modified cellulose fibers it is considered that the interaction between the cellulose fibers can be moderately weakened.
• the compatibility with the medium is improved without the cellulose fibers being agglomerated, the dispersion stability of the cellulose fiber complex is improved, and the viscosity is increased.
• the "anion-modified cellulose fiber" used in the present invention is a cellulose fiber that has been anion-modified so as to contain an anionic group in the cellulose fiber.
• the average fiber length and the like of the anion-modified cellulose fiber differ depending on the production method. For example, when the anion-modified cellulose fiber has not been subjected to the shortening treatment, the preferable range such as the average fiber length is the same as that of the raw material cellulose fiber. When the anion-modified cellulose fiber has been subjected to the short-fiber treatment, the preferable range such as the average fiber length is the same as that of the short-fiber cellulose fiber described later.
• the average degree of polymerization of the anion-modified cellulose fiber is preferably 30 or more, more preferably 50 or more, still more preferably 60 or more, from the viewpoint of obtaining a molded product having excellent dispersion stability and mechanical strength. It is more preferably 70 or more, still more preferably 80 or more, and from the viewpoint of improving dispersion stability, it is preferably 700 or less, more preferably 500 or less, still more preferably 400 or less, and from the viewpoint of improving transparency. Therefore, it is preferably 300 or less, more preferably 250 or less, still more preferably 200 or less, and even more preferably 180 or less.
• the average degree of polymerization of the anion-modified cellulose fiber is preferably 30 or more, more preferably 50 or more, still more preferably 60 or more, still more, from the viewpoint of obtaining a molded product having excellent mechanical strength. It is preferably 70 or more, more preferably 80 or more, and from the viewpoint of improving transparency and dispersion stability, it is 300 or less, preferably 250 or less, more preferably 200 or less, still more preferably 180 or less. From the above viewpoint, the average degree of polymerization of the anion-modified cellulose fiber is preferably 30 or more and 300 or less, more preferably 50 or more and 300 or less, and further preferably 50 or more and 250 or less.
• the average degree of polymerization of the anion-modified cellulose fiber By setting the average degree of polymerization of the anion-modified cellulose fiber to 300 or less, regardless of the introduction rate of one or more amines selected from polyvalent amines and monoamines having a reactive functional group into the anionic group of the cellulose fiber, Dispersion stability and transparency can be improved.
• the average degree of polymerization of the cellulose fibers can be measured by the method described in Examples.
• a commercially available cellulose fiber having an average degree of polymerization within the above range may be used as it is, or a cellulose raw material having an average degree of polymerization exceeding the above range may be averaged by subjecting an appropriate treatment prior to use.
• the degree of polymerization may be adjusted.
• a cellulose raw material having an average degree of polymerization exceeding the above range may be used for anion modification while performing an appropriate treatment, or a cellulose raw material having an average degree of polymerization within the above range may be subjected to an appropriate treatment.
• the average degree of polymerization may be changed.
• anionic group contained in the anion-modified cellulose fiber examples include a carboxy group, a sulfonic acid group and a (phosphorous acid) group, and a carboxy group is preferable from the viewpoint of introduction efficiency into the cellulose fiber.
• the content of the anionic group of the anion-modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, from the viewpoint of improving viscosity thickening and dispersion stability.
• mmol / g is the number of moles of anionic groups in 1 g of anion-modified cellulose fibers, and is before the introduction of the modifying group described later. The same applies hereinafter.
• the content of the anionic group of the anion-modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, from the viewpoint of improving transparency and dispersion stability. More preferably 0.5 mmol / g or more, still more preferably 0.8 mmol / g or more, and preferably 3 mmol / g or less, more preferably 2 mmol / g or less, still more preferably 1.8 mmol / g or less. be.
• the content of the anionic group of the anionic modified cellulose fiber is preferably 0.1 mmol / g or more and 3 mmol / g or less, more preferably 0.2 mmol / g or more and 2 mmol / g or less, and further. It is preferably 0.5 mmol / g or more and 1.8 mmol / g or less.
• the content of anionic groups means the total amount of anionic groups in the cellulose fibers constituting the anion-modified cellulose fibers, and can be measured by the method described in Examples.
• the anionic-modified cellulose fiber can be obtained by subjecting the target cellulose fiber to an oxidation treatment or an anionic group addition treatment to introduce at least one or more anionic groups.
• the type of anionic group is one or more.
• Examples of the cellulose fiber to be anion-modified include the following (A) and (B).
• (A) Raw material cellulose fiber (B) Shortened cellulose fiber obtained by shortening the raw material cellulose fiber Among these, from the viewpoint of introduction efficiency into the cellulose fiber and from the viewpoint of reducing the load required for production. , (A) Raw material cellulose fiber is preferable.
• natural cellulose fiber is preferable from the viewpoint of reducing the environmental load.
• the natural cellulose fiber include wood pulp such as softwood pulp and broadleaf pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as straw pulp and bagas pulp; and bacterial cellulose and the like.
• wood pulp such as softwood pulp and broadleaf pulp
• cotton pulp such as cotton linter and cotton lint
• non-wood pulp such as straw pulp and bagas pulp
• bacterial cellulose and the like As the raw material cellulose fiber, one of the above can be used alone or in combination of two or more.
• the average fiber length of the raw material cellulose fiber is preferably 800 ⁇ m or more, more preferably 1,000 ⁇ m or more, further preferably 1,500 ⁇ m or more, and preferably 10,000 ⁇ m or less. , More preferably 5,000 ⁇ m or less, still more preferably 3,000 ⁇ m or less.
• the average fiber diameter of the raw material cellulose fibers is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 20 ⁇ m or more, and preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, from the viewpoint of availability and cost reduction. , More preferably 80 ⁇ m or less.
• the average aspect ratio of the raw material cellulose fibers is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, and preferably 200 or less, more preferably 100 or less, from the viewpoint of availability and cost reduction. , More preferably 80 or less.
• the average fiber length, average fiber diameter, and average aspect ratio of the cellulose fibers can be measured by the methods described in Examples.
• the cellulose fibers to be treated for shortening the fibers include the following (B1) to (B3).
• (B1) Raw Material Cellulose Fiber The raw material cellulose fiber is the same as the raw material cellulose fiber (A).
• (B2) anion-modified cellulose fibers are preferable as the cellulose fibers to be treated for shortening fibers from the viewpoint of improving dispersion stability and improving the efficiency of shortening fibers.
• Examples of the method for introducing an anionic group into the cellulose fiber include the following (b1) to (b3).
• (B1) Method of converting a hydroxy group of cellulose into a carboxy group
• (b2) One selected from the group consisting of a compound having a carboxy group in the hydroxy group of cellulose, an acid anhydride thereof, and a derivative thereof.
• Method of reacting the above (b3) Method of introducing a sulfonic acid group or a (sub) phosphate group into a cellulose fiber Among these, the method of (b1) is preferable.
• (B1) Method of Oxidizing Hydroxyl Group of Cellulose to Convert to Carboxylic Acid
• the method of oxidizing the hydroxy group of cellulose is not particularly limited.
• an oxidizing agent such as sodium hypochlorite and a bromide such as sodium bromide are reacted with 2,2,6,6-tetramethyl-1-piperidin-N-oxyl (TEMPO) as a catalyst for oxidation treatment.
• TEMPO 2,2,6,6-tetramethyl-1-piperidin-N-oxyl
• the method can be mentioned. More specifically, the method described in JP2011-140632A can be referred to.
• a preferred embodiment of the anion-modified cellulose fiber is one derived from TEMPO oxidation, that is, a cellulose fiber in which the C6 position of the cellulose constituent unit is a carboxy group (hereinafter, also referred to as “oxide cellulose fiber”).
• (B2) Method of reacting a hydroxy group of cellulose with one or more selected from the group consisting of a compound having a carboxy group, an acid anhydride thereof, and a derivative thereof
• the compound having the carboxy group is not particularly limited.
• halogenated acetic acid and the like can be mentioned, and more specifically, chloroacetic acid and the like can be mentioned.
• the acid anhydrides of the compounds having a carboxy group and their derivatives are also not particularly limited.
• acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride and adipic anhydride, imidized acid anhydrides of compounds having a carboxy group, and acid anhydrides of compounds having a carboxy group.
• acid anhydrides of compounds having a carboxy group examples thereof include derivatives of. These compounds may be substituted with hydrophobic groups.
• (B3) Method of introducing a sulfonic acid group or a (sub) phosphate group into a cellulose fiber As a method of introducing a sulfonic acid group into a cellulose fiber, a method of adding sulfuric acid to the cellulose fiber and heating the fiber can be mentioned.
• a method for introducing a (sub) phosphoric acid group into a cellulose fiber a method of mixing a powder or an aqueous solution of phosphoric acid or a phosphoric acid derivative with a dry or wet cellulose fiber, or a method of mixing phosphoric acid or a dispersion liquid of the cellulose fiber with phosphoric acid or Examples thereof include a method of adding an aqueous solution of a phosphoric acid derivative. When these methods are adopted, generally, after mixing or adding a powder or aqueous solution of phosphoric acid or a phosphoric acid derivative, dehydration treatment, heat treatment and the like are performed.
• the average fiber length of the anion-modified cellulose fiber is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 10 ⁇ m or more, and dispersion stable, from the viewpoint of obtaining a molded product having excellent mechanical strength. From the viewpoint of property, transparency, thickening, etc., it is preferably 2500 ⁇ m or less, more preferably 1000 ⁇ m or less, still more preferably 500 ⁇ m or less, still more preferably 400 ⁇ m or less, still more preferably 300 ⁇ m or less.
• the average fiber length of the anion-modified cellulose fiber is preferably 1 ⁇ m or more and 2500 ⁇ m or less, more preferably 1 ⁇ m or more and 1000 ⁇ m or less, still more preferably 1 ⁇ m or more and 500 ⁇ m or less, still more preferably 5 ⁇ m or more and 400 ⁇ m or less, still more preferably. Is 10 ⁇ m or more and 300 ⁇ m or less.
• the average fiber diameter of the anion-modified cellulose fiber is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 20 ⁇ m or more, and dispersion stable, from the viewpoint of obtaining a molded product having excellent mechanical strength.
• the average fiber diameter of the anion-modified cellulose fiber is preferably 5 ⁇ m or more and 300 ⁇ m or less, and more preferably 10 ⁇ m or more and 100 ⁇ m or less.
• the average aspect ratio of the anion-modified cellulose fiber is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, still more preferably 10 or more, from the viewpoint of obtaining a molded product having excellent mechanical strength. , More preferably 15 or more, and from the viewpoint of dispersion stability, transparency, viscosity thickening, etc., it is preferably 200 or less, more preferably 100 or less, still more preferably 80 or less. From the above viewpoint, the average aspect ratio of the anion-modified cellulose fiber is preferably 2 or more and 200 or less, and more preferably 3 or more and 100 or less.
• the average fiber length, average fiber diameter, and average aspect ratio of the anion-modified cellulose fiber and the shortened anion-modified cellulose fiber can be measured by the method described in Examples.
• the raw material cellulose fiber may be shortened to obtain a shortened cellulose fiber, and then an anionic group may be introduced into the shortened cellulose fiber to obtain an anion-modified cellulose fiber.
• the shortening treatment can be regarded as a pretreatment for the defibration treatment described later. Further, when the fiber length of the raw material cellulose fiber is 1,000 ⁇ m or less, the shortening treatment can be omitted.
• the short fiber treatment is one or more selected from the group consisting of (i) alkali treatment, (ii) acid treatment, (iii) heat treatment, ultraviolet treatment, electron beam treatment, mechanical treatment and enzyme treatment of the target cellulose fiber. It can be carried out by applying a processing method.
• the solid content of the target cellulose fiber is preferably 0.1% by mass or more and 10.0% by mass or less, and the pH is preferably 8.0 or more.
• the medium of the solution or dispersion in the alkaline treatment is preferably water or ethanol.
• Examples of the alkali that can be used for pH adjustment include sodium hydroxide, potassium hydroxide and the like.
• the solution or dispersion may contain hydrogen peroxide, which is preferably 0.5 parts by mass or more and 2.5 parts by mass or less, based on 100 parts by mass of the anionic group-containing cellulose fiber.
• the solid content of the target cellulose fiber is preferably 0.1% by mass or more and 10.0% by mass or less, and the pH is preferably 0.1 or more.
• examples thereof include a method in which a solution or dispersion having a pH of 4.0 or less is prepared, and the solution or dispersion is heated at preferably 80 ° C. or higher and 120 ° C. or lower for 5 minutes or more and 240 minutes or less.
• the medium of the solution or dispersion in the acid treatment is preferably water or ethanol.
• Examples of the acid that can be used for pH adjustment include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid, citric acid and phosphoric acid, and more preferably hydrochloric acid, sulfuric acid, nitric acid and phosphorus. Acid, acetic acid, citric acid, more preferably hydrochloric acid.
• the solid content of the target cellulose fiber is preferably 0.1% by mass or more and 80% by mass or less, and optionally inorganic salts, inorganic fine particles, organic fine particles, or an interface.
• a method of preparing a solution or dispersion which may contain an activator, a preservative, etc., and heating this solution or dispersion at preferably 50 ° C. or higher and 230 ° C. or lower for 4 hours or longer and 2500 hours or lower. Can be mentioned.
• the medium of the solution or dispersion in the heat treatment is preferably water, ethanol, isopropanol, methyl ethyl ketone, ethyl acetate, toluene, cyclohexanone, N, N-dimethylformamide and the like.
• (B3) Modified Cellulose Fiber A Modified Cellulose Fiber obtained by introducing an anionic group into a raw material cellulose fiber and then further introducing a modifying group.
• the modified cellulose fiber has a modifying group introduced (bonded) into the anionic group of the anion-modified cellulose fiber. It was done.
• the bonding mode between the anionic group and the modifying group in the modified cellulose fiber is such that a compound having a modifying group in the anionic group existing in the anionic modified cellulose fiber is preferably used as an ionic bond and an ionic bond from the viewpoint of improving dispersion stability. / Or can be achieved by covalent bonding.
• Examples of the compound having a modifying group include an amine compound and a phosphonium compound, and these compounds include, for example, a chain or cyclic saturated or unsaturated hydrocarbon group, an aromatic hydrocarbon group and the like. , A copolymerization site and the like can be introduced.
• the compound having a modifying group can be appropriately selected depending on the mode of bonding with the anionic group.
• the modifying group also includes a polyvalent amine, an amine having a reactive functional group, and an amine having no reactive functional group, which will be described later.
• the polyvalent amine used in the present invention is not particularly limited as long as it is a compound having two or more amino groups in the molecule, but from the viewpoint of availability, and from the viewpoint of improving dispersion stability, viscosity thickening, and transparency. , And one or more selected from diamines and triamines are preferable from the viewpoint of obtaining a molded product having excellent mechanical strength.
• the polyvalent amine may appropriately have a reactive functional group described later in the structure. It is preferable to exclude polyvalent amines having a polysiloxane structure from the viewpoint of improving dispersion stability, thickening and transparency, and obtaining a molded product having excellent mechanical strength.
• the weight average molecular weight of the polyvalent amine is preferably 60 or more, more preferably 80 or more, still more preferably 100 or more, still more preferably 200 or more, from the viewpoint of improving dispersion stability, viscosity thickening, and transparency. It is even more preferably 300 or more, and from the viewpoint of improving transparency, it is preferably 10,000 or less, more preferably 6000 or less, still more preferably 4000 or less, and even more preferably 3000 or less.
• the number of polyvalent amines used may be plural.
• the weight average molecular weight of the polyvalent amine can be measured by the GPC method described in ⁇ Condition 1> of paragraph [0117] of International Publication No. 2016/10403. It is also possible to refer to the catalog value of each product.
• polyvalent amines include aliphatic diamines, aliphatic triamines, monocyclic aromatic diamines, condensed polycyclic aromatic diamines, bis (diaminophenyl), 4,4'-diaminobiphenyl, and bis (aminophenoxy).
• a primary amine is preferable, one or more selected from an aliphatic primary diamine and an aliphatic primary triamine is more preferable, and an aliphatic primary diamine is further preferable.
• the polyvalent amine has an oxyalkanediyl group as a polymerization site or a copolymerization site because dispersion stability, viscosity thickening, and transparency are improved.
• the average number of moles of the oxyalkanediyl group added is 1 or more, preferably 2 or more and 90 or less, more preferably 2 or more and 70 or less, and further preferably 3 or more and 50 or less.
• a plurality of oxyalkanediyl groups may be the same or different from each other.
• the oxyalkandyl group preferably contains one or more selected from an oxypropylene group and an oxyethylene group, and more preferably contains an oxypropylene group.
• an aliphatic primary diamine having an oxyalkanediyl group and an aliphatic primary triamine are preferable, and an aliphatic primary diamine having a polyoxyalkandyl group is more preferable.
• aliphatic primary diamine having an oxyalkanediyl group a compound represented by the following formula (1) or (2) is preferably mentioned.
• a and c indicate the average number of moles of propylene oxide (PO) added, and b indicates the average number of moles of ethylene oxide (EO) added.
• the average number of moles of PO added a and c are preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and further independently, respectively, from the viewpoint of improving dispersion stability, viscosity thickening, and transparency. It is preferably 5 or more, and preferably 70 or less, more preferably 60 or less, still more preferably 50 or less, still more preferably 40 or less.
• the average number of moles of EO added b is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, still more preferably 5 or more, from the viewpoint of improving dispersion stability, viscosity thickening, and transparency. Then, it is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and even more preferably 20 or less.
• polyvalent amine having a polyoxyalkandyl group as described above examples include polyoxyalkylene diamine and polyoxyalkylene triamine.
• these commercially available products include Jeffamine series products manufactured by Huntsman of the United States. More specifically, polyoxypropylene (PO) diamines such as Jeffamine D-230, D-400, D-600, D-2000, and D-4000, Jeffamine ED-600, and ED- (PO / EO) copolymer diamines such as 900 and ED-2003, polyoxyethylenediamines such as Jeffamine EDR-148 and EDR-176, Jeffamine T-403, T-3000, T-5000 and the like.
• PO copolymer triamine is preferably mentioned.
• the (PO / EO) copolymer site of the copolymer diamine and triamine may be a random copolymer or a block copolymer.
• the above polyvalent amines can be used alone or in combination of two or more.
• a monoamine having a reactive functional group can react with a medium such as a resin from the viewpoint of improving dispersion stability, viscosity thickening, transparency, and obtaining a molded product having excellent mechanical strength. It has a group.
• the amine having a reactive functional group is preferably excluded from the viewpoint of improving dispersion stability, viscosity thickening and transparency, and from the viewpoint of obtaining a molded product having excellent mechanical strength.
• the weight average molecular weight of the monoamine is preferably 60 or more, more preferably 70 or more, still more preferably 80 or more, still more preferably 90 or more, and preferably 2000 or less, more preferably. Is 1000 or less, more preferably 500 or less.
• the weight average molecular weight of a monoamine having a reactive functional group can be measured by the GPC method described in ⁇ Condition 1> of paragraph [0117] of International Publication No. 2016/10403. It is also possible to refer to the catalog value of each product.
• the reactive functional group is not particularly limited as long as it is a functional group having reactivity other than the amino group bonded to cellulose.
• Specific examples of the reactive functional group include an epoxy group, a carboxy group, a hydroxy group, a thiol group, a vinyl group, an allyl group, an alkenyl group, an acryloyl group, a methacryloyl group, an aldehyde group, an isocyanate group, a hydrazide group and an oxazoline group.
• Examples thereof include a carbodiimide group, an azetidineium group, a pyridinium group, an imidazolium group, an alkoxide group, a methylol group and a silanol group.
• a carbodiimide group an azetidineium group, a pyridinium group, an imidazolium group, an alkoxide group, a methylol group and a silanol group.
• one or more selected from an epoxy group, a carboxy group, a hydroxy group, a thiol group, an allyl group, an alkenyl group, and an acryloyl group are preferable, and one or more selected from an allyl group and an acryloyl group are more preferable.
• Examples of the monoamine having a reactive functional group used in the present invention include the above-mentioned primary monoamine having a reactive functional group, secondary monoamine, tertiary monoamine, and quaternary ammonium, and the number of carbon atoms thereof is determined. It is preferably 2 or more, more preferably 6 or more, and preferably 30 or less, more preferably 24 or less, still more preferably 18 or less.
• Examples of the primary monoamine include aliphatic monoamines having the above-mentioned reactive functional groups, aromatic monoamines, heterocyclic-containing monoamines, alicyclic monoamines, polyoxyethylene amines, polyoxypropylene amines, polyoxyethylene / propyleneamines, and the like. Derivatives of.
• primary, secondary or tertiary monoamines having the above-mentioned reactive functional groups are preferable from the viewpoint of reactivity and the viewpoint of improving dispersion stability, thickening and transparency.
• a primary monoamine having the reactive functional group of the above is more preferable, and an aliphatic primary monoamine having at least one monoamine selected from a hydrocarbon group and a polyether group is more preferable.
• aliphatic monoamine having a reactive functional group examples include vinylamine, (mono, di or tri) allylamine, (mono, di or tri) oleylamine, 2- (dimethylamino) having the above reactive functional group.
• Amino groups such as ethyl acrylate, 2- (diethylamino) ethyl acrylate, 3- (dimethylamino) propyl acrylate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 3- (dimethylamino) propyl methacrylate, etc.
• Acrylic acid ester or methacrylic acid ester (mono, di or tri) ethanolamine, heptaminol, isoetaline, (mono, di or tri) propanolamine, sphingosine, (mono, di or tri) methanolamine, dimethylethanolamine, N -Methylethanolamine, aromatic amine type epoxy resin monomer, aminophenol type epoxy resin monomer, various amino acids and the like can be mentioned. From the viewpoint of reactivity, (mono, di or tri) allylamine, 2- (dimethylamino) ethyl acrylate Acrylic acid esters and methacrylic acid esters having amino groups such as, (mono, di or tri) ethanolamine and the like are preferable.
• aromatic monoamine having a reactive functional group examples include aminophenol and aminobenzenethiol
• heterocyclic-containing monoamine having a reactive functional group examples include N, N-dimethyl-4-. Examples thereof include aminopyridine and 2-aminopyridine.
• a cellulose fiber composite obtained by binding a monoamine having no reactive functional group as an amine to an anion-modified cellulose fiber is used.
• the monoamine having no reactive functional group preferably has at least one selected from a hydrocarbon group and a polyether group.
• monoamines having no reactive functional group include propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, 2-ethylhexylamine, dihexylamine, trihexylamine, octylamine, dioctylamine, and trioctylamine.
• a monoamine having no reactive functional group has an oxyalkanediyl group
• the oxyalkandyl group is selected from an oxypropylene group and an oxyethylene group. It is preferable to contain one or more kinds, and more preferably to contain an oxypropylene group.
• the average number of moles of the oxyalkanediyl group added is 1 or more, preferably 2 or more and 100 or less, more preferably 2 or more and 70 or less, and further preferably 3 or more and 50 or less.
• a plurality of alkanediyl groups may be the same or different from each other.
• a compound represented by the following formula (3) is preferable.
• R 2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms
• x represents the average number of moles of ethylene oxide (EO) added
• y represents propylene oxide (PO).
• the average number of added moles of is shown.
• the average number of moles of EO added x is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, still more preferably 5 or more, from the viewpoint of improving dispersion stability, viscosity thickening, and transparency. Then, it is preferably 100 or less, more preferably 70 or less, and further preferably 50 or less.
• the average number of moles of PO added is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, more preferably 5 or more, from the viewpoint of improving dispersion stability, viscosity thickening, and transparency. It is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less.
• the ratio (y / x) of the average number of moles added is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0., from the viewpoint of improving dispersion stability, viscosity thickening, and transparency. It is 3 or more, more preferably 1 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less.
• Examples of commercially available monoamines having no reactive functional group as described above include Jeffamine M-600, M-1000, M-2005, and M-2070 manufactured by Huntsman, USA. And so on.
• the monoamines that do not have the above-mentioned reactive functional groups can be used alone or in combination of two or more.
• one or more amines (total amines) selected from polyvalent amines and monoamines having a reactive functional group can be adjusted by the introduction rate of the amine represented by the following formula (1).
• Amine introduction rate (%) [Amine amount bonded to anionic group introduced into cellulose fiber (mmol / g) / Content of anionic group introduced into cellulose fiber (mmol / g)] ⁇ 100 ( 1)
• the "amine amount bonded to the anionic group introduced into the cellulose fiber" in the above formula (1) is more specifically "a polyvalent amine bonded to the anionic group introduced into the cellulose fiber and a reactive functional".
• the "amine amount” means the average bond amount (mmol / g) of amine
• the "content of anionic group introduced into the cellulose fiber” means an amine when the anionic group is a carboxy group. It means the carboxy group content (mmol / g) in the cellulose fiber before introduction.
• the introduction rate of is the sum of the introduction rates of each amine. It is considered that amine is mainly introduced into the surface of the cellulose fiber.
• the introduction rate of the amine represented by the above formula (1) is 60% or less, preferably 55% or less, more preferably 55% or less from the viewpoint of improving the dispersion stability and the viscosity thickening. From the viewpoint of obtaining a molded product having 50% or less, more preferably 45% or less, still more preferably 40% or less, and having excellent mechanical strength, it is preferably 5% or more, more preferably 10% or more, and further. It is preferably 15% or more. From the above viewpoint, the introduction rate of the amine represented by the above formula (1) is preferably 5% or more and 60% or less, more preferably 5% or more and 55% or less, still more preferably 10% or more and 50% or less. More preferably, it is 10% or more and 45% or less.
• the total amine of the polyvalent amine, the monoamine having a reactive functional group and the monoamine not having a reactive functional group has a dispersion stability depending on the introduction rate of the amine represented by the following formula (2). From the viewpoint of improving the viscosity, it is preferably 40% or more and 100% or less, more preferably 70% or more and 100% or less, and further preferably 90% or more and 100% or less.
• Amine introduction rate (%) [Average bond amount of amine (mmol / g) / Carboxylic group content in cellulose fiber before introduction of amine (mmol / g)] ⁇ 100
• the "average amount of amines bonded (mmol / g)" in the above formula (2) is more specifically "a polyvalent amine bonded to an anionic group introduced into a cellulose fiber, a monoamine having a reactive functional group”.
• the average binding amount (mmol / g) of one or more total amines selected from monoamines having no reactive functional groups is more specifically "a polyvalent amine bonded to an anionic group introduced into a cellulose fiber, a monoamine having a reactive functional group”.
• the introduction rate of the amine is 100% or less, preferably 80% from the viewpoint of improving dispersion stability and improving viscosity and transparency.
• it is more preferably 60% or less, preferably 55% or less, more preferably 50% or less, still more preferably 45% or less, still more preferably 40% or less from the viewpoint of improving viscosity and transparency.
• it is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more.
• the introduction rate of the amine represented by the above formula (1) is preferably 10% or more and 100% or less from the viewpoint of improving dispersion stability and transparency, but from the viewpoint of improving viscosity thickening. Therefore, a molded product having excellent mechanical strength is obtained, preferably 60% or less, more preferably 55% or less, further preferably 50% or less, still more preferably 45% or less, still more preferably 40% or less. From the viewpoint, it is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more.
• the total amine of the polyvalent amine, the monoamine having a reactive functional group and the monoamine not having a reactive functional group has a dispersion stability in terms of the introduction rate of the amine represented by the above formula (2). From the viewpoint of improving transparency, it is preferably 40% or more and 100% or less, more preferably 70% or more and 100% or less, and further preferably 90% or more and 100% or less.
• the introduction rate of a monoamine having no reactive functional group represented by the following formula (3) is preferably 5% or more, more preferably 10% or more, from the viewpoint of improving viscosity and transparency. It is more preferably 20% or more, more preferably 30% or more, and from the viewpoint of obtaining a molded product having excellent mechanical strength, it is preferably 95% or less, more preferably 90% or less, still more preferably 70% or less, and more. It is preferably 50% or less. From the above viewpoint, the introduction rate of the monoamine having no reactive functional group represented by the following formula (3) is preferably 5% or more and 95% or less, more preferably 10% or more and 90% or less, still more preferably 10. % Or more and 70% or less.
• Introduction rate of monoamine without reactive functional group [Amount of monoamine without reactive functional group bonded to anionic group introduced into cellulose fiber (mmol / g) / Anion introduced into cellulose fiber Content of sex groups (mmol / g)] x 100 (3)
• the introduction rate of the monoamine having no reactive functional group is the sum of the introduction rates of each amine.
• Ratio of the introduction rate of monoamines without reactive functional groups to the total introduction rate of monoamines with polyvalent amines and reactive functional groups is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0. It is 15 or more, and is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, still more preferably 1 or less, from the viewpoint of improving the mechanical strength of the molded product.
• the ratio of the introduction rate of the monoamine is preferably 0.01 or more and 10 or more. Below, it is more preferably 0.05 or more and 5 or less, still more preferably 0.1 or more and 3 or less, still more preferably 0.15 or more and 1 or less.
• the amine introduction rate can be calculated by measuring the amount of amine bound in the cellulose fiber composite by infrared absorption spectroscopy (IR). Specifically, it can be carried out by the method described in the examples.
• the cellulose fiber composite of the first invention is formed by binding an anion-modified cellulose fiber with one or more amines selected from polyvalent amines and monoamines having a reactive functional group.
• the bond may be either a covalent bond or an ionic bond, but from the viewpoint of ease of production, it is preferable that the bond is an ionic bond between the anionic group of the anionic modified cellulose fiber and the amine.
• the cellulose fiber composite of the second invention is formed by binding an anion-modified cellulose fiber having an average degree of polymerization of 300 or less to one or more amines selected from polyvalent amines and monoamines having a reactive functional group.
• the bond may be either a covalent bond or an ionic bond, but from the viewpoint of ease of production, it is preferable that the bond is an ionic bond between the anionic group of the anionic modified cellulose fiber and the amine.
• the mass ratio [(B) / (A)] in the cellulose fiber composite of the second invention is preferably 0.02 or more, more preferably 0.1 or more, from the viewpoint of improving dispersion stability and transparency. More preferably 0.3 or more, still more preferably 0.5 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, even more preferably 8 or less, even more preferably 5. It is as follows.
• the mass ratio of the monoamine (C) having no reactive functional group to the anion-modified cellulose fiber (A) in the cellulose fiber composite [(C) / (A) ] is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.5 or more, and preferably 10 or less, from the viewpoint of improving dispersion stability, thickening, and transparency. It is more preferably 5 or less, still more preferably 3 or less.
• the cellulose fiber composite can be produced by mixing an anion-modified cellulose fiber with one or more amines selected from polyvalent amines and monoamines having a reactive functional group. From the viewpoint of ionic bonding the anionic group and the amine, the anionic modified cellulose fiber is preferably in the acid type. Specifically, the mixture can be obtained, for example, by dispersing the components in an aqueous medium with a stirrer. As the aqueous medium, a liquid medium containing at least 10% by mass or more of water is preferable.
• the cellulose fiber complex can also be produced, for example, by dispersing it in a non-aqueous medium such as ethyl acetate containing only 10% by mass or less of water with a stirrer.
• the content of the aqueous medium in the aqueous composition during the production of the cellulose fiber composite is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more. It is preferably 70% by mass or more.
• known additives such as a dispersant, a viscosity modifier, a water-soluble polymer, and an antioxidant can be contained, if necessary. Since the cellulose fiber composite of the present invention is excellent in dispersion stability, thickening viscosity, and transparency, it can be suitably used for various industrial products such as daily miscellaneous goods, home appliances, packaging materials for home appliances, and automobile parts. can.
• the cellulose fiber composite of the present invention is obtained by mixing an anion-modified cellulose fiber with one or more amines selected from polyvalent amines and monoamines having a reactive functional group, and then further refining the fibers as necessary.
• the miniaturization treatment is a mechanical treatment, and by performing the miniaturization treatment, it can be converted into fine cellulose fibers (nanofibers) having a nanoscale fiber length and fiber diameter. By defibrating the cellulose fibers into nanofibers, a highly transparent cellulose nanofiber dispersion can be obtained. It is also possible to obtain a fine cellulose fiber composite by further finely processing the shortened anion-modified cellulose fibers to obtain fine cellulose fibers in advance and then adding a polyvalent amine.
• the device used for refining the cellulose fiber is not particularly limited. Examples thereof include a breaker, a beater, a low-pressure homogenizer, a high-pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a short-screw extruder, a twin-screw extruder, an ultrasonic stirrer, and the like.
• a strong shearing force it is preferable to apply a strong shearing force to the dispersion of cellulose fibers. From the viewpoint of miniaturization efficiency, it is preferable to use a wet high-pressure homogenizer capable of applying a strong shearing force.
• the high-pressure homogenizer pressurizes (high pressure) the fluid and ejects the fluid from a very narrow gap provided in the flow path, so that the fluid is dispersed and defibrated by the total energy such as collision between particles and shearing force due to pressure difference. , Grinding, and micronization.
• the pressure applied to the dispersion using the high-pressure homogenizer is preferably 50 MPa or more, more preferably 100 MPa or more, still more preferably 120 MPa or more, from the viewpoint of miniaturization efficiency.
• the number of processing passes is preferably 1 time or more, preferably 2 times or more, and preferably 20 times or less, more preferably 15 times or less, still more preferably 10 times or less. be.
• the average fiber length of the cellulose fiber composite or the fine cellulose fiber composite obtained by the above-mentioned miniaturization treatment is preferably 20 nm or more, more preferably 20 nm or more from the viewpoint of obtaining a molded product having excellent mechanical strength.
• the average fiber diameter of the cellulose fiber composite or the fine cellulose fiber composite is preferably 1 nm or more, more preferably 2 nm or more, still more preferably 2.5 nm or more, from the viewpoint of obtaining a molded product having excellent mechanical strength. From the viewpoint of improving dispersion stability and thickening, it is preferably 60 nm or less, more preferably 40 nm or less, and further preferably 20 nm or less.
• the average aspect ratio (average fiber length / average fiber diameter) of the cellulose fiber composite or the fine cellulose fiber composite is preferably 5 or more, more preferably 10 or more, and further, from the viewpoint of obtaining a molded product having excellent mechanical strength.
• the average fiber length of the cellulose fiber composite or the fine cellulose fiber composite obtained by the above-mentioned miniaturization treatment is preferably 20 nm or more, more preferably 20 nm or more from the viewpoint of obtaining a molded product having excellent mechanical strength.
• the average fiber diameter of the cellulose fiber composite or the fine cellulose fiber composite is preferably 1 nm or more, more preferably 2 nm or more, still more preferably 3 nm or more, and from the viewpoint of obtaining a molded product having excellent mechanical strength. From the viewpoint of improving dispersion stability and transparency, it is preferably 60 nm or less, more preferably 40 nm or less, and further preferably 20 nm or less.
• the average aspect ratio (average fiber length / average fiber diameter) of the cellulose fiber composite or the fine cellulose fiber composite is preferably 5 or more, more preferably 10 or more, and further, from the viewpoint of obtaining a molded product having excellent mechanical strength.
• the average fiber length of the cellulose fiber composite or the fine cellulose fiber composite obtained by the above-mentioned miniaturization treatment is preferably 20 nm or more and 900 nm or less, more preferably 40 nm or more and 700 nm or less. Further preferably, it is 60 nm or more and 600 nm or less, and the average fiber diameter is preferably 1 nm or more and 60 nm or less, more preferably 1 nm or more and 40 nm or less, further preferably 2 nm or more and 20 nm, and an average aspect ratio (average fiber length / average fiber diameter).
• the average fiber length, average fiber diameter, and average aspect ratio of the cellulose fiber composite and the fine cellulose fiber composite can be measured by the method described in Examples using an atomic force microscope (AFM).
• the dispersion of the present invention is formed by dispersing the cellulose fiber composite of the present invention in a medium.
• a dispersion containing the cellulose fiber complex having excellent dispersion stability can be obtained. Since such a dispersion is excellent in handleability, it can be suitably used for various industrial applications such as daily miscellaneous goods, home electric appliances parts, packaging materials for home electric appliances parts, and automobile parts.
• the medium is not particularly limited, and water; an alcohol solvent such as ethanol and isopropanol; a ketone solvent such as acetone and methyl ethyl ketone; a diester of ethyl acetate, methyl methacrylate, succinic acid and triethylene glycol monomethyl ether.
• Ester solvents such as: dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide and other amide solvents; hydrocarbon solvents such as toluene; acetic acid, acetonitrile, dichloromethane, chloroform, dimethylsulfoxide, tetrahydrofuran and the like
• organic solvents monomers, prepolymers, polymers and the like, and these can be used alone or in combination of two or more.
• one or more selected from water, alcohol-based solvent, ketone-based solvent, and amide-based solvent are preferable from the viewpoint of dispersion stability and viscosity thickening.
• the blending amount of the cellulose fiber composite in the dispersion is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and preferably 90% by mass or more. % Or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 65% by mass or less.
• the dispersion of the present invention uses the cellulose fiber composite of the present invention and the medium as a stirrer, a disperser, a beating machine, a low-pressure homogenizer, a high-pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, and a roll mill. , Short-screw kneader, 2-screw kneader, short-screw extruder, twin-screw extruder, mechanical processing using an ultrasonic stirrer, or the like.
• the dispersion treatment conditions such as temperature and pressure can be appropriately adjusted as necessary.
• the resin composition of the present invention comprises a blend of the cellulose fiber complex of the present invention and a resin.
• the resin contained in the resin composition used in the present invention is not particularly limited, and examples thereof include thermoplastic resins, curable resins, cellulosic resins, and rubber resins. Further, a resin precursor can also be blended. Such a resin or a resin precursor may be used alone or in combination of two or more.
• thermoplastic resin examples include saturated polyester resins such as polylactic acid resin; olefin resins such as polyethylene resin and polypropylene resin; vinyl chloride resin, vinylidene chloride resin, styrene resin, vinyl ether resin, polyvinyl alcohol resin, polyvinyl acetal resin, and polyvinyl acetate. Vinyl resins such as resins; (meth) acrylic resins; polyamide resins; polycarbonate resins; polysulfone resins; polyurethane resins; phenoxy resins and the like can be mentioned.
• an olefin resin, a polycarbonate resin, a (meth) acrylic resin, a vinyl chloride resin and a polyurethane resin are preferable, and a (meth) acrylic resin is more preferable, and the weight is 50.
• a (meth) acrylic resin containing% or more of methyl (meth) acrylate as a monomer unit is more preferable.
• the (meth) acrylic resin means a methacrylic resin and / or an acrylic resin.
• the curable resin examples include a photocurable resin and / or a thermosetting resin.
• the photocurable resin undergoes a polymerization reaction by using a photopolymerization initiator that generates radicals and cations by irradiation with active energy rays such as ultraviolet rays and electron beams.
• a photocurable resin is preferable because it has few agglomerates and can obtain a dispersion liquid or a molded product having excellent transparency.
• the photopolymerization initiator include the compounds described in paragraph [0113] of JP-A-2018-024967. With the photopolymerization initiator, for example, a monomer (monofunctional monomer, polyfunctional monomer), an oligomer having a reactive unsaturated group, a resin, or the like can be polymerized.
• Examples of the monomer include a (meth) acrylic monomer such as (meth) acrylic acid ester, an acryloyl-based monomer such as acryloylmorpholin, a vinyl-based monomer such as vinylpyrrolidone, isobornyl (meth) acrylate, and adamantyl.
• Monofunctional monomers such as (meth) acrylates having crosslinked cyclic hydrocarbon groups such as (meth) acrylates, di (meth) acrylates such as ethylene glycol di (meth) acrylates, propylene glycol di (meth) acrylates, and hexanediol diacrylates.
• Examples thereof include 3 to 8-functional monomers such as meta) acrylate-based bifunctional monomers, dipentaerythritol hexaacrylates, and glycerintri (meth) acrylates.
• Examples of the oligomer or resin having a reactive unsaturated group include (meth) acrylates such as bisphenol A-alkylene oxide adducts, epoxy (meth) acrylates (bisphenol A type epoxy (meth) acrylates, novolak type epoxy (meth) acrylates and the like.
• Polyester (meth) acrylate (aliphatic polyester type (meth) acrylate, aromatic polyester type (meth) acrylate, etc.), urethane (meth) acrylate (polyester type urethane (meth) acrylate, polyether type urethane (meth) acrylate, etc.) Etc.), silicone (meth) acrylate and the like.
• thermosetting resin examples include epoxy resin, phenoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, polyurethane resin, silicon resin and polyimide resin, and the dispersion is excellent in dispersibility.
• Epoxy resin, phenoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, and polyurethane resin are preferable, and epoxy resin, phenol resin, phenoxy resin, and polyurethane resin are more preferable, because a liquid can be obtained.
• Cellulose resin examples include organic acid esters such as cellulosic mixed acylate such as cellulose acetate (cellulose acetate) and cellulose acetate propionate; inorganic acid esters such as cellulose nitrate and cellulose phosphate; organic acid inorganic acids such as cellulose nitrate acetate.
• Mixed acid ester Cellulose ether ester such as acetylated hydroxypropyl cellulose and the like can be mentioned.
• Cellulose acetate includes cellulose triacetate (acetyl substitution degree 2.6 to 3), cellulose diacetate (acetyl substitution degree: 2 to 2.6), and cellulose monoacetate.
• the rubber-based resin include diene-based rubber and non-diene-based rubber.
• diene rubber modification of natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, butyl rubber, butadiene-acrylonitrile copolymer rubber, chloroprene rubber, epoxidized natural rubber, hydride natural rubber and the like. Examples include natural rubber.
• non-diene rubber examples include butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, urethane rubber, silicone rubber, fluororubber, acrylic rubber, polysulfide rubber, epichlorohydrin rubber and the like.
• the resin composition of the present invention a higher effect of improving mechanical strength can be obtained by appropriately selecting the resin to be blended according to the structure of the modifying group of the cellulose fiber composite.
• the modifying group a introduced into the cellulose fiber composite is an amino group, a hydroxy group, a thiol group, a carboxy group, or an alkoxide group, an epoxy resin or an isocyanate-based curable resin (the resin itself contains a curable isocyanate group).
• ester resin when isocyanate is used as a curing agent), ester resin, urethane resin, thioester resin, thiourethane resin, as well as resins having a carboxylic acid anhydride structure, a carboxylic acid halide structure, a lactone structure, and a lactam structure.
• resins having a functional group reactive with the modifying group a in the skeleton are preferable.
• the modifying group b introduced into the cellulose fiber composite is a vinyl group, an allyl group, an alkenyl group, an acryloyl group, or a methacryloyl group
• a curable resin having radical curability photocurable resin such as acrylic resin, rubber, etc.
• Etc. photocurable resin
• other resins having a functional group reactive with the modifying group b in the skeleton are preferable.
• the modifying group c introduced into the cellulose fiber composite is a carboxy group, an epoxy group, a carboxy group, an aldehyde group, or an isocyanate group, an epoxy resin, an ester resin, a urethane resin, a thioester resin, a thiourethane resin, or the like.
• a resin having a functional group reactive with the modifying group c in the skeleton is preferable.
• the modifying group introduced into the cellulose fiber composite is an oxazoline group
• a resin having a functional group reactive with an oxazoline group such as a carboxy group, a hydroxy group, a thiol group and an amino group in the skeleton is preferable.
• a resin having a functional group reactive with the silanol group such as a silicone resin in the skeleton is preferable.
• the composition of these cellulose fiber composites and a resin can be produced by mixing the cellulose fiber composite of the present invention with the above resin, or after mixing with a precursor of the above resin such as a monomer or an oligomer. , A resin composition can also be produced by polymerization.
• the amount of the cellulose fiber composite in the resin composition of the present invention can be appropriately determined depending on the physical characteristics of the resin and the molding method, but from the viewpoint of exerting the blending effect of the cellulose fiber composite, the resin 100 is converted into the blending amount. It is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 1 part by mass or more with respect to parts by mass. It is 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably 10 parts by mass or less.
• the resin composition of the present invention can be used as a plasticizer, a crystal nucleating agent, a filler, a hydrolysis inhibitor, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, an antistatic agent, an antifogging agent, and light, if necessary.
• Stabilizers, pigments, fungicides, antibacterial agents, foaming agents, polysaccharides, fragrances and the like can be blended.
• the resin composition contains a rubber-based resin, as components other than the above, if desired, a reinforcing filler such as carbon black or silica, various chemicals, such as a vulcanizing agent, a vulcanization accelerator, and aging Various additives such as an inhibitor, a scorch inhibitor, zinc oxide, stearic acid, process oil, and vegetable oil can be blended in a general amount.
• a reinforcing filler such as carbon black or silica
• various chemicals such as a vulcanizing agent, a vulcanization accelerator, and aging
• additives such as an inhibitor, a scorch inhibitor, zinc oxide, stearic acid, process oil, and vegetable oil can be blended in a general amount.
• the resin composition can be prepared by subjecting the cellulose fiber complex and the above resin to a dispersion treatment with a high-pressure homogenizer together with a dispersion medium and other components, if necessary. Further, each of these raw materials is agitated with a Henschel mixer, a rotation / revolution type stirrer, or the like, or melt-kneaded using a known kneader such as a closed kneader, a single-screw or twin-screw extruder, or an open roll type kneader.
• a known kneader such as a closed kneader, a single-screw or twin-screw extruder, or an open roll type kneader.
• the molded product of the present invention is formed by molding the cellulose fiber composite of the present invention or a resin composition containing the cellulose fiber composite and a resin.
• molding method a known molding method such as extrusion molding, injection molding, press molding, casting molding or solvent casting method can be applied.
• the cellulose fiber composite and the resin composition of the present invention are excellent in dispersion stability, and the mechanical strength such as tensile elastic modulus and tensile strength of various resin products which are molded products is excellent. It is presumed that this is because the cellulose fiber composite having excellent dispersion stability can have a pseudo-crosslinked structure in the resin.
• the use of the molded product of the present invention is not particularly limited.
• It can be used for composite materials.
• a molded product having excellent transparency can be obtained, it can be suitably applied to applications such as transparent resin materials, adhesives, adhesives, paints, electronic materials, fiber composite materials, etc., and also has mechanical strength. Since an excellent molded product can be obtained, it can be suitably applied to applications such as three-dimensional molding materials, cushioning materials, repair materials, sealing materials, heat insulating materials, sound absorbing materials, tires, automobile parts, and packaging materials.
• the present invention further discloses the following [1] to [49].
• [1] A cellulose fiber composite in which one or more amines selected from polyvalent amines and monoamines having a reactive functional group are bonded to anion-modified cellulose fibers.
• a cellulose fiber complex that satisfies at least one of the following conditions 1 and 2.
• Condition 1 The introduction rate of the amine represented by the following formula (1) is 60% or less.
• Amine introduction rate (%) [Amine amount bonded to anionic group introduced into cellulose fiber (mmol / g) / Content of anionic group introduced into cellulose fiber (mmol / g)] ⁇ 100 ( 1)
• Condition 2 The average degree of polymerization of the anion-modified cellulose fiber is 300 or less.
• polyvalent amines are aliphatic diamines, aliphatic triamines, monocyclic aromatic diamines, condensed polycyclic aromatic diamines, bis (diaminophenyl), 4,4'-diaminobiphenyl, bis (aminophenoxy), bis.
• the reactive functional group is an epoxy group, a carboxy group, a hydroxy group, a thiol group, a vinyl group, an allyl group, an alkenyl group, an acryloyl group, a methacryloyl group, an aldehyde group, an isocyanate group, a hydrazide group, an oxazoline group or a carbodiimide group.
• the cellulose fiber composite according to any one of [1] to [21] above, which is one or more selected from an azetidineium group, a pyridinium group, an imidazolium group, an alkoxide group, a methylol group, and a silanol group.
• Ratio of introduction rate of monoamine having no reactive functional group to total introduction rate of monoamine having polyvalent amine and reactive functional group (introduction rate of monoamine having no reactive functional group / introduction rate of monoamine having no reactive functional group / polyvalent amine and reaction
• Ratio of introduction rate of monoamine having no reactive functional group to total introduction rate of monoamine having polyvalent amine and reactive functional group (introduction rate of monoamine having no reactive functional group / introduction rate of monoamine having no reactive functional group / polyvalent amine and reaction
• [45] A dispersion in which the cellulose fiber composite according to any one of [1] to [44] is dispersed in a medium.
• a resin composition obtained by blending the cellulose fiber complex according to any one of [1] to [44] above with a resin.
• a molded product obtained by molding the cellulose fiber composite according to any one of the above [1] to [44] or the resin composition according to the above [46].
• [48] The cellulose fiber composite according to any one of [1] to [44] above, wherein the anion-modified cellulose fiber is mixed with one or more amines selected from polyvalent amines and monoamines having a reactive functional group. How to make a body.
• the method for producing a cellulose fiber complex according to the above [48] which further performs a miniaturization treatment.
• the dispersion liquid is front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 ⁇ m / Measurement was performed under the conditions of pixel, inner diameter of syringe: 6515 ⁇ m, spacer thickness: 1000 ⁇ m, image recognition mode: ghost, threshold value: 8, analytical sample volume: 1 mL, sampling: 15%. 10,000 or more cellulose fibers were measured, their average ISO fiber length was calculated as the average fiber length, the average ISO fiber diameter was calculated as the average fiber diameter, and the average aspect ratio was calculated.
• a medium is added to the cellulose complex to be measured, a dispersion having a concentration of 0.0001% by mass is prepared, and the dispersion is dropped onto mica (mica) and dried, and the sample is used as an observation sample.
• a force microscope (AFM), Digital instrument, Nanoscope III Tapping mode AFM, probe used by Nanosensors, Point Probe (NCH)
• the fiber height of the cellulose fibers in the observation sample was measured. It was measured. At that time, in a microscope image in which the cellulose fibers could be confirmed, 100 or more cellulose fibers were extracted, and the average fiber length and the average fiber diameter were measured.
• the average aspect ratio was calculated from the average fiber length and the average fiber diameter.
• the dried cellulose fiber composite was measured by the ATR method using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JASCO Corporation, trade name: FT / IR4600), and was subjected to ionic bonding by the following formula.
• the introduction rate of amine was calculated by determining the average binding amount of amine.
• the following shows the case where the anionic group is a carboxy group (-COOH). In the case of an anionic group other than the carboxy group, the value of the peak intensity may be appropriately changed, and the average bond amount and introduction rate of the amine may be calculated.
• the individual amine introduction rate is calculated from the above amine introduction rate. At that time, it is assumed that the individual amines present at the time of the reaction have reacted in proportion to the molar ratio.
• anion-modified cellulose fiber 1-1 (oxide cellulose fiber) was obtained.
• the average fiber length of the anion-modified cellulose fiber 1-1 was 2022 ⁇ m, the average aspect ratio was 50, the carboxy group content was 1.5 mmol / g, and the average degree of polymerization was 387.
• Preparation Example 1-2 (Preparation of Shortened Anion-Modified Cellulose Fiber 1-2) (1) Oxidation Treatment 100 g of eucalyptus-derived broadleaf bleached kraft pulp (manufactured by CENIBRA) is sufficiently stirred with 9,900 g of ion-exchanged water, and then TEMPO (manufactured by ALDRICH, Free radical, 98) is added to the pulp mass of 100 g. Mass%) 1.25 g, sodium bromide 12.5 g, and sodium hypochlorite 28.4 g were added in this order. Using a pH stud, 0.5 M sodium hydroxide was added dropwise to keep the pH at 10.5. After the reaction was carried out at 20 ° C.
• the average fiber length of the anion-modified cellulose fibers 1-2 was 133 ⁇ m, the average fiber diameter was 35 ⁇ m, the average aspect ratio was 4.5, the carboxy group content was 1.3 mmol / g, and the average degree of polymerization was 89. ..
• Example 1-1 (1) Preparation of Cellulose Fiber Complex 0.15 g of the anion-modified cellulose fiber 1-1 obtained in Preparation Example 1-1 was charged into a beaker equipped with a magnetic stirrer and a stirrer in an absolute dry mass. Subsequently, 0.09 g of aliphatic polyether diamine (manufactured by Huntsman, USA, trade name: Jeffamine D-2000) and 0.36 g of aliphatic monoamine (manufactured by Huntsman, USA, trade name: Jeffamine M-2070) were charged. It was dissolved in 30 g of water.
• aliphatic polyether diamine manufactured by Huntsman, USA, trade name: Jeffamine D-2000
• Jeffamine M-2070 aliphatic monoamine
• the obtained mixed solution was stirred at room temperature (25 ° C.) for 1 hour, and a suspension of a cellulose fiber composite in which a polyvalent amine was bonded to an anion-modified cellulose fiber (cellulose fiber (without modifying group) content 0.5 mass). %) was obtained.
• (2) Miniaturization treatment The suspension obtained in (1) above is subjected to 5-pass treatment at 150 MPa with a high-pressure homogenizer (manufactured by Yoshida Kikai Kogyo Co., Ltd., trade name: NanoVeta L-ES) for miniaturization treatment. rice field. By this treatment, a dispersion in which the fine cellulose fiber composite was dispersed in water (cellulose fiber (without modifying group) content 0.5% by mass) was obtained. The average fiber length of this fine cellulose fiber composite was 542 nm, the average fiber diameter was 3.2 nm, and the average aspect ratio was 169.
• Example 1-1 the fine cellulose fiber composite was used as each solvent in the same manner as in Example 1-1, except that the amount of anion-modified cellulose fibers was kept constant and the conditions shown in Tables 1 and 2 were changed. A dispersed dispersion (cellulose fiber (without modifying group) content 0.5% by mass) was obtained.
• Test Example 1-1 (Dispersion Stability Test) The obtained dispersion of the fine cellulose fiber complex was allowed to stand at room temperature (25 ° C.) for 1 day, and the transparency and the presence or absence of a precipitate were visually confirmed and evaluated based on the following evaluation criteria.
• evaluation criteria A: It is in a transparent state and no precipitate is formed.
• C A part of the cellulose fiber is generated as a precipitate.
• Evaluation A is particularly excellent in nano-dispersion stability, and evaluation B has dispersion stability to the extent that it does not interfere with actual use.
• Test Example 1-2 viscosity evaluation test
• E-type viscometer manufactured by Toki Sangyo Co., Ltd., VISCOMETER TVE-35H, cone rotor: 1 ° 34
• the measurement was carried out under the conditions of 25 ° C., 1 rpm and 1 minute using a temperature controller (VISCOMATE VM-150III manufactured by Toki Sangyo Co., Ltd.) (using ′ ⁇ R24).
• the dispersion containing the cellulose fiber composite having an introduction rate of the amine represented by the formula (1) of 60% or less has dispersion stability without agglomeration of the cellulose fiber composite. It can be seen that the viscosity is excellent and the viscosity increase is also improved.
• Example 1-23 (Preparation of Monomer Composition) 20 g (1 g of fine cellulose fibers) in which the fine cellulosic fiber composite obtained in Example 1-5 is dispersed in DMF and an acrylic monomer (hexanediol diacrylate, viscosity 6 mPa ⁇ s) as a matrix component are eliminated. 10 g of the mixture was mixed with a dry mass, stirred for 3 minutes using a rotating and revolving stirrer (manufactured by Shinky Co., Ltd., trade name: Awatori Rentaro), and defoamed for 3 minutes. Then, DMF was completely removed by an evaporator to obtain an acrylic monomer composition containing a fine cellulose fiber composite (cellulose fiber (without modifying group) content: 1% by mass with respect to the monomer). The results are shown in Table 3.
• Example 1-23 the fine cellulose fiber composite was prepared in the same manner as in Example 1-23, except that the type and matrix component of the dispersion of the fine cellulose fiber composite used were changed to the combinations shown in Table 3.
• a monomer composition (cellulose fiber content: 1% by mass based on the monomer) blended with various matrix components was obtained. The results are shown in Table 3.
• Examples 1-26 to 1-28, Comparative Example 1-6 an epoxy monomer (manufactured by Mitsubishi Chemical Co., Ltd., bisphenol F type liquid type, trade name: jER807, viscosity 6300 mPa ⁇ s) was used as a matrix component, and the dispersion of the fine cellulose fiber composite used was used.
• Monomer composition containing fine cellulose fiber composites in various matrix components (cellulose fiber (without modifying group) content: content: 1% by mass based on the monomer) was obtained. The results are shown in Table 3.
• the obtained mixed solution was stirred at 95 ° C. for 24 hours and then dehydrated to obtain shortened anion-modified cellulose fibers 2-1.
• the average fiber length of the anion-modified cellulose fiber 2-1 was 133 ⁇ m, the average aspect ratio was 3.3, the carboxy group content was 1.3 mmol / g, and the average degree of polymerization was 89.
• Preparation Example 2-2 (Preparation of anion-modified cellulose fiber 2-2) (1) Oxidation treatment 100 g of bleached kraft pulp fiber (manufactured by West Freder Co., Ltd., trade name: Hinton) of coniferous tree is sufficiently stirred with 9,900 g of ion-exchanged water, and then TEMPO (ALDRICH) is applied to 100 g of the pulp fiber. , Free radical, 98% by mass) 1.25 g, sodium bromide 12.5 g, sodium hypochlorite 37.2 g were added in this order. Using a pH stud, 0.5 M sodium hydroxide was added dropwise to keep the pH at 10.5. After the reaction was carried out at 20 ° C.
• the obtained mixed solution was stirred at 95 ° C. for 24 hours, washed thoroughly, and then dehydrated to obtain anion-modified cellulose fibers 2-2.
• the obtained anion-modified cellulose fiber 2-2 had an average fiber length of 186 ⁇ m, an average aspect ratio of 4.5, a carboxy group content of 1.5 mmol / g, and an average degree of polymerization of 163.
• Preparation Example 2-3 (Preparation of anion-modified cellulose fibers 2-3) Only the same oxidation treatment as in Preparation Example 2-2 (1) was carried out to obtain anion-modified cellulose fibers 2-3 without performing the short fiber treatment in Preparation Example 2-2 (2).
• the obtained anion-modified cellulose fibers 2-3 had an average fiber length of 2022 ⁇ m, an average aspect ratio of 50, a carboxy group content of 1.5 mmol / g, and an average degree of polymerization of 387.
• Preparation Example 2-4 (Preparation of anion-modified cellulose fiber 2-4) After the same oxidation treatment as in Preparation Example 2-2 (1), the short fiber treatment in the same manner as in Preparation Example 2-1 (2) was carried out to obtain anion-modified cellulose fibers 2-4.
• the obtained anion-modified cellulose fibers 2-4 had an average fiber length of 210 ⁇ m, an aspect ratio of 4.6, a carboxy group content of 1.5 mmol / g, and an average degree of polymerization of 187.
• Example 2-1 Preparation of Cellulose Fiber Complex
• a beaker equipped with a magnetic stirrer and a stirrer the water content of the anion-modified cellulose fiber 2-1 obtained in Preparation Example 2-1 was replaced with ethanol, and then the absolute dry mass was 0. .15g was charged.
• 0.39 g of an aliphatic polyether diamine manufactured by Huntsman, USA, trade name: Jeffamine D-2000 was charged and dissolved in 30 g of N, N-dimethylformamide (DMF).
• the obtained mixed solution was stirred at room temperature (25 ° C.) for 1 hour, and a suspension of a cellulose fiber composite in which a polyvalent amine was bonded to an anion-modified cellulose fiber (cellulose fiber (without modifying group) content 0.5 mass). %) was obtained.
• (2) Miniaturization treatment The suspension obtained in (1) above is subjected to 5-pass treatment at 150 MPa with a high-pressure homogenizer (manufactured by Yoshida Kikai Kogyo Co., Ltd., trade name: NanoVeta L-ES) for miniaturization treatment. rice field. By this treatment, a dispersion in which the fine cellulose fiber composite was dispersed in DMF (cellulose fiber (without modifying group) content 0.5% by mass) was obtained. The average fiber length of this fine cellulose fiber composite was 117 nm, the average fiber diameter was 3.5 nm, and the average aspect ratio was 37.
• Example 2-1 the fine cellulose fiber composite was dispersed in various solvents in the same manner as in Example 2-1 except that the amount of anion-modified cellulose fibers was kept constant and changed to the conditions shown in Table 2. A body (cellulose fiber content 0.5% by mass) was obtained.
• the characteristics of the obtained fine cellulose fiber complex were evaluated by the methods of Test Examples 2-1 and 2-2 below. The results are shown in Tables 4 and 5. The details of each component in Tables 4 and 5 are the same as the details of each component in Tables 1 and 2.
• the monoamine (C-1) OA in Table 5 is octylamine.
• Test Example 2-1 (Dispersion Stability Test) The obtained dispersion of the fine cellulose fiber complex was allowed to stand at room temperature (25 ° C.) for 1 day, and the transparency and the presence or absence of a precipitate were visually confirmed and evaluated based on the following evaluation criteria.
• evaluation criteria A: It is in a transparent state and no precipitate is formed.
• C A part of the cellulose fiber is generated as a precipitate.
• Evaluation A is particularly excellent in nano-dispersion stability, and evaluation B has dispersion stability to the extent that it does not interfere with actual use.
• Test Example 2-2 Transparency Evaluation Test
• the light transmittance of the dispersion was measured as follows, and the transparency was evaluated.
• the light transmittance was measured under normal temperature and pressure. Specifically, 30 mL of each dispersion immediately after the dispersion treatment is transferred to a screw tube (No. 7 manufactured by AS ONE Corporation), the dispersion is shaken together with the screw tube, and a sample in a visually uniform state has an optical path length of 10 mm. 3 mL was placed in a quartz cell, and immediately, the absorbance at a wavelength of 660 nm was measured using a double beam spectrophotometer (“U-2910” manufactured by Hitachi High-Tech Science Co., Ltd.). The medium used for preparing each dispersion was a blank (that is, the light transmittance was 100%), and the light transmittance (%) was determined from the absorbance of each dispersion.
• the dispersion containing the cellulose fiber composite having an average degree of polymerization of the anion-modified cellulose fiber of 300 or less is excellent in dispersion stability without agglomeration of the cellulose fiber composite, and is also a dispersion. It can be seen that the transparency of is also high. On the other hand, when an anion-modified cellulose fiber complex having an average degree of polymerization of more than 300 was used, aggregates of the cellulose fiber complex were formed, and the transparency of the dispersion was remarkably low.
• Example 2-26 20 g of a dispersion in which the fine cellulosic fiber composite obtained in Example 2-22 is dispersed in ethyl acetate (1 g of fine cellulosic fibers) and an acrylic resin monomer as a matrix resin (manufactured by Toa Synthetic Co., Ltd., trade name: Arontack) 10 g of S-1511X (viscosity 4000 mPa ⁇ s) was mixed in an absolute dry mass, stirred for 3 minutes using a rotating and revolving stirrer (manufactured by Shinky Co., Ltd., trade name: Awatori Rentaro), and defoamed for 3 minutes. Then, a resin composition containing a fine cellulose fiber complex was obtained (cellulose fiber content: 1% by mass with respect to the monomer). The light transmittance of the obtained resin monomer composition was 41%. The results are shown in Table 6.
• Example 2-26 the fine cellulose fiber composite was prepared in the same manner as in Example 2-26, except that the type of the dispersion and the matrix resin of the fine cellulose fiber complex used were changed to the combinations shown in Table 6.
• a monomer composition (complex content: 1% by mass based on the monomer) blended with various resins was obtained. The results are shown in Table 6.
• Example 2-26 an epoxy monomer (manufactured by Mitsubishi Chemical Co., Ltd., bisphenol F type liquid type, trade name: jER807, viscosity 6300 mPa ⁇ s) was used as a matrix component, and the dispersion of the fine cellulose fiber composite used was used.
• the monomer composition containing the cellulose fiber composite having an average degree of polymerization of the anion-modified cellulose fibers of 300 or less has high transparency of the monomer composition without agglomeration of the cellulose fiber composites.
• anion-modified cellulose fibers having an average degree of polymerization of more than 300 were used, aggregates of the cellulose fiber composites were formed, and the transparency of the monomer composition was remarkably low.
• Examples 2-36 to 2-37, Comparative Example 2-6 Manufacturing of resin molded products 4 g of a dispersion in which the fine cellulose fiber composite obtained in Example 2-17 was dispersed in DMF (0.2 g of fine cellulose fibers) and a polystyrene resin as a matrix resin (manufactured by Sigma Aldrich Co., Ltd., number average molecular weight 170,000). , Serial No. 441147-1KG) and 30 g of DMF were mixed and stirred with a magnetic stirrer at room temperature (25 ° C.) for 2 hours to obtain a resin solution. The obtained solution was poured into a glass petri dish having a diameter of 9 cm and dried at 90 ° C. for 12 hours to obtain a resin molded product containing a fine cellulose fiber composite. The characteristics of the obtained fine cellulose fiber-containing resin molded product were evaluated by the method of Test Example 2-3 below. The results are shown in Table 7.
• Test Example 2-3 evaluation of transparency
• the Haze value of the obtained resin molded product was measured with a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd., trade name: HM-150 type). The lower the Haze value of the resin molded product, the more transparent it is.
• the resin molded product containing the cellulose fiber composite having an average degree of polymerization of anion-modified cellulose of 300 or less has high transparency of the resin molded product without agglomeration of the cellulose fiber composite.
• an anion-modified cellulose complex having an average degree of polymerization of more than 300 was used, aggregates of the cellulose fiber complex were formed, and the transparency of the resin molded product was remarkably low.
• Example 2-38 Manufacturing of resin molded product
• the introduction rate of 2-dimethylaminoethyl acrylate is 60%
• the introduction rate of Jeffamine M-2070 (C-1) is 30%.
• a dispersion in which the fine cellulose fiber composite was dispersed in ethanol was obtained (cellulose fiber content: 0.5% by mass), except that the dispersion medium was changed to ethanol.
• a urethane acrylate compound (Shikou UV-7000B, manufactured by Mitsubishi Chemical Co., Ltd.) was mixed with 4.02 g (4.73 g of 4-acryloyl morpholine) of the obtained dispersion, and at room temperature (25 ° C.) in a magnetic stirrer. After stirring for 2 hours, 0.20 g of 1-hydroxycyclohexylphenyl ketone was further added and stirred to obtain a photocurable film precursor composition in which the fine cellulose fiber composite was dispersed.
• a urethane acrylate compound Shikou UV-7000B, manufactured by Mitsubishi Chemical Co., Ltd.
• Reference Example 2-1 (Manufacturing of resin molded product) Fine cellulose fiber composite in the same manner as in Example 2-38 except that 3.73 g of 4-acryloyl morpholine and 1.60 g of a urethane acrylate compound (UV-7000B) were mixed to obtain a photocurable film precursor composition. A cured film (resin molded product) containing no body was obtained. The film thickness of the obtained cured film was about 76 ⁇ m.
• Test Example 2-4 Evaluation of reinforcing property of resin molded product
• a dumbbell type test piece JIS K 6251, dumbbell-shaped No. 7 type
• This dumbbell type test piece was subjected to a tensile test using an autograph (manufactured by Shimadzu Corporation, Autograph Precision Universal Testing Machine, AGS-10kNX) at a tensile speed of 1 mm / min, and the tensile elastic modulus and tensile strength were performed. I asked for strength. The larger the value, the higher the mechanical strength.
• Table 8 shows the relative values with the numerical value of Reference Example 2-1 as 100.
• Example 2-39 Manufacturing of resin molded product (1) Preparation of Resin Composition in which Micronized Cellulose Fiber Composite is Dispersed In a beaker equipped with a magnetic stirrer and a stirrer, the water content of the shortened anion-modified cellulose fiber obtained in Preparation Example 1 was replaced with DMF. Later, 0.4 g of absolute dry mass was charged. Subsequently, 0.13 g of Jeffamine M-2070 and 0.045 g of diallylamine were charged, dissolved in 80 g of DMF, and stirred at room temperature (25 ° C.) for 1 hour.
• the obtained mixture (coating liquid) was coated on a copper foil (18 ⁇ m thick, manufactured by Furukawa Electric Co., Ltd.) with a coating thickness of 1.0 mm using an applicator.
• the solvent was removed by drying at 80 ° C. for 1 hour, and then thermosetting at 150 ° C. for 1 hour to obtain a resin molded product (coating film) in which the finely divided cellulose fiber composite was dispersed.
• the film thickness of the obtained cured film was 137 m.
• Example 2-39 (2) finely divided cellulose is used in the same manner as in Example 2-39, except that 10.0 g of epoxy resin (jER828 manufactured by Mitsubishi Chemical Co., Ltd.) is used instead of the resin composition. A resin molded product containing no fiber composite was obtained. The film thickness of the obtained cured film was 129 ⁇ m. Table 8 shows the relative values with the numerical value of Reference Example 2-2 as 100.
• epoxy resin jER828 manufactured by Mitsubishi Chemical Co., Ltd.
• the resin molded product containing the cellulose fiber composite having an average degree of polymerization of anion-modified cellulose of 300 or less has high mechanical strength of the resin molded product without agglomeration of the cellulose fiber composite.
• the cellulose fiber composite of the present invention has high dispersibility, high viscosity, and high transparency of the dispersion, various industries such as daily miscellaneous goods, home electric appliances, packaging materials for home appliances, automobile parts, etc. It can be suitably used in applications.

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