Polyol Composition

Abstract

To provide a polyol composition that contains cellulose fibers with excellent dispersibility and transparency.SOLUTION: A polyol composition contains a polyol and modified cellulose fibers. The modified cellulose fibers have cellulose I-type crystal and an average fiber length of 500 nm or less and are one or more selected from modified cellulose fibers (A) and / or modified cellulose fibers (B). The modified cellulose fibers (A): modified cellulose fibers with modifying groups bound to ionic groups of cellulose fibers. Modified cellulose fibers (B): modified cellulose fibers with modifying groups bound to hydroxy groups of cellulose fibers.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyol composition and a method for producing the same. [Background technology]

[0002] Traditionally, plastic materials derived from petroleum, a finite resource, have been widely used, but in recent years, technologies with less environmental impact have come into the spotlight. Against this technological background, materials made from cellulose fibers, a biomass that exists in abundance in nature, and particularly fine cellulose fibers, are attracting attention because of their significantly improved mechanical properties.

[0003] Patent Document 1 describes a polyol composition (A) containing cellulose nanofibers (a), and discloses the production of a polyurethane resin composition containing a polyurethane resin obtained by reacting the polyol composition with a polyisocyanate (B). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-194162 Summary of the Invention [Problem to be solved by the invention]

[0005] However, Patent Document 1 is not sufficient in terms of dispersibility of cellulose fibers in the polyol composition. It is believed that the use of a polyol composition containing highly dispersible cellulose fibers leads to excellent transparency of the obtained resin composition, as well as improved strength and impact resistance.

[0006] The present invention relates to a polyol composition that is excellent in dispersibility of cellulose fibers and transparency. [Means for solving the problem]

[0007] The present invention relates to the following [1] to [3]. [1] A polyol composition containing a polyol and modified cellulose fibers, wherein the modified cellulose fibers have cellulose type I crystals, have an average fiber length of 500 nm or less, and are one or more types selected from the group consisting of the following modified cellulose fibers (A) and modified cellulose fibers (B). Modified cellulose fiber (A): Modified cellulose fiber in which a modifying group is bonded to the ionic group of a cellulose fiber containing an ionic group. Modified cellulose fiber (B): Modified cellulose fiber in which a modifying group is bonded to the hydroxyl group of the cellulose fiber. [2] A method for producing the polyol composition according to [1], comprising a step of micronizing modified cellulose fibers having an average fiber length of more than 500 nm in a polyol, wherein the modified cellulose fibers subjected to the micronization step are one or more types selected from the group consisting of the following modified cellulose fibers (A) and modified cellulose fibers (B). Modified cellulose fiber (A): Modified cellulose fiber in which a modifying group is bonded to the ionic group of a cellulose fiber containing an ionic group. Modified cellulose fiber (B): Modified cellulose fiber in which a modifying group is bonded to the hydroxyl group of the cellulose fiber. [3] A polymerization product of the polyol composition described in [1] above. [Effects of the Invention]

[0008] According to the present invention, a polyol composition having excellent dispersibility for cellulose fibers and excellent transparency can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] As a result of intensive research into the above-mentioned problems, the inventors of the present invention have newly discovered that by blending modified cellulose fibers having a specific fiber length with a polyol, a polyol composition having excellent dispersibility and transparency of the modified cellulose fibers can be obtained. Although the mechanism behind this is unclear, it is presumed that the modified cellulose fibers having a specific fiber length have high dispersibility in polyol compounds.

[0010] [Polyol composition] The polyol composition of the present invention comprises a polyol and modified cellulose fibers.

[0011] [Polyol] Representative examples of polyols are not particularly limited as long as they are compounds containing two or more hydroxy groups, and include, for example, ester-based polyols, ether-based polyols, polymer polyols, phenolic resin-based polyols, and Mannich polyols, which are described in "Polyurethane Resin Handbook" edited by Iwata Keiji (published by Nikkan Kogyo Shimbun, September 25, 1987).

[0012] Examples of ether polyols include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, butanediol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sucrose, and polyether polyols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to the polyhydric alcohols. Examples of ester polyols include polyester polyols obtained by polycondensation of aliphatic carboxylic acids such as malonic acid, succinic acid, and adipic acid, or aromatic carboxylic acids such as phthalic acid, with aliphatic glycols such as ethylene glycol, diethylene glycol, and propylene glycol.

[0013] From the viewpoint of dispersibility, the average molecular weight of the polyol is preferably 100 or more, more preferably 200 or more, and even more preferably 400 or more. From the viewpoint of dispersibility, the average molecular weight is preferably 15,000 or less, more preferably 10,000 or less, and even more preferably 8,000 or less. In this specification, the average molecular weight of the polyol is a mass average molecular weight.

[0014] [Modified cellulose fiber] The modified cellulose fiber contained in the polyol composition of the present invention is one or more types selected from the group consisting of the following modified cellulose fiber (A) and modified cellulose fiber (B), and preferably contains one or more modifying groups selected from the group consisting of (a) hydrocarbon groups and (b) polymer groups. Modified cellulose fiber (A): Modified cellulose fiber in which a modifying group is bonded to the ionic group of a cellulose fiber containing an ionic group. Modified cellulose fiber (B): Modified cellulose fiber in which a modifying group is bonded to the hydroxyl group of the cellulose fiber.

[0015] From the viewpoint of reducing environmental impact, natural cellulose fibers are preferably used as the raw material for the modified cellulose fibers. Examples of natural cellulose fibers include wood pulps such as softwood pulp and hardwood pulp, cotton pulps such as cotton linter and cotton lint, non-wood pulps such as straw pulp and bagasse pulp, and bacterial cellulose. These fibers may be used alone or in combination of two or more.

[0016] The average fiber diameter and average fiber length of the raw cellulose fibers are not particularly limited. The average fiber diameter is, for example, preferably 1 μm or more from the viewpoint of availability and cost reduction, and from the same viewpoint, preferably 100 μm or less. The average fiber length is, for example, preferably 1,000 μm or more from the viewpoint of availability and cost reduction, and from the same viewpoint, preferably 10,000 μm or less. The average fiber diameter and average fiber length of the raw cellulose fibers can be measured by the method described in the Examples below.

[0017] <Modified cellulose fiber (A)> The modified cellulose fiber (A) in the present invention is a modified cellulose fiber obtained by bonding a modifying group to the ionic group of a cellulose fiber containing an ionic group.

[0018] (ionic group) The cellulose fibers containing ionic groups are cellulose fibers that have been modified so as to contain ionic groups.

[0019] Examples of ionic groups include anionic groups and cationic groups. In this specification, cellulose fibers having anionic groups are also referred to as "anion-modified cellulose fibers." Examples of anionic groups include carboxyl groups, sulfonic acid groups, and phosphate groups, while examples of cationic groups include groups containing an onium group such as ammonium, phosphonium, or sulfonium. From the viewpoint of incorporation efficiency into the modified cellulose fiber (A), anionic groups are preferred as ionic groups, and carboxyl groups are more preferred as anionic groups. From the viewpoint of introducing a modifying group, the anion-modified cellulose fibers are preferably oxidized cellulose fibers or carboxymethylated cellulose fibers, and more preferably cellulose fibers in which the C6 position of the cellulose structural unit is a carboxyl group.

[0020] When the ionic group is an anionic group, the counter ion of the anionic group is one or more selected from the group consisting of metal ions and protons. The metal ion is preferably a monovalent cation, such as a lithium ion, a sodium ion, or a potassium ion. From the viewpoint of reaction efficiency to form modified cellulose fibers, a proton is preferred.

[0021] The content of ionic groups in cellulose fibers containing ionic groups is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, and even more preferably 0.6 mmol / g or more, from the viewpoint of stable micronization and introduction of modifying groups. From the same viewpoint, the upper limit is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less, and even more preferably 2.0 mmol / g or less. When the ionic groups are anionic groups, the content of the anionic groups can be measured by the method described in the Examples below.

[0022] (modifying group) In the modified cellulose fiber (A), the modifying group is bonded to the ionic group of the cellulose fiber containing the ionic group, and the bonding mode here includes an ionic bond and a covalent bond (e.g., an amide bond, an ester bond, a urethane bond, etc.).

[0023] The modifying group in the modified cellulose fiber (A) preferably contains one or more modifying groups selected from the group consisting of (a) hydrocarbon groups and (b) polymer groups. These groups may be introduced into the modified cellulose fiber (A) either alone or in combination of two or more. From the viewpoint of dispersibility, it is preferred that the modified cellulose fiber (A) contains both the (a) hydrocarbon group and the (b) polymer group.

[0024] From the viewpoint of improving dispersibility and transparency, the number of carbon atoms in the hydrocarbon group as the modifying group is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and from the same viewpoint, it is preferably 30 or less, more preferably 25 or less, even more preferably 24 or less, even more preferably 20 or less, and even more preferably 18 or less. Unless otherwise specified, the number of carbon atoms in the hydrocarbon group means the number of carbon atoms in one modifying group.

[0025] Specific examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, a tert-pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, an octadecyl group, a docosyl group, and an octacosanyl group.

[0026] Specific examples of the chain unsaturated hydrocarbon group include an ethylene group, a propylene group, a butene group, an isobutene group, an isoprene group, a pentene group, a hexene group, a heptene group, an octene group, a nonene group, a decene group, a dodecene group, a tridecene group, a tetradecene group, and an octadecene group.

[0027] Specific examples of the cyclic saturated hydrocarbon group include a cyclopropane group, a cyclobutyl group, a cyclopentane group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, a cyclotridecyl group, a cyclotetradecyl group, and a cyclooctadecyl group.

[0028] The aromatic hydrocarbon group is, for example, selected from the group consisting of an aryl group and an aralkyl group. In the aryl group and the aralkyl group, the aromatic ring itself may be substituted or unsubstituted.

[0029] Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a diphenyl group, a triphenyl group, a terphenyl group, and groups in which these groups are substituted with the substituents described below.

[0030] Examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, phenylpentyl, phenylhexyl, phenylheptyl, and phenyloctyl groups, and groups in which the aromatic group of these groups is further substituted with a substituent. Examples of other aromatic hydrocarbon groups include diphenylmethyl, triphenylmethyl, and groups in which the aromatic group of these groups is further substituted with a substituent.

[0031] When the modifying group is a hydrocarbon group and the hydrocarbon group has a substituent, the substituent may be, for example, a linear or branched alkoxy group having 1 to 6 carbon atoms; a linear or branched alkoxycarbonyl group having 1 to 6 carbon atoms in the alkoxy group; a halogen atom such as a bromine atom or an iodine atom; an acyl group having 1 to 6 carbon atoms; an aralkyl group; an aralkyloxy group; an alkylamino group having 1 to 6 carbon atoms; a dialkylamino group having 1 to 6 carbon atoms in the alkyl group; a hydroxy group, an ether, an amide, etc. The above-mentioned various hydrocarbon groups may themselves be bonded to another hydrocarbon group as a substituent.

[0032] The polymer group is a functional group containing a polymer structure. From the viewpoint of improving dispersibility, the molecular weight of the polymer group is preferably 100 or more, more preferably 200 or more, more preferably 300 or more, more preferably 400 or more, even more preferably 600 or more, even more preferably 1,000 or more, and even more preferably 1,500 or more. From the same viewpoint, the molecular weight is preferably 10,000 or less, more preferably 7,000 or less, even more preferably 5,000 or less, even more preferably 4,000 or less, even more preferably 3,500 or less, and even more preferably 2,500 or less.

[0033] From the viewpoint of improving dispersibility, the polymer group is preferably a functional group having a repeating structure linked by a structure having an oxygen atom, more preferably a functional group having a repeating structure linked by an oxygen atom, such as a polyoxyalkylene structure (alkylene oxide chain) or a polysiloxane structure (silicone chain), more preferably a functional group having a polyoxyalkylene structure, and even more preferably an alkoxypolyoxyalkylene group.

[0034] From the viewpoint of ensuring the chemical stability of the modified cellulose fiber and its dispersion stability as a filler, the polyoxyalkylene structure is preferably a (co)polymer structure of one or more oxyalkylenes selected from oxyalkylenes having from 2 to 8 carbon atoms, more preferably a (co)polymer structure of one or more oxyalkylenes selected from oxyalkylenes having from 2 to 4 carbon atoms, even more preferably a (co)polymer structure of one or two oxyalkylenes selected from ethylene oxide (EO) and propylene oxide (PO), and even more preferably a copolymer structure in which ethylene oxide (EO) and propylene oxide (PO) are polymerized randomly or in blocks.

[0035] Examples of the group containing a copolymer structure ((EO / PO) copolymer structure) in which ethylene oxide (EO) and propylene oxide (PO) are polymerized randomly or in a block manner include a group represented by the following formula (i'), which can be introduced using a compound represented by the following formula (i):

[0036] [ka]

[0037] [In the formula, R 1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an aminoalkyl group thereof, EO and PO are present randomly or in blocks, a is a positive number indicating the average number of moles of EO added, and b is a positive number indicating the average number of moles of PO added. Here, "the aminoalkyl group" means a group in which one of the hydrogen atoms constituting the linear or branched alkyl group having 1 to 6 carbon atoms is substituted with an amino group. In formula (i), an alkylene group having 1 to 3 carbon atoms may be present between the amino group and EO or PO.]

[0038] R 1 When R is a straight or branched alkyl group having 1 to 6 carbon atoms, the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, or a sec-propyl group.1 may be a hydrogen atom.

[0039] From the viewpoint of improving dispersibility and transparency, a is preferably 1 or more, more preferably 3 or more, even more preferably 6 or more, even more preferably 11 or more, even more preferably 15 or more, even more preferably 20 or more, even more preferably 25 or more, and even more preferably 30 or more. From the same viewpoint, a is preferably 100 or less, more preferably 70 or less, even more preferably 60 or less, even more preferably 50 or less, and even more preferably 40 or less.

[0040] From the viewpoint of improving dispersibility and transparency, b is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more. From the same viewpoint, b is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, even more preferably 25 or less, even more preferably 20 or less, even more preferably 15 or less, and even more preferably 10 or less.

[0041] Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, and a propylene group.

[0042] The PO content (mol %) in the (EO / PO) copolymer structure can be calculated based on the above a and b, specifically, by b × 100 / (a + b). From the viewpoint of further improving dispersibility, the PO content is preferably 1 mol % or more, more preferably 5 mol % or more, even more preferably 7 mol % or more, and even more preferably 10 mol % or more. From the same viewpoint, it is preferably 100 mol % or less, more preferably 90 mol % or less, even more preferably 85 mol % or less, even more preferably 75 mol % or less, even more preferably 60 mol % or less, even more preferably 50 mol % or less, even more preferably 40 mol % or less, and even more preferably 30 mol % or less.

[0043] From the viewpoint of improving dispersibility, the molecular weight of the (EO / PO) copolymer structure is preferably 100 or more, more preferably 200 or more, even more preferably 300 or more, more preferably 400 or more, even more preferably 500 or more, even more preferably 600 or more, even more preferably 1,000 or more, and even more preferably 1,500 or more. From the same viewpoint, the molecular weight is preferably 10,000 or less, more preferably 7,000 or less, even more preferably 5,000 or less, even more preferably 4,000 or less, even more preferably 3,500 or less, and even more preferably 2,500 or less.

[0044] The amine having an EO / PO copolymer structure represented by formula (i) is a modifying compound for introducing the modifying group represented by formula (i'), and details of the amine are described, for example, in Japanese Patent No. 6105139.

[0045] The amine having an EO / PO copolymer structure (also referred to as "EOPO amine") may be, for example, a commercially available product, and specific examples include Jeffamine M-2070, Jeffamine M-2005, Jeffamine M-2095, Jeffamine M-1000, Jeffamine M-600, Jeffamine M-3085, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-3000, and Jeffamine T-5000, all manufactured by HUNTSMAN.

[0046] From the viewpoint of improving dispersibility, the average bond amount of modifying groups in the modified cellulose fiber (A) is preferably 0.01 mmol / g or more, more preferably 0.05 mmol / g or more, even more preferably 0.1 mmol / g or more, even more preferably 0.3 mmol / g or more, and even more preferably 0.5 mmol / g or more. From the same viewpoint, it is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less, even more preferably 2.0 mmol / g or less, even more preferably 1.8 mmol / g or less, and even more preferably 1.5 mmol / g or less. When any two or more types of modifying groups are simultaneously introduced into the modified cellulose fiber (A), the average bond amount of the modifying groups is preferably such that the total amount of the introduced modifying groups is within the above-mentioned range.

[0047] The introduction rate of the modifying group in the modified cellulose fiber (A) is preferably 10% or more from the viewpoints of dispersibility and transparency, and is preferably 99% or less from the viewpoint of obtaining a molded product with excellent mechanical strength. When any two or more types of modifying groups are simultaneously introduced as the modifying groups, it is preferable that the total introduction rate be within the above range, provided that it does not exceed the upper limit of 100%.

[0048] The average bond amount and introduction rate of the modifying group can be adjusted by the amount and type of compound used to introduce the modifying group, i.e., the modifying compound, the reaction temperature, the reaction time, the type of solvent, etc. The average bond amount (mmol / g) and introduction rate (%) of the modifying group refer to the amount and rate of the modifying group introduced (bonded) to the ionic group in the modified cellulose fiber (A). For example, when the ionic group is anionic, the average bond amount and introduction rate of the modifying group are calculated by the method described in the Examples below.

[0049] (Method for producing modified cellulose fiber (A)) The modified cellulose fiber (A) can be produced by any known method, as long as it can introduce a modifying group into the ionic group of the cellulose fiber containing an ionic group. For example, when the ionic group is a carboxy group, the modified cellulose fiber (A) can be produced by referring to paragraphs 0017 to 0106 of JP 2018-024967 A. Alternatively, the carboxy group can be introduced into the cellulose fiber by reacting the cellulose fiber with a halogenated acetic acid such as chloroacetic acid, an acid anhydride of a dicarboxylic acid compound such as maleic anhydride, succinic anhydride, phthalic anhydride, or adipic anhydride, an imidized product of an acid anhydride of a compound having a carboxy group, or a derivative of an acid anhydride of a compound having a carboxy group. When the ionic group is a sulfonic acid group, a method for introducing the sulfonic acid group into the cellulose fiber includes adding sulfuric acid to the cellulose fiber and heating the resulting mixture. When the ionic group is a phosphate group, methods for introducing the phosphate group into cellulose fibers include mixing a powder or aqueous solution of phosphoric acid or a phosphoric acid derivative with dry or wet cellulose fibers, or adding an aqueous solution of phosphoric acid or a phosphoric acid derivative to a dispersion of cellulose fibers. A method for introducing a modifying group includes mixing a compound having a modifying group with cellulose fibers having a phosphate group. When the ionic group is a cationic group, a method for introducing the cationic group into cellulose fibers includes treating cellulose fibers with a cationizing agent in the presence of an alkali. When producing modified cellulose fiber (A), the aspect ratio reduction treatment and microfine-refining process described in JP 2018-024967 A can be omitted.

[0050] <Modified cellulose fiber (B)> The modified cellulose fiber (B) in the present invention is a modified cellulose fiber in which a modifying group is bonded to a hydroxy group of a cellulose fiber.

[0051] (modifying group) In the modified cellulose fiber (B), the cellulose fiber and the modifying group are bonded via an ether bond. In this specification, "bonded via an ether bond" means that the modifying group reacts with the hydroxy group of the cellulose fiber to form an ether bond.

[0052] The modifying group in the modified cellulose fiber (B) is preferably a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include saturated or unsaturated, straight-chain or branched-chain aliphatic hydrocarbon groups, aromatic hydrocarbon groups such as phenyl groups, and alicyclic hydrocarbon groups such as cyclohexyl groups. Examples of the substituent in the hydrocarbon group which may have a substituent in the present invention include halogen atoms, oxyalkylene groups such as oxyethylene groups, and hydroxy groups.

[0053] A preferred embodiment of such modified cellulose fiber (B) (referred to as "embodiment 1") is, for example, a cellulose fiber having one or more modifying groups selected from the group consisting of the modifying group represented by the following general formula (1) and the modifying group represented by the following general formula (2) bonded to the cellulose fiber via an ether bond, and having a cellulose type I crystal structure. -CH2-CH(R 0 )-R 1 (1) -CH2-CH(R 0 )-CH2-(OA) n -OR 1 (2) [wherein R in general formula (1) and general formula (2) 0 represents a hydrogen atom or a hydroxy group, and R 1 each independently represents a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms, preferably 3 to 30 carbon atoms, and in general formula (2), n is a number of 0 to 50, and A is a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms.

[0054] A specific example of the first aspect is a modified cellulose fiber represented by the following general formula (3).

[0055] [ka]

[0056] [In the formula, R may be the same or different and represent hydrogen or a modifying group selected from the modifying group represented by the general formula (1) and the modifying group represented by the general formula (2), except for the case where all R are simultaneously hydrogen. m is preferably an integer of 20 to 3000.]

[0057] The modified cellulose fiber (B) represented by the general formula (3) has a repeating structure of cellulose units into which the above-mentioned modifying group has been introduced. From the viewpoint of dispersibility, the number of repeating units, m, in the general formula (3), is preferably an integer of 20 or more and 3000 or less.

[0058] (Optionally substituted hydrocarbon group) The modified cellulose fiber (B) of aspect 1 is introduced with one or more modifying groups selected from the modifying groups represented by the above general formula (1) and the following general formula (2), either singly or in any combination. Note that even when the modifying group introduced is only one of the above groups, the same modifying group may be introduced within each group, or two or more types may be introduced in combination.

[0059] From the viewpoint of dispersibility, R in general formula (1) and general formula (2) 0 is preferably a hydroxy group.

[0060] R in general formula (1) 1 From the viewpoint of dispersibility, the number of carbon atoms is preferably 25 or less. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a hexadecyl group, an octadecyl group, an isooctadecyl group, an icosyl group, a triacontyl group, a phenyl group, and a methylphenyl group.

[0061] R in general formula (2) 1The number of carbon atoms in R in the general formula (1) is preferably 4 or more from the viewpoint of dispersibility, and is preferably 27 or less from the viewpoint of availability and improving reactivity. 1 The same can be mentioned.

[0062] In general formula (2), A forms an oxyalkylene group together with the adjacent oxygen atom. From the viewpoints of availability and cost, the number of carbon atoms in A is preferably 2 or more, and from the same viewpoints, preferably 4 or less. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0063] In general formula (2), n represents the number of moles of alkylene oxide added, and is preferably 3 or more from the viewpoints of dispersibility, availability, and cost, and is preferably 40 or less from the same viewpoints.

[0064] From the viewpoint of dispersibility, the combination of A and n in general formula (2) is preferably a combination in which A is a linear or branched divalent saturated hydrocarbon group having 2 to 3 carbon atoms and n is a number of 0 to 20.

[0065] Specific examples of the modifying group represented by general formula (1) include, for example, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an isooctadecyl group, an icosyl group, a propylhydroxyethyl group, a butylhydroxyethyl group, a pentylhydroxyethyl group, a hexylhydroxyethyl group, a heptylhydroxyethyl group, an octylhydroxyethyl group, a 2-ethylhexylhydroxyethyl group, a nonylhydroxyethyl group, a decylhydroxyethyl group, a undecylhydroxyethyl group, a dodecylhydroxyethyl group, a hexadecylhydroxyethyl group, an octadecylhydroxyethyl group, an isooctadecylhydroxyethyl group, an icosylhydroxyethyl group, and a triacontylhydroxyethyl group.

[0066] Specific examples of the modifying group represented by general formula (2) include, for example, a 3-butoxy-2-hydroxy-propyl group, a 3-hexoxyethyleneoxide-2-hydroxy-propyl group, a 3-hexoxy-2-hydroxy-propyl group, a 3-octoxyethyleneoxide-2-hydroxy-propyl group, a 3-octoxy-2-hydroxy-propyl group, a 6-ethyl-3-hexoxy-2-hydroxy-propyl group, a 6-ethyl-3-hexoxyethyleneoxide-2-hydroxy-propyl group, a 3-detoxyethyleneoxide-2-hydroxy-propyl group, Examples thereof include a 3-dethoxy-2-hydroxypropyl group, a 3-undethoxyethyleneoxide-2-hydroxypropyl group, a 3-undethoxy-2-hydroxypropyl group, a 3-dodethoxyethyleneoxide-2-hydroxypropyl group, a 3-dodethoxy-2-hydroxypropyl group, a 3-hexadethoxyethyleneoxide-2-hydroxypropyl group, a 3-hexadethoxy-2-hydroxypropyl group, a 3-octadethoxyethyleneoxide-2-hydroxypropyl group, a 3-octadethoxy-2-hydroxypropyl group, etc. The number of moles of alkylene oxide added may be from 0 to 50, and examples thereof include the above-mentioned substituents having an oxyalkylene group such as ethylene oxide, with the number of moles added being 10, 12, 13, or 20 moles.

[0067] (Molar substitution (MS)) In the modified cellulose fiber (B) of Aspect 1, the molar amount of modifying groups introduced per mole of anhydroglucose unit of cellulose (molar substitution: MS) cannot be generally limited depending on the type of modifying group. However, from the viewpoint of dispersibility, it is preferably 0.0001 moles or more, more preferably 0.01 moles or more, and even more preferably 0.1 moles or more. Also, from the viewpoint of having a cellulose type I crystal structure, it is preferably 1.5 moles or less, more preferably 1.2 moles or less, and even more preferably 1 mole or less. Here, when the bonded modifying groups are composed of multiple types of modifying groups, the MS of the bonded modifying groups is the sum of the MS of each modifying group. In this specification, the MS of the modifying groups in the modified cellulose fiber (B) can be measured according to the method described in the Examples below.

[0068] <Method for producing modified cellulose fiber (B)> In the modified cellulose fiber (B) of the present invention, as described above, a modifying group, preferably a hydrocarbon group optionally having the modifying group, is bonded to the cellulose fiber via an ether bond, and the introduction of the modifying group can be carried out according to any known method without particular limitation. Specific examples of methods for producing the modified cellulose fiber (B) of embodiment 1 are described below.

[0069] (Method for producing modified cellulose fiber (B) of embodiment 1) A specific example of a method for producing the modified cellulose fiber (B) of Aspect 1 is a method in which a specific compound is reacted with raw cellulose fiber in the presence of a base.

[0070] In order to reduce the number of manufacturing steps, pre-micronized cellulose fibers may be used as the raw cellulose fibers, and in this case, the average fiber diameter is preferably 1 nm or more from the viewpoints of availability and cost. Although there is no particular upper limit, it is preferably 500 nm or less from the viewpoint of handleability.

[0071] (base) The base is not particularly limited, but from the viewpoint of promoting the etherification reaction, one or more selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, primary to tertiary amines, quaternary ammonium salts, imidazole and its derivatives, pyridine and its derivatives, and alkoxides are preferred. Specific examples include the bases described in paragraphs 0053 to 0058 of JP 2017-053077 A.

[0072] The amount of base is preferably 0.01 equivalents or more relative to the anhydroglucose units of the raw cellulose fiber from the viewpoint of proceeding with the etherification reaction, and is preferably 10 equivalents or less from the viewpoint of production costs.

[0073] The raw cellulose fibers and the base may be mixed in the presence of a solvent, which is not particularly limited and includes, for example, water, isopropanol, t-butanol, dimethylformamide, toluene, methyl isobutyl ketone, acetonitrile, dimethyl sulfoxide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, hexane, 1,4-dioxane, and mixtures thereof.

[0074] There are no particular limitations on the temperature or time for mixing the raw material cellulose fiber and base, provided that they can be mixed uniformly.

[0075] Next, a modifying compound (also referred to herein as an "etherifying agent"), preferably a compound for introducing an optionally substituted hydrocarbon group, is added to the mixture of the raw cellulose fibers and base obtained above, and the raw cellulose fibers are reacted with the compound. As such a compound, it is preferable to use a compound having a reactive cyclic structural group, and it is more preferable to use a compound having an epoxy group.

[0076] Examples of compounds to which the modifying group represented by general formula (1) can be bonded via an ether bond include the alkylene oxide compounds described in paragraphs 0079 to 0084 of JP-A No. 2017-053077.

[0077] Examples of compounds to which the modifying group represented by general formula (2) can be bonded via an ether bond include the glycidyl ether compounds described in paragraphs 0085 to 0091 of JP-A No. 2017-053077.

[0078] The amount of the modifying compound can be determined based on the desired introduction rate of the modifying group in the resulting modified cellulose fiber (B), but from the standpoint of reactivity, it is preferably 0.01 equivalents or more relative to the anhydroglucose units of the raw cellulose fiber, and from the standpoint of production costs, it is preferably 10 equivalents or less.

[0079] (Etherification reaction) The etherification reaction between the compound and the raw cellulose fiber can be carried out by mixing them in the presence of a solvent. The solvent is not particularly limited, and the solvents exemplified as those usable in the presence of the base can be used. For details of the etherification reaction, please refer to paragraphs 0070 to 0075 of JP 2017-053077 A.

[0080] The modified cellulose fibers (B) of embodiment 1 thus obtained may be subjected to a known pulverization treatment, for example, treatment using a high-pressure homogenizer in an organic solvent.

[0081] In either case of the modified cellulose fibers (A) and (B), the modified cellulose fibers can be used in the form of a dispersion, or the solvent can be removed from the dispersion by drying or other treatment to obtain dried powdery modified cellulose fibers, which can then be used. Here, "powdered" refers to a powder in which the modified cellulose fibers are agglomerated, and does not mean cellulose particles.

[0082] Examples of powdered modified cellulose fibers include a dried product obtained by directly drying the cellulose fiber dispersion, a dried product powdered by mechanical processing, a cellulose fiber dispersion powdered by a known spray drying method, and a cellulose fiber dispersion powdered by a known freeze drying method. The spray drying method is a method in which the cellulose fiber dispersion is sprayed in the atmosphere and dried.

[0083] <Characteristics of modified cellulose fiber> Modified cellulose fibers have a cellulose type I crystalline structure due to the use of natural cellulose fibers as their raw material. Cellulose type I refers to the crystalline form of natural cellulose, and cellulose type I crystallinity refers to the proportion of cellulose type I crystalline regions in the total cellulose. The presence or absence of cellulose type I crystalline structure can be determined by the presence of a peak at 2θ = 22.6° in X-ray diffraction measurements.

[0084] From the viewpoint of dispersibility, the cellulose type I crystallinity of the modified cellulose fiber is preferably 30% or more, more preferably 35% or more, even more preferably 40% or more, and even more preferably 45% or more. From the viewpoint of the cost of the cellulose raw material used, it is preferably 95% or less, more preferably 90% or less, even more preferably 85% or less, and even more preferably 80% or less. In this specification, the cellulose type I crystallinity of cellulose fiber, modified cellulose fiber, etc. is specifically measured by the method described in the Examples below.

[0085] The average fiber length of the modified cellulose fiber is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 50 nm or more from the viewpoint of production efficiency and improvement of mechanical properties, and is 500 nm or less, preferably 400 nm or less, and more preferably 300 nm or less from the viewpoint of dispersibility. The average fiber length of the modified cellulose fiber can be measured by the method described in the Examples below.

[0086] The average fiber diameter of the modified cellulose fiber is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 3 nm or more from the viewpoint of production efficiency and improvement of mechanical properties, and is preferably 30 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and even more preferably 5 nm or less from the viewpoint of dispersibility. The average fiber diameter of the modified cellulose fiber can be measured by the method described in the Examples below.

[0087] From the viewpoint of improving production efficiency and mechanical properties, the average aspect ratio of the modified cellulose fiber is preferably 1 or more, more preferably 5 or more, even more preferably 8 or more, and even more preferably 35 or more, and from the viewpoint of dispersibility, it is preferably 100 or less, more preferably less than 100, even more preferably 80 or less, even more preferably 55 or less, and even more preferably 50 or less. The average aspect ratio of the modified cellulose fiber can be measured by the method described in the examples below.

[0088] The polyol content in the polyol composition of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, from the viewpoint of containing polyol, and is preferably 99.9% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less, from the viewpoint of containing modified cellulose fiber.

[0089] The content of modified cellulose fiber in the polyol composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of the expression of the effects of the modified cellulose fiber, and is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of dispersibility.

[0090] The mass ratio of modified cellulose fiber to polyol in the polyol composition of the present invention is preferably 0.001 or more, more preferably 0.005 or more, and even more preferably 0.01 or more, from the viewpoint of expressing the effects of the modified cellulose fiber, and is preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.1 or less, from the viewpoint of dispersibility.

[0091] When two or more types of modified cellulose fibers are used, the content of the modified cellulose fibers refers to the total amount, and when two or more types of polyols are used, the content of the polyols refers to the total amount. The content of the modified cellulose fibers in the polyol composition and the mass ratio of modified cellulose fiber / polyol are calculated using the cellulose fiber (equivalent amount) in the modified cellulose fibers, excluding the modifying groups.

[0092] The polyol composition of the present invention may optionally contain components such as plasticizers, fillers, pigments, thixotropy-imparting agents, process oils, UV inhibitors, reinforcing materials, aggregates, curing accelerators, flame retardants, thickeners, leveling agents, etc. These other components may be used alone or in combination of two or more.

[0093] [Method for producing polyol composition] The method for producing the polyol composition of the present invention is not particularly limited, but a preferred example is a production embodiment that includes a step of micronizing modified cellulose fibers having an average fiber length of more than 500 nm in a polyol.

[0094] In this production embodiment, the modified cellulose fibers subjected to the micronization treatment are one or more types selected from the group consisting of the modified cellulose fibers (A) and modified cellulose fibers (B) described above. Furthermore, from the viewpoint of dispersibility, it is preferable to use modified cellulose fibers that have been shortened to an average fiber length of 1 μm or more and 1,000 μm or less as the modified cellulose fibers subjected to the micronization treatment. The average fiber length of such short cellulose fibers is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 30 μm or more, and even more preferably 50 μm or more, and is preferably 1,000 μm or less, more preferably 800 μm or less, even more preferably 500 μm or less, and even more preferably 400 μm or less. The average fiber diameter is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more, and is preferably 300 μm or less, more preferably 100 μm or less, and even more preferably 60 μm or less.

[0095] Known methods can be used for the fiber shortening treatment, and the target cellulose fibers can be shortened by alkaline hydrolysis treatment, acid hydrolysis treatment, hydrogen peroxide treatment, ultraviolet treatment, electron beam treatment, hot water decomposition treatment, mechanical treatment, enzyme treatment, etc. Note that the modified cellulose fibers to be subjected to the micronization treatment may be shortened before or after the introduction of the above-mentioned modifying groups or ionic groups. For example, a production mode can be mentioned in which ionic groups are introduced into the raw cellulose fibers, followed by the fiber shortening treatment, and then modifying groups are introduced, and the resulting shortened modified cellulose fibers are micronized in a polyol.

[0096] Suitable devices that can be used in the micronization treatment include known dispersing machines. For example, a mixer with a stirring blade, a disintegrator, a beater, a low-pressure homogenizer, a high-pressure homogenizer grinder, cutter mill, ball mill, jet mill, roll mill, single-shaft kneader , twin-screw mixer, single-screw extruder, twin-screw extruder, ultrasonic mixer, home juicer mixer, etc. The operating conditions of the device can be set appropriately by referring to the attached instruction manual. That's fine.

[0097] The polyol composition of the present invention has excellent dispersibility for modified cellulose fibers and can therefore be suitably used in the production of polyester resin compositions and polyurethane resin compositions. The polymerization product of the polyol composition of the present invention will now be described.

[0098] [Polymerization product of polyol composition] The polymerization product of the polyol composition in the present invention is preferably at least one selected from the group consisting of polyester resin compositions and polyurethane resin compositions.

[0099] When the polymerization product of the polyol composition is a polyester resin composition, the desired polyester resin composition can be obtained by selecting a polycarboxylic acid (having two or more carboxyl groups in the molecule) such as an aromatic polycarboxylic acid (e.g., terephthalic acid, 2,6-naphthalenedicarboxylic acid) or an aliphatic polycarboxylic acid (e.g., adipic acid, sebacic acid, (iso)phthalic acid) according to the required physical properties and reactivity, and carrying out an appropriate polymerization reaction according to a conventional method.

[0100] When the polymerization product of the polyol composition is a polyurethane resin composition, the desired polyurethane resin composition can be obtained by selecting an isocyanate (having two or more isocyanate groups in the molecule) such as an aromatic isocyanate, such as tolylene diisocyanate or diphenylmethane diisocyanate, or an aliphatic isocyanate, such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate or tetramethylxylylene diisocyanate, depending on the desired physical properties and reactivity, and carrying out an appropriate polymerization reaction according to a conventional method.

[0101] The amount of modified cellulose in the polymerization product of the polyol composition of the present invention is, in terms of cellulose (excluding modifying groups, etc.), preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, in terms of the expression of physical properties, calculated based on the blending amount. From the viewpoint of handleability, the amount is preferably 35% by mass or less, more preferably 25% by mass or less, and even more preferably 15% by mass or less.

[0102] The catalyst can be appropriately selected depending on the type of resin, and for example, in the case of a polyurethane resin composition, examples of the catalyst include amine catalysts, organometallic catalysts, etc. The catalysts may be used alone or in combination of two or more.

[0103] The proportion of the catalyst can be appropriately selected depending on the type of curing agent, etc., but is preferably 0.01 to 100 parts by mass, for example, per 100 parts by mass of the polyol composition.

[0104] [Other ingredients] The polymerization product of the polyol composition of the present invention may contain, within the scope of the present invention, for example, plasticizers, crystal nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, lubricants such as hydrocarbon waxes and anionic surfactants, UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, mildew inhibitors, antibacterial agents, foaming agents, surfactants; polysaccharides such as starches and alginic acid; natural proteins such as gelatin, glue, and casein; inorganic compounds such as tannins, zeolites, ceramics, and metal powders; fragrances; flow control agents; leveling agents; conductive agents; UV dispersants; and deodorizers. Furthermore, other polymeric materials and other compositions may also be added within the scope of the present invention, within the scope of the present invention.

[0105] The polymerization product of the polyol composition of the present invention can be molded by appropriately using a known molding method such as coating molding, extrusion molding, injection molding, press molding, cast molding or solvent casting. [Example]

[0106] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Note that "normal pressure" refers to 101.3 kPa and "normal temperature" refers to 25°C.

[0107] [Average fiber diameter, average fiber length, and average aspect ratio of anion-modified cellulose fibers, shortened anion-modified cellulose fibers, and refined modified cellulose fibers] Deionized water or DMF is added to the cellulose fibers or a polyol composition containing the cellulose fibers to prepare a dispersion with a concentration of 0.0001% by mass. The dispersion is then dropped onto mica and dried to form an observation sample. The fiber height (height difference between fiber-containing and fiber-free areas) of the cellulose fibers in the observation sample is measured using an atomic force microscope (AFM, Nanoscope III Tapping mode AFM, manufactured by Digital Instruments, Inc.; the probe is a Point Probe (NCH) manufactured by Nanosensors, Inc.). In this case, 100 cellulose fibers are randomly selected from a microscopic image in which the cellulose fibers can be seen, and the number-average fiber diameter is calculated from their fiber height. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated from the average fiber length / average fiber diameter.

[0108] [Average fiber diameter and average fiber length of raw cellulose fibers] Deionized water is added to the cellulose fibers to be measured to prepare a dispersion containing 0.01% by mass of cellulose. The dispersion is measured using a wet dispersion image analysis particle size distribution analyzer (manufactured by Jusco International, product name: IF-3200) under the following conditions: front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 μm / pixel, syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold: 8, analysis sample volume: 1 mL, and sampling: 15%. One hundred cellulose fibers are measured, and the average ISO fiber diameter and average ISO fiber length are calculated as the average fiber diameter and average fiber length, respectively.

[0109] [Solid content in dispersion] The measurement is performed using a halogen moisture meter (Shimadzu Corporation; product name "MOC-120H"), with 1 g of sample measured every 30 seconds at a constant temperature of 150°C, and the value when the mass loss is 0.1% or less of the initial amount of the sample is taken as the solid content.

[0110] [Anionic Group Content of Anion-Modified Cellulose Fibers and Modified Cellulose Fibers] A dry mass of 0.5 g of the cellulose fiber to be measured is placed in a beaker and mixed with deionized water or a 2:1 (volume ratio) methanol / water mixture to a total volume of 55 mL. 5 mL of 0.01 M aqueous sodium chloride solution is then added to prepare a dispersion. The dispersion is stirred until the cellulose fiber to be measured is fully dispersed. 0.1 M hydrochloric acid is added to the dispersion to adjust the pH to 2.5-3. Using an automatic titrator (manufactured by DKK-TOA Corporation, product name "AUT-701"), 0.05 M aqueous sodium hydroxide solution is added dropwise to the dispersion with a waiting time of 60 seconds, and the conductivity and pH values ​​are measured every minute. Measurements are continued until the pH reaches approximately 11, and a conductivity curve is obtained. The sodium hydroxide titration amount is determined from this conductivity curve, and the anionic group content of the cellulose fiber to be measured is calculated using the following formula: Anionic group content (mmol / g) = [Titer of aqueous sodium hydroxide solution (mL) × Concentration of aqueous sodium hydroxide solution (0.05 M)] / [Mass of cellulose fiber to be measured (0.5 g)]

[0111] [Average bond amount and introduction rate of modifying groups in modified cellulose fiber (A)] The average bond amount of the modifying group is determined by the following IR measurement method, and the average bond amount and introduction rate are calculated using the following formula. Specifically, the IR measurement involves measuring the infrared absorption spectrum of the dried modified cellulose fiber by the ATR method using an infrared absorption spectrometer (IR) (Nicolet 6700, manufactured by Thermo Fisher Scientific), and the average bond amount and introduction rate of the modifying group are calculated using formulas A and B. The following describes the case where the anionic group is a carboxy group, i.e., the case of oxidized cellulose fiber. The following "1720 cm" -1The "peak intensity" is the peak intensity derived from the carbonyl group. In the case of an anionic group other than a carboxy group, the wave number value may be appropriately changed to calculate the average bond amount and introduction rate of the modifying group. <Formula A-1 (Ionic bond)> Average binding amount of modifying group (mmol / g) = a × (bc) ÷ b a: Carboxylic group content of oxidized cellulose fiber (mmol / g) b: 1720 cm of oxidized cellulose fiber -1 Peak intensity of c: 1720 cm of modified cellulose fiber -1 Peak intensity of <Formula A-2 (in the case of an amide bond)> Average bond amount of modifying group (mmol / g) = de d: Carboxylic group content of oxidized cellulose fiber (mmol / g) e: Carboxylic group content of modified cellulose fiber (mmol / g) <Formula B> Modification group introduction rate (mol%) = 100 × f / g f: Average binding amount of the modification group (mmol / g) g: Carboxylic group content of oxidized cellulose fiber (mmol / g)

[0112] [Degree of introduction of substituents (MS) in modified cellulose fiber (B)] First, the introduced mass (mass%) of the substituents contained in the cellulose to be measured is calculated according to the Zeisel method, which is known as a method for analyzing the average number of moles of alkoxy groups added to a cellulose ether, as described in Analytical Chemistry, Vol. 51, No. 13, 2172 (1979), "The Japanese Pharmacopoeia, 15th Edition (section on the analytical method for hydroxypropyl cellulose)" and the like. The procedure is as follows: (i) Add 0.1 g of n-tetradecane to a 200 mL measuring flask and fill to the mark with hexane to prepare an internal standard solution. (ii) 70 mg of purified and dried cellulose to be measured and 80 mg of adipic acid are weighed out accurately into a 10 mL vial, and 2 mL of hydroiodic acid is added and the vial is sealed. (iii) The mixture in the vial is heated in a block heater at 160°C for 1 hour while being stirred with a stirrer tip. (IV) After heating, add 2 mL of the internal standard solution and 2 mL of diethyl ether to the vial, and stir at room temperature for 1 minute. (v) The upper layer (diethyl ether layer) of the mixture separated into two phases in the vial is analyzed by gas chromatography (manufactured by SHIMADZU Corporation, trade name: GC2010Plus). (vi) Analyze the cellulose in the same manner as (ii) to (v), except that the cellulose to be measured is changed to 5 mg, 10 mg, or 15 mg of the etherification agent used to modify it, and create a calibration curve for the etherification agent. (vii) The substituents contained in the cellulose to be measured are quantified based on the prepared calibration curve and the analysis results of the cellulose to be measured. The analytical conditions are as follows:

[0113] Column: Agilent Technologies, product name: DB-5 (12 m, 0.2 mm x 0.33 μm) Column temperature: 30°C (10 min hold) → 10°C / min → 300°C (10 min hold) Injector temperature: 300℃ Detector temperature: 300℃ Injection volume: 1 μL

[0114] Next, the molar substitution (MS) is calculated from the introduced mass of the obtained substituent using the following mathematical formula (1) or (2). Formula (1): When only one type of substituent is introduced MS=(W / Mw) / ((100-W) / 162.14) W: Mass of substituents introduced into modified cellulose fiber (mass%) Mw: Molecular weight of the introduced etherification agent (g / mol)

[0115] Formula (2): When two types of substituents are introduced MS1=(W1 / Mw1) / ((100-W1-W2) / 162.14) MS2=(W2 / Mw2) / ((100-W1-W2) / 162.14) MS1: Molar substitution of the first substituent MS2: Molar substitution of the second type of substituent W1: Mass of the first type of substituent introduced into the modified cellulose fiber (mass%) W2: Mass of the second type of substituent introduced into the modified cellulose fiber (mass%) Mw1: Molecular weight of the first etherification agent introduced (g / mol) Mw2: Molecular weight of the second etherification agent introduced (g / mol)

[0116] [Cellulose fiber (equivalent amount) in modified cellulose fiber] The cellulose amount (equivalent amount) in a modified cellulose fiber is the amount of cellulose in the modified cellulose fiber excluding the modifying group. In the modified cellulose fiber of the present invention, the formula weight of the modifying group may be considerably larger (for example, than the molecular weight of glucose). Therefore, in this specification, when it is appropriate to explain the difference in formula weight of the modifying group without considering the difference, the amount of cellulose constituting the modified cellulose fiber (equivalent amount) is expressed rather than the amount of modified cellulose fiber. The cellulose fiber (equivalent amount) in the modified cellulose fiber is measured by the following method.

[0117] (1) When one type of "modifying compound" is added The amount of cellulose fiber (equivalent amount) is calculated by the following formula E. <Formula E> Amount of cellulose fiber (equivalent amount) (g) = mass of modified cellulose fiber (g) / [1 + molecular weight of modifying compound (g / mol) × average bond amount of modifying group (mmol / g) × 0.001] (2) When two or more types of "modifying compounds" are added The amount of cellulose fiber (equivalent amount) is calculated taking into consideration the molar ratio of each compound (that is, the molar ratio when the total molar amount of the compounds added is taken as 1).

[0118] In addition, when the bonding mode between the cellulose fiber and the modifying compound is an ionic bond, in the above formula, the "molecular weight of the modifying compound" refers to the "molecular weight of the entire modifying compound including the copolymer portion" when the modifying compound is a primary amine, secondary amine, or tertiary amine, and refers to "(molecular weight of the entire modifying compound including the copolymer portion) - (molecular weight of the anionic component)" when the compound having a modifying group is a quaternary ammonium compound or a phosphonium compound. On the other hand, when the bonding mode between the cellulose fiber and the modifying compound is an amide bond, in the above formula, if the modifying compound is a primary amine or a secondary amine, the "molecular weight of the modifying compound" is "(the molecular weight of the entire compound having the modifying group, including the copolymer portion) - 18".

[0119] [Confirmation of crystalline structure in various cellulose fibers] The crystalline structure of various cellulose fibers such as modified cellulose fibers is confirmed by measurement under the following conditions using an X-ray diffractometer (MiniFlexII, manufactured by Rigaku Corporation). The measurement conditions were as follows: X-ray source: Cu / Kα-radiation, tube voltage: 30 kV, tube current: 15 mA, measurement range: diffraction angle 2θ = 5 to 45°, X-ray scan speed: 10° / min. The measurement sample was a cellulose fiber to be measured, with an area of ​​320 mm. 2 The cellulose is compressed into a pellet with a thickness of 1 mm. The degree of crystallinity of the cellulose type I crystal structure is calculated from the obtained X-ray diffraction intensity using the following formula C.

[0120] <Formula C> Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] x 100 [In the formula, I 22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, I 18.5 indicates the diffraction intensity of the amorphous portion (diffraction angle 2θ=18.5°).

[0121] On the other hand, if the crystallinity obtained by the above formula C is 35% or less, in order to improve calculation accuracy, it is preferable to calculate based on the following formula D, in accordance with the description on pages 199-200 of the "Wood Science Experiment Manual" (edited by the Japan Wood Research Society; published in April 2000). Therefore, when the crystallinity obtained by the above formula C is 35% or less, the value calculated based on the following formula D can be used as the crystallinity.

[0122] <Formula D> Cellulose type I crystallinity (%) = [Ac / (Ac+Aa)] x 100 (In the formula, Ac is the sum of the peak areas of the lattice planes (002 plane) (diffraction angle 2θ=22.6°), (011 plane) (diffraction angle 2θ=15.1°), and (0-11 plane) (diffraction angle 2θ=16.2°) in X-ray diffraction, and Aa is the peak area of ​​the amorphous portion (diffraction angle 2θ=18.5°). Each peak area is determined by fitting the obtained X-ray diffraction chart with a Gaussian function.)

[0123] Preparation Example 1 (Preparation of Anion-Modified Cellulose Fiber) Bleached coniferous kraft pulp (Fletcher Challenge Canada, trade name "Machenzie", CSF 650 ml) was used as the natural cellulose fiber. A commercially available TEMPO (Aldrich, free radical, 98% by mass) was used. A commercially available sodium hypochlorite (Fujifilm Wako Pure Chemical Industries, Ltd.) was used. A commercially available sodium bromide (Fujifilm Wako Pure Chemical Industries, Ltd.) was used.

[0124] First, 100 g of bleached softwood kraft pulp fiber was thoroughly stirred with 9900 g of deionized water. Then, 1.25 g of TEMPO, 12.5 g of sodium bromide, and 28.4 g of 5% by mass sodium hypochlorite were added in this order per 10 g of pulp. Using a pH stud, 0.5 M sodium hydroxide was added dropwise to maintain the pH at 10.5. After 120 minutes (20°C), the sodium hydroxide addition was stopped to obtain oxidized pulp. The resulting oxidized pulp was thoroughly washed with deionized water and then dehydrated. The anionic groups in the resulting anion-modified cellulose fiber were carboxyl groups, and the carboxyl group content was 1.3 mmol / g. The average fiber diameter and average fiber length of the oxidized cellulose fiber were 41 μm and 1058 μm, respectively.

[0125] Preparation Example 2 (Preparation of Short Anion-Modified Cellulose Fiber) A vial equipped with a magnetic stirrer and a stirring bar was charged with 7.2 g (bone dry mass) of the oxidized cellulose fibers obtained in Preparation Example 1, and deionized water was added until the mass of the treatment solution reached 360 g. The resulting mixture was stirred at 95°C for 24 hours and then dehydrated to obtain shortened anion-modified cellulose fibers. The anionic groups in the resulting anion-modified cellulose fibers were carboxyl groups, and the carboxyl group content was 1.3 mmol / g. The shortened cellulose fibers had an average fiber diameter of 41 μm and an average fiber length of 133 μm.

[0126] Example 1 A beaker equipped with a magnetic stirrer and a stirring bar was charged with 0.16 g (bone-dry mass) of the shortened anion-modified cellulose fibers obtained in Preparation Example 2. Subsequently, 0.41 g of EOPO amine (Huntsman, USA, trade name: Jeffamine M-2005) was charged and dissolved in 40 g of acetone. The resulting mixture was stirred at room temperature (25°C) for 1 hour to obtain modified cellulose fibers in which EOPO amine was bonded to the anion-modified cellulose fibers. Subsequently, 15 g of polyol (Fujifilm Wako Pure Chemical Industries, Ltd., count: polypropylene glycol, molecular weight 2000) was added, and the mixture was stirred for another 1 hour at 25°C. The mixture was subjected to a dispersion treatment five times at 150 MPa using a high-pressure homogenizer (Yoshida Kikai Kogyo Co., Ltd., Nanovaita L-ES). The solvent was removed from the resulting dispersion to obtain a polyol composition containing modified cellulose fibers and polypropylene glycol. The modified cellulose fibers in the polyol composition had an average fiber diameter of 4 nm, an average fiber length of 160 nm, an average aspect ratio of 40, an average bonding amount of modifying groups of 1.27 mmol / g, and a cellulose type I crystal structure.

[0127] Example 2 A polyol composition was obtained in the same manner as in Example 1, except that 0.20 g of EOPO amine (manufactured by Huntsman, USA, trade name: Jeffamine M-2005) and 0.01 g of octylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added as the amines. The average bond amount of the modifying group was 0.67 mmol / g.

[0128] Example 3 A beaker equipped with a magnetic stirrer and a stirring bar was charged with 3.12 g (bone-dry mass) of the shortened anion-modified cellulose fibers obtained in Preparation Example 2. Next, 8.01 g of EOPO amine (Huntsman, USA, trade name: Jeffamine M-2005), 0.71 g of the condensing agent 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM), and 0.13 g of N-methylformaldehyde (NMM) were added and dissolved in 85 g of DMF. The reaction solution was reacted at room temperature (25°C) for 14 hours. After the reaction was completed, the mixture was filtered and washed with deionized water to remove the DMT-MM salt. Then, the mixture was washed with acetone and solvent-exchanged to obtain modified cellulose fibers in which the EOPO amine was linked to the anion-modified cellulose fibers via amide bonds. Next, 0.96 g of modified cellulose fibers with EOPO amines linked via amide bonds (bone-dry mass) and 15 g of polyol (Fujifilm Wako Pure Chemical Industries, Ltd., count: polypropylene glycol, molecular weight 2000) were added and stirred for an additional 1 hour at 25°C. Using a high-pressure homogenizer (Yoshida Kikai Kogyo Co., Ltd., Nanovaita L-ES), the mixture was subjected to dispersion treatment five times at 150 MPa. The solvent was removed from the resulting dispersion to obtain a polyol composition containing modified cellulose fibers and polypropylene glycol. The average bond amount of the modifying group was 0.98 mmol / g.

[0129] Comparative Example 1 A polyol composition was obtained in the same manner as in Example 1, except that EOPO amine was not added.

[0130] Comparative Example 2 A polyol composition was obtained in the same manner as in Example 1, except that the anion-modified cellulose obtained in Preparation Example 1 was used instead of the anion-modified cellulose obtained in Preparation Example 2. The average fiber diameter of the modified cellulose fibers in the polyol composition was 4 nm, and the average fiber length was 800 nm.

[0131] Test example 1 (Transparency evaluation test) The polyol compositions obtained in each of the Examples and Comparative Examples were used to measure the light transmittance of the dispersions and evaluate their transparency as follows: The light transmittance measurements were carried out at room temperature and normal pressure. Specifically, 3 mL of the polyol composition was placed in a quartz cell with an optical path length of 10 mm, 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 Corporation). The medium used to prepare each dispersion was used as a blank (i.e., light transmittance 100%), and the light transmittance (%) was calculated from the absorbance of each dispersion.

[0132] [Table 1]

[0133] Table 1 shows that the polyol compositions of Examples 1 to 3, which contain modified cellulose fibers with an average fiber length of 500 nm or less, all had superior dispersibility and transparency compared to Comparative Example 1, which contains unmodified cellulose fibers, and Comparative Example 2, which has a large average aspect ratio and average fiber length. [Industrial Applicability]

[0134] The polyol composition of the present invention can be suitably used for producing polyurethane resin compositions and polyester resins.

Claims

1. A polyol composition containing one or more polyols selected from the group consisting of ester-based polyols, ether-based polyols, polymer polyols, and Mannich polyols, and modified cellulose fibers, wherein the modified cellulose fibers have cellulose type I crystals, an average fiber length of 500 nm or less, an average aspect ratio of less than 100, and are one or more types selected from the group consisting of the following modified cellulose fibers (A): Modified cellulose fiber (A): A modified cellulose fiber obtained by bonding one or more modifying groups selected from the group consisting of hydrocarbon groups having 3 to 18 carbon atoms and groups containing a copolymer structure in which ethylene oxide and propylene oxide are polymerized randomly or in a block form to the carboxy group of a cellulose fiber containing a carboxy group.

2. The polyol composition according to claim 1, wherein the average aspect ratio of the modified cellulose fiber is 35 or more and less than 100.

3. The polyol composition according to claim 1 or 2, which is a polyol composition for producing a polyester resin composition or a polyurethane resin composition.

4. A method for producing the polyol composition according to any one of claims 1 to 3, comprising a step of micronizing modified cellulose fibers having an average fiber length of more than 500 nm in a polyol, wherein the modified cellulose fibers subjected to the micronization step are one or more types selected from the group consisting of the following modified cellulose fibers (A): Modified cellulose fiber (A): A modified cellulose fiber obtained by bonding one or more modifying groups selected from the group consisting of hydrocarbon groups having 3 to 18 carbon atoms and groups containing a copolymer structure in which ethylene oxide and propylene oxide are polymerized randomly or in a block form to the carboxy group of a cellulose fiber containing a carboxy group.

5. A polymerization product of the polyol composition according to any one of claims 1 to 3.

6. The polymerization product of the polyol composition according to claim 5, which is a polyester resin composition or a polyurethane resin composition.

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