Thickening composition

Abstract

To provide a thickening composition whose viscosity can be greatly increased by an increase in temperature.SOLUTION: This thickening composition is obtained by formulating an anion-modified cellulose fiber, a tertiary amine and a compound having ≥ 160 °C boiling point at 1 atm and liquid at 25 °C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thickening composition. [Background technology]

[0002] In recent years, it has been reported that materials containing fine cellulose fibers can be used to improve various mechanical properties, increase viscosity to improve paint application properties, and improve dispersion stability of compounds. Patent document 1 reports that in a non-aqueous liquid containing anion-modified cellulose fibers modified with primary and secondary amines, the decrease in viscosity due to temperature increase is suppressed, and the processability at high temperatures is improved by maintaining the viscosity. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-001634 Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, there are fields such as optical film manufacturing, coating, precision adhesion, optical fiber manufacturing, and stereolithography, where it is required to maintain or increase the viscosity of the liquid composition to be applied even at high temperatures. Therefore, if it is desired to significantly increase the viscosity at high temperatures, it is necessary to significantly increase the amount of anion-modified cellulose fibers blended, which in turn increases the viscosity at around room temperature, leading to deterioration in handleability.

[0005] Accordingly, the present invention is directed to providing thickened compositions that can exhibit a large increase in viscosity with increasing temperature. [Means for solving the problem]

[0006] That is, the present invention relates to the following [1] to

[12] . [1] A thickening composition comprising the following components (A), (B), and (C): Component (A): Anion-modified cellulose fiber Component (B): a tertiary amine, and Component (C): A compound that has a boiling point of 160°C or higher at 1 atmosphere and is liquid at 25°C [2] The thickening composition according to [1], which is a thickening composition for use at temperatures of 50°C or higher. [3] The thickening composition according to [1] or [2], wherein the total amount of the components (A), (B) and (C) in the thickening composition is 90 mass% or more. [4] The thickening composition according to any one of [1] to [3], wherein the blending amount of the component (B) is 1 part by mass or more and 5,000 parts by mass or less per 100 parts by mass of the component (A). [5] The thickening composition according to any one of [1] to [4], wherein the amount of component (A) blended is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of component (C). [6] The thickening composition according to any one of [1] to [5], wherein the blending amount of the component (A) in the thickening composition is 0.1% by mass or more and 10% by mass or less. [7] The thickening composition according to any one of the above [1] to [6], wherein the molecular weight of the component (B) is 50 or more and 10,000 or less. [8] The thickening composition according to any one of [1] to [7], wherein the amount of the component (C) blended is 50% by mass or more of the amount blended in the thickening composition. [9] A method for producing a laminate, comprising the step of applying a thickening composition comprising the above-mentioned components (A), (B), and (C) onto a substrate at 50°C or higher.

[10] The method for producing a thickening composition according to the above [9], wherein the thickening composition is the thickening composition according to any one of the above [1] to [8].

[11] A method for thickening a composition, comprising a step of heating a thickening composition obtained by blending the above-mentioned components (A), (B), and (C).

[12] The thickening method according to the above

[11] , wherein the thickening composition is the thickening composition according to any one of the above [1] to [8]. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a thickening composition that can greatly increase its viscosity with an increase in temperature. DETAILED DESCRIPTION OF THE INVENTION

[0008] The inventors of the present invention have investigated various cellulose derivative materials and manufacturing conditions, and have found that the use of a tertiary amine as a modifier for anion-modified cellulose fibers increases the viscosity of a non-aqueous liquid containing anion-modified cellulose fibers with increasing temperature. This significantly increases the viscosity of the liquid at high temperatures, achieving both room temperature handleability and high-temperature processability.

[0009] <Thickening composition> The thickening composition of the present invention comprises the following components (A), (B) and (C). Component (A): Anion-modified cellulose fiber Component (B): a tertiary amine, and Component (C): A compound that has a boiling point of 160°C or higher at 1 atmosphere and is liquid at 25°C

[0010] The thickening composition of the present invention is preferably a composition for use at temperatures of 50° C. or higher. From the viewpoint of exerting a high thickening effect, it is preferably used at 50° C. or higher, more preferably 80° C. or higher. On the other hand, from the viewpoint of the stability of the thickening composition, it is preferably used at 200° C. or lower, more preferably 150° C. or lower.

[0011] The mechanism by which the thickening action of the thickening composition of the present invention occurs is unclear, but is believed to be as follows. It is believed that the anion-modified cellulose fibers in the composition form ionic bonds with the amine, thereby allowing the anion-modified cellulose fibers to be dispersed without agglomerating. However, when the amine is a tertiary amine, the ionic bond with the anion-modified cellulose fibers is weaker than in the case of primary or secondary amines due to significant steric hindrance around the amino group, and it is believed that the tertiary amine is more likely to dissociate from the anion-modified cellulose fibers as the temperature increases. Therefore, it is believed that as the temperature increases, the tertiary amine dissociates from the anion-modified cellulose fibers, causing the well-dispersed anion-modified cellulose fibers to aggregate, resulting in thickening.

[0012] [Component (A)] Component (A) in the present invention is anionically modified cellulose fiber. Anion-modified cellulose fibers are cellulose fibers having anionic groups, such as one or more groups selected from the group consisting of carboxyl groups, (phosphite) groups, and sulfonic acid groups, in the molecule. From the viewpoints of availability and improving the viscosity of thickening compositions with increasing temperature, anion-modified cellulose fibers having carboxyl groups as anionic groups (referred to as "oxidized cellulose fibers") are preferred, and anion-modified cellulose fibers in which the hydroxymethyl groups at the C6 position of the glucose units constituting the cellulose fibers have been selectively converted to carboxyl groups (referred to as "TEMPO-oxidized cellulose fibers") are more preferred. The counter ions of the anionic groups are preferably protons, sodium ions, potassium ions, etc., and more preferably protons. The introduction of anionic groups into cellulose fibers can be achieved, for example, by the methods described herein.

[0013] The anionic group content in component (A) is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, even more preferably 0.6 mmol / g or more, even more preferably 0.7 mmol / g or more, and even more preferably 0.8 mmol / g or more, from the viewpoint of introducing a stable component (B) and enhancing dispersibility through the introduction of component (B). Furthermore, from the viewpoint of improving handleability, it is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, even more preferably 2 mmol / g or less, and even more preferably 1.9 mmol / g or less. The term "anionic group content" refers to the total amount of anionic groups in the glucose constituting the cellulose fiber, and is specifically measured by the method described in the Examples below.

[0014] From the viewpoint of improving the viscosity of the thickening composition, the average fiber diameter of the anion-modified cellulose fiber is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 15 μm or more, while from the same viewpoint, it is preferably 300 μm or less, more preferably 100 μm or less, and even more preferably 60 μm or less.

[0015] The average fiber length of the anionically modified cellulose fiber is preferably 700 μm or more, more preferably 900 μm or more, and even more preferably 1,000 μm or more, from the viewpoints of improving the viscosity of the thickening composition due to an increase in temperature and of availability and economy, while from the same viewpoints, it is preferably 10,000 μm or less, more preferably 5,000 μm or less, even more preferably 3,000 μm or less, and even more preferably 2,000 μm or less. The average fiber diameter and average fiber length of the anion-modified cellulose fibers can be measured according to the method described in the Examples below.

[0016] The anionically modified cellulose fibers may be those that have been subjected to a micronization treatment to have nanometer-sized fibers, and such anionically modified cellulose fibers are also referred to as micronized anionically modified cellulose fibers. The average fiber diameter of the anion-modified finely divided cellulose fibers is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 3 nm or more from the viewpoints of handleability, availability, and cost; and is preferably 300 nm or less, more preferably 200 nm or less, even more preferably 100 nm or less, even more preferably 50 nm or less, and even more preferably 10 nm or less from the viewpoints of improving handleability and dispersibility. The average fiber length of the anion-modified finely divided cellulose fibers is preferably 10 nm or more, more preferably 30 nm or more, even more preferably 50 nm or more, and even more preferably 100 nm or more from the viewpoint of improving dispersibility of the anion-modified finely divided cellulose fibers; and is preferably 1,000 nm or less, more preferably 500 nm or less, even more preferably 300 nm or less, and even more preferably 200 nm or less from the viewpoints of improving dischargeability and dispersibility of the anion-modified finely divided cellulose fibers. The average fiber diameter and average fiber length of the anion-modified finely divided cellulose fibers are determined by the method described in the Examples below.

[0017] The average aspect ratio of the anion-modified cellulose fiber and the refined anion-modified cellulose fiber is, from the viewpoint of improving the dispersibility of the refined anion-modified cellulose fiber, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more, and, from the viewpoint of improving the dispersibility of the refined anion-modified cellulose fiber, is preferably 300 or less, more preferably 200 or less, even more preferably 100 or less, even more preferably 60 or less, and even more preferably 50 or less. The average aspect ratio of the anion-modified cellulose fiber and the refined anion-modified cellulose fiber is determined by the method described in the examples below.

[0018] The anion-modified cellulose fibers preferably have a cellulose type I crystal structure from the viewpoint of enhancing dispersibility. The crystallinity of the anion-modified cellulose fibers is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more from the viewpoint of enhancing dispersibility. Furthermore, from the viewpoint of raw material availability, it is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less. In this specification, the crystallinity of various cellulose fibers refers to the cellulose type I crystallinity calculated from the diffraction intensity value by X-ray diffraction, and can be measured according to the method described in the Examples below. Cellulose type I refers to the crystalline form of native cellulose, and cellulose type I crystallinity refers to the proportion of crystalline regions in the entire cellulose fiber. The presence or absence of the cellulose type I crystal structure can be determined by the presence of a peak at 2θ = 22.6° in X-ray diffraction measurement.

[0019] [Component (B)] Component (B) in the present invention is a tertiary amine.

[0020] The molecular weight of component (B) is preferably 50 or more, more preferably 100 or more, and even more preferably 200 or more, from the viewpoint of dispersibility in various media such as polymerizable compounds and organic solvents, and is preferably 50,000 or less, more preferably 20,000 or less, even more preferably 10,000 or less, and even more preferably 8,000 or less, from the viewpoint of various mechanical properties of the material. When component (B) is a component having a molecular weight distribution, the number average molecular weight of component (B) is preferably 50 or more, more preferably 1,000 or more, from the viewpoint of dispersibility in various media such as organic solvents and thickening compositions, and is preferably 50,000 or less, more preferably 20,000 or less, even more preferably 10,000 or less, and even more preferably 8,000 or less, from the viewpoint of various mechanical properties of the material.

[0021] As component (B), a tertiary monoamine or a tertiary polyamine is preferred, and a tertiary monoamine or a tertiary diamine is more preferred. The tertiary monoamine includes a tertiary amine represented by the following formula (A1). R 1 R 2 R 3 N (A1) [In the formula, R 1 , R 2 and R 3 are monovalent hydrocarbon groups or functional groups represented by the following formula (B1), and may be the same or different from each other. -(AO) p -H (B1) (In the formula, AO represents a divalent alkyleneoxy group, and p represents a number of 1 to 100 indicating the average number of moles of alkylene oxide added (wherein the p AOs may be the same or different). Preferred AOs include an ethylene oxide group and a propylene oxide group.)

[0022] R in formula (A1) 1 , R 2 and R 3 From the viewpoint of improving the viscosity of the thickening composition with an increase in temperature, the group is preferably a monovalent hydrocarbon group having 1 to 22 carbon atoms or a functional group represented by the formula (B1), more preferably a monovalent linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms or a functional group represented by the formula (B1), and even more preferably a monovalent linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms or a functional group represented by the formula (B1). In addition, from the viewpoint of improving the viscosity of the thickened composition due to an increase in temperature, it is preferable that R 1 , R 2 and R 3 At least one of the groups is a monovalent hydrocarbon group.

[0023] Examples of the tertiary amine represented by formula (A1) include trihexylamine, trioctylamine, tridecylamine, tridodecylamine, dihexylmonomethylamine, dioctylmonomethylamine, didecylmonomethylamine, didodecylmonomethylamine, dimethyloctylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethyloctadecylamine, dimethyloleylamine, dimethylbehenylamine, dimethylcoconutamine, and polyether-type tertiary amines represented by the following formula (A2).

[0024] [ka]

[0025] (In the formula, R is a monovalent hydrocarbon group, AO is a divalent alkylene oxide group, and n and m are each numbers indicating the average number of moles of AO added. Preferred examples of R include alkyl groups having 10 to 20 carbon atoms. Preferred examples of AO include an ethylene oxide group and a propylene oxide group. Preferred values ​​of n and m are numbers from 1 to 100. The sum of n and m (n+m) is preferably 1 or more, more preferably 10 or more, and even more preferably 20 or more, and is preferably 200 or less, more preferably 100 or less, and even more preferably 50 or less.)

[0026] Preferred polyether-type tertiary amines include polyoxyethylene octylamine, polyoxyethylene laurylamine, polyoxyethylene stearylamine, and polyoxyethylene oleylamine.

[0027] The tertiary diamine includes a tertiary amine represented by the following formula (A3). R 4 R 5 NM-NR 6 R 7 (A3) [In the formula, R 4 , R 5 , R 6 and R 7are monovalent hydrocarbon groups or functional groups represented by the formula (B1) above, and may be the same or different from each other. M is an alkylene group having 1 to 10 carbon atoms.

[0028] R in formula (A3) 4 , R 5 , R 6 and R 7 From the viewpoint of improving the viscosity of the thickening composition with an increase in temperature, the aryl group is preferably a monovalent hydrocarbon group having 1 to 22 carbon atoms or a functional group represented by the formula (B1) above, and more preferably a monovalent linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, or a functional group represented by the formula (B1) above.

[0029] Examples of the tertiary amine represented by formula (A3) include polyoxyethylene stearyl propylene diamine, polyoxyethylene lauryl propylene diamine, polyoxyethylene coconut propylene diamine, polyoxyethylene beef tallow propylene diamine, and polyoxyethylene-polyoxypropylene block polymers of ethylene diamine.

[0030] Tertiary polyamines include polymeric compounds having dialkylamino groups in the side chains, such as polymers of 2-(dimethylamino)ethyl methacrylate.

[0031] As component (B), a tertiary amine may be used alone or in combination of two or more kinds.

[0032] In the present invention, amines other than component (B) (e.g., primary amines, secondary amines, quaternary ammonium salts, etc.) may be present in the composition. However, from the viewpoint of increasing the viscosity of the thickening composition with increasing temperature, it is preferable that the amount of such amines is small, and it is even more preferable that such amines are not present.

[0033] Component (B) may further have a substituent, such as an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, or a hexyloxy group; Examples include alkoxy-carbonyl groups having 1 to 6 carbon atoms in the alkoxy group, such as t-butoxycarbonyl, pentyloxycarbonyl, and isopentyloxycarbonyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; acyl groups having 1 to 6 carbon atoms, such as acetyl and propionyl groups; aralkyl groups; aralkyloxy groups; alkylamino groups having 1 to 6 carbon atoms; dialkylamino groups having 1 to 6 carbon atoms in the alkyl group; and hydroxy groups.

[0034] [Component (C)] Component (C) in the present invention is a compound that has a boiling point of 160°C or higher at 1 atmosphere and is liquid at 25°C. As component (C), any compound having such properties can be used without any particular limitation, and examples thereof include the following polymerizable compounds and solvents.

[0035] Examples of polymerizable compounds include compounds having an α,β-unsaturated carbonyl group, such as (meth)acrylic acid monomers; (meth)acrylamide monomers; (meth)acrylonitrile monomers; styrene monomers; and vinyl monomers such as vinyl acetate, N-vinylcarbazole, N-vinylcaprolactam, ethyl vinyl ether, and butyl vinyl ether. Among these, (meth)acrylic acid monomers are preferred from the viewpoint of dispersibility of modified cellulose fibers. Note that "(meth)acrylic" includes both acrylic and methacrylic. For example, "(meth)acrylic acid" includes both acrylic acid and methacrylic acid. "(meth)acrylonitrile" includes both acrylonitrile and methacrylonitrile.

[0036] Examples of monofunctional (meth)acrylic acid monomers include 4-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, cyclodecyl (meth)acrylate, Examples of the acrylate include tetrafluorooctyl (meth)acrylate, cyclodecylmethyl (meth)acrylate, tricyclodecyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (poly)ethylene glycol monomethyl ether (meth)acrylate, (poly)ethylene glycol monolauryl ether (meth)acrylate, (poly)propylene glycol monomethyl ether (meth)acrylate, octafluorooctyl (meth)acrylate, tetrafluoroethyl (meth)acrylate, (meth)acrylate of an ethylene oxide adduct of nonylphenol, (meth)acryloyloxyethyl phosphate, and (meth)acryloyloxyphthalic acid.

[0037] Examples of polyfunctional (meth)acrylic acid monomers include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, tripropylene di(meth)acrylate, tripropylene glycol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, poly(propylene glycol) di(meth)acrylate, tri(propylene glycol) di(meth)acrylate, propoxylated neopentyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, bisphenol A di(meth)acrylate, and bisphenol Examples of the ethylene oxide adduct include di(meth)acrylate, trimethylolpropane propoxylate tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol propoxylate tri(meth)acrylate, pentaerythritol propoxylate tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0038] Specific examples of the solvent include alcohol solvents such as glycerin; ketone solvents such as methylhexyl ketone, diisobutyl ketone, diacetone alcohol, and isophorone; Ether solvents such as 2-butoxyethanol; ester solvents such as polycarboxylic acid esters (e.g., phthalates, succinates, adipates, etc.) and fatty acid esters of aliphatic polyols such as glycerin; highly polar solvents such as dimethyl sulfoxide (DMSO), ethylene carbonate, N,N-dimethylacetamide (DMAc), and N-methylpyrrolidone; halogenated solvents such as o-dichlorobenzene; non-aromatic hydrocarbon solvents such as petroleum ether, liquid paraffin, squalane, and squalene; aromatic hydrocarbon solvents such as trimethylbenzene; nitrile solvents such as benzonitrile; t-butyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol, 1-methoxy-2-propanol, dipropylene glycol monomethyl ether, methyl dipropylene glycol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, (mono, di, tri, poly) ethylene glycol, Glycol ether-based solvents such as ethylene glycol methyl ether, ethylene glycol monophenyl ether, (mono-, di-, tri-, poly)ethylene glycol dimethyl (ethyl) ether, (mono-, di-, tri-, poly)ethylene glycol monobutyl ether, polyethylene glycol, methoxypolyethylene glycol, polyoxyethylene bisphenol A, and polyoxypropylene bisphenol A (glycol ether-based solvents include the following glycol ether (ester)-based solvents: glycol ether ester-based solvents (e.g., butyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, methoxybutyl acetate, methyl methoxybutyl acetate, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether propionate, dimethyl carbonate, etc.).

[0039] [Method for producing thickening composition] The thickening composition can be produced, for example, by introducing anionic groups into raw cellulose fibers to produce component (A) (step 1), and then mixing component (A), component (B), and component (C) (step 2).

[0040] (Process 1) Raw material: cellulose fiber As the cellulose fiber that is the raw material for component (A), natural cellulose is preferred from an environmental perspective, and examples thereof include wood pulp such as softwood pulp and hardwood pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as straw pulp and bagasse pulp; and bacterial cellulose, and these can be used alone or in combination of two or more.

[0041] The average fiber diameter of the raw cellulose fibers is not particularly limited, but from the viewpoints of handleability and cost, it is preferably 5 μm or more, more preferably 7 μm or more, and from the same viewpoints, it is preferably 500 μm or less, more preferably 300 μm or less. The average fiber diameter of the raw cellulose fibers is determined by the method described in the Examples below.

[0042] The average fiber length of the raw cellulose fibers is not particularly limited, but from the viewpoints of availability and cost, it is preferably 5 μm or more, more preferably 25 μm or more, and from the same viewpoints, it is preferably 5,000 μm or less, more preferably 3,000 μm or less. The average fiber length of the raw cellulose fibers can be determined by the method described in the Examples below.

[0043] Method for introducing anionic groups Examples of the anionic group include a carboxy group, a (phosphorous) group, and a sulfonic acid group. Methods for introducing carboxy groups as anionic groups into cellulose fibers include, for example, a method of oxidizing hydroxy groups of the cellulose fibers to convert them into carboxy groups, and a method of reacting the hydroxy groups of the cellulose fibers with at least one selected from the group consisting of compounds having carboxy groups, acid anhydrides of compounds having carboxy groups, and derivatives thereof.

[0044] Examples of methods for oxidizing the hydroxy groups of cellulose fibers include those described in JP 2015-143336 and JP 2015-143337, which involve reacting raw cellulose fibers with an oxidizing agent such as sodium hypochlorite and a bromide such as sodium bromide using 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst. By oxidizing cellulose fibers using TEMPO as a catalyst, the hydroxymethyl group at the C6 position of the glucose in the cellulose fiber structural unit is selectively converted to a carboxy group, resulting in the production of TEMPO-oxidized cellulose fibers, as described below.

[0045] Methods for introducing (phosphorous) groups as anionic groups into cellulose fibers include a method of mixing a powder or aqueous solution of (phosphorous) acid or a (phosphorous) acid derivative with dry or wet cellulose fibers, a method of adding an aqueous solution of (phosphorous) acid or a (phosphorous) acid derivative to a dispersion of cellulose fibers, etc. When these methods are employed, dehydration treatment, heat treatment, etc. are generally carried out after mixing or adding a powder or aqueous solution of (phosphorous) acid or a (phosphorous) acid derivative.

[0046] An example of a method for introducing phosphate groups as anionic groups into cellulose fibers is the method described in Japanese Patent No. 7196051, in which raw cellulose fibers are impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea to convert the hydroxy groups of the cellulose fibers into phosphate esters. As a method for introducing sulfonic acid groups as anionic groups into cellulose fibers, a method of adding sulfuric acid to cellulose fibers and heating the fibers can be given.

[0047] (Process 2) From the viewpoint of increasing the viscosity of the thickening composition with an increase in temperature, it is preferable to mix components (A), (B), and (C) by first mixing components (A) and (B) and then adding and mixing component (C). The amounts and ratios of the components used in step 2 are as described below.

[0048] After completion of step 2, post-treatment may be carried out as appropriate to remove unreacted compounds, etc. Examples of post-treatment methods that can be used include filtration, centrifugation, dialysis, etc.

[0049] Water or an organic solvent is used as a medium in step 2 above. From the viewpoint of enhancing dispersibility, the melting point of the organic solvent is preferably below 0° C., more preferably −50° C. or lower, and even more preferably −60° C. or lower. From the same viewpoint, on the other hand, those with a melting point of −100° C. or higher are preferred. From the viewpoint of enhancing dispersibility, the boiling point of the organic solvent is preferably 150° C. or lower, more preferably 100° C. or lower, and even more preferably 90° C. or lower. On the other hand, from the viewpoint of reducing the amount of organic solvent used, those with a boiling point of 70° C. or higher are preferred.

[0050] Specific examples of organic solvents include alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as methanol, ethanol, propanol, and 1-methoxy-2-propanol (PGME); ketones having 3 to 6 carbon atoms, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; formic acid esters of alkyl groups having 1 to 4 carbon atoms, such as methyl formate and ethyl formate; acetate esters of alkyl groups having 1 to 4 carbon atoms, such as methyl acetate and ethyl acetate; propionic acid esters of alkyl groups having 1 to 4 carbon atoms, such as methyl propionate and ethyl propionate; butyric acid esters of alkyl groups having 1 to 4 carbon atoms, such as methyl butyrate and ethyl butyrate; P-based glycol ethers such as 2-methoxy-1-methylethyl acetate (PGMEA); saturated or unsaturated hydrocarbons having 1 to 6 carbon atoms; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride and chloroform; lower alkyl ethers having 2 to 5 carbon atoms; and polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and dimethyl sulfoxide. These may be used alone or in combination of two or more.

[0051] (Fine processing) By micronizing the raw cellulose fibers or anion-modified cellulose fibers, it is possible to reduce the micrometer-scale cellulose fibers to the nanometer-scale, which is preferable because reducing the average fiber diameter to nanometer size improves dispersibility. In the present invention, from the viewpoint of dispersibility of the anion-modified cellulose fibers after micronization, it is preferable to carry out a micronization step after mixing the components (A) and (B).

[0052] The micronization treatment can be carried out by a known micronization treatment method. For example, to obtain fibers having an average fiber diameter on the nanometer scale, a treatment method using a grinder such as a mass colloider or a treatment method using a high-pressure homogenizer in a medium may be carried out.

[0053] The medium may be one or more of the above organic solvents. The amount of the medium used may be any amount that can disperse the anion-modified cellulose fibers, and is preferably at least 1 time by mass, more preferably at least 2 times by mass, and preferably not more than 500 times by mass, more preferably not more than 200 times by mass, relative to the anion-modified cellulose fibers.

[0054] As the apparatus used in the micronization treatment, in addition to a high-pressure homogenizer, known dispersers are also suitably used. For example, a disintegrator, a beater, a low-pressure homogenizer, a grinder, a mass colloider, a cutter mill, a ball mill, a jet mill, a single-screw extruder, a twin-screw extruder, an ultrasonic agitator, a household juicer mixer, etc. can be used. In addition, the solids concentration of the anion-modified cellulose fiber in the micronization treatment is preferably 50 mass% or less.

[0055] (Short fiber processing) In the present invention, various cellulose fibers, i.e., raw cellulose fibers, anion-modified cellulose fibers, and finely divided cellulose fibers, may be subjected to a fiber shortening treatment. By subjecting such fiber shortening treatment to such a treatment, dispersibility can be improved. The fiber shortening treatment can be carried out by subjecting the target cellulose fibers to one or more treatment methods 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.

[0056] [Composition of thickening composition] The amount of component (A) in the thickening composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of increasing the viscosity of the thickening composition as the temperature increases, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 4% by mass or less, from the viewpoint of handleability during production.

[0057] The amount of amino groups in component (B) relative to component (A) in the thickening composition is preferably 0.01 mmol / g or more, more preferably 0.1 mmol / g or more, and even more preferably 0.5 mmol / g or more, from the viewpoint of improving the viscosity of the thickening composition, and from the same viewpoint, is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and even more preferably 1 mmol / g or less.

[0058] In the thickening composition, the molar percentage of amino groups in component (B) relative to the anionic groups in component (A) is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more, from the viewpoint of improving the viscosity of the thickening composition; and from the same viewpoint, it is preferably 100 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less.

[0059] The blending ratio of component (A) to component (B) in the thickening composition is, from the viewpoint of improving the viscosity of the thickening composition, preferably 1 part by mass or more of component (B) per 100 parts by mass of component (A), more preferably 10 parts by mass or more, and even more preferably 30 parts by mass or more; and from the same viewpoint, preferably 5,000 parts by mass or less of component (B) per 100 parts by mass of component (A), more preferably 1,000 parts by mass or less, even more preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less.

[0060] The amount of component (B) in the thickening composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of increasing the viscosity of the thickening composition as the temperature increases, 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 handling during production.

[0061] Regarding the blending ratio of component (A) to component (C) in the thickening composition, from the viewpoint of increasing the viscosity of the thickening composition with increasing temperature, the blending amount of component (A) per 100 parts by mass of component (C) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more; from the same viewpoint, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

[0062] The amount of component (C) in the thickening composition 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 increasing the viscosity of the thickening composition as the temperature increases, and from the same viewpoint, it is preferably less than 100% by mass, more preferably 98% by mass or less, and even more preferably 97% by mass or less.

[0063] The total amount of component (A), component (B) and component (C) in the thickening composition is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more, from the viewpoint of improving the viscosity of the thickening composition.

[0064] The viscosity of the thickening composition at 100°C is preferably 400 Pa·s or more, more preferably 450 Pa·s or more, and even more preferably 500 Pa·s or more, from the viewpoint of suppressing dripping during application, and is preferably 100,000 Pa·s or less, more preferably 10,000 Pa·s or less, and even more preferably 5,000 Pa·s or less, from the viewpoint of ease of handling. The viscosity of the thickening composition at 100°C can be determined by the measurement method described in the Examples below.

[0065] The composition of the present invention may contain other components in addition to those mentioned above, such as plasticizers, 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, within the range that does not impair the effects of the present invention. Similarly, polymeric materials and resin compositions other than the above-mentioned polymerizable compounds may also be added within the range that does not impair the effects of the present invention.

[0066] The thickening composition of the present invention thickens preferably when heated to 50°C or higher, and is therefore suitable for applications where suppression of dripping when used at 50°C or higher is required, such as various coating agents, adhesives, and paints.

[0067] <Method of manufacturing laminate> The method for producing a laminate of the present invention includes a step of applying the thickening composition of the present invention, which is obtained by blending the above-mentioned components (A), (B), and (C), to a substrate at 50°C or higher. The laminate is formed from a substrate, such as a film, an electronic component such as a printed circuit board, or an optical component such as a lens or an optical fiber, and a coating layer. The laminate can be produced by applying a thickening composition to the substrate and curing the thickening composition as needed. Furthermore, a laminate is formed, for example, from a plurality of films as substrates and, if necessary, an adhesive layer, and the thickening composition of the present invention functions as an adhesive when applied between the films, or functions as a coating agent when applied to the surface of the films. When producing a laminate, it may be produced at temperatures of 50°C or higher depending on the properties of the substrate, etc. The viscosity-increasing composition of the present invention does not decrease but rather increases in viscosity even at temperatures of 50°C or higher, which can suppress dripping and is extremely advantageous for maintaining the shape of the laminate. Furthermore, when component (C) is a polymerizable compound, the method for producing a laminate of the present invention preferably includes a step of curing the thickening composition.

[0068] <Method of thickening the composition> The thickening composition of the present invention, which is obtained by blending the above-mentioned components (A), (B) and (C), is thickened by heating. Therefore, there is provided a method for thickening a composition, which comprises a step of heating the thickening composition of the present invention, which is obtained by blending the above-mentioned components (A), (B), and (C), and preferably the step of heating the thickening composition is a step of raising the temperature of the thickening composition to 50°C or higher. [Example]

[0069] The present invention will be specifically described below with reference to examples. Note that the following examples are merely illustrative of the present invention and are not intended to limit the present invention in any way. Note that "normal pressure" refers to a state in which no pressure or pressure is applied, and "normal temperature" refers to 25°C.

[0070] [Average fiber diameter and average fiber length of cellulose fibers and (shortened) anion-modified cellulose fibers] Deionized water was added to the cellulose fibers to be measured or a suspension containing the cellulose fibers to be measured to prepare a dispersion containing 0.01% by mass of cellulose fibers. The dispersion was 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, analytical sample volume: 1 mL, and sampling: 15%. The cellulose fibers were then approximated as a rectangle, with the length of the minor axis being the fiber diameter and the length of the major axis being the fiber length. Each value was measured for 100 cellulose fibers, and the average was calculated.

[0071] [Average fiber diameter and average fiber length of cellulose fibers after micronization treatment] Deionized water or N,N-dimethylformamide (DMF) was added to the cellulose fibers to be measured or a dispersion containing the cellulose fibers to prepare a dispersion with a content of 0.0001% by mass. The dispersion was dropped onto mica and dried to prepare an observation sample. The fiber height (height difference between the presence and absence of fibers) of the cellulose fibers in the observation sample was measured using an atomic force microscope (AFM) (Digital Instruments, Nanoscope II Tapping mode AFM; Nanosensors, Point Probe (NCH) probe). In this case, 100 cellulose fibers were extracted from the microscopic image in which the cellulose fibers were visible, and the average fiber diameter was calculated from their fiber height. The average fiber length was calculated from the distance in the fiber direction.

[0072] [Confirmation of crystalline structure in various cellulose fibers] The crystal structures of various celluloses, such as cellulose raw materials and anion-modified cellulose fibers, were confirmed by measurement using a diffractometer (Rigaku Corporation, MiniFlex II) under the following conditions. Measurement pellet preparation conditions: A pressure of 10 to 20 MPa was applied to the target cellulose using a tablet press to form pellets with an area of ​​320 mm 2 × 1 mm thick smooth pellets were prepared. X-ray diffraction analysis conditions: step angle 0.01°, scan speed 10° / min, measurement range: diffraction angle 2θ = 5 to 40° X-ray source: Cu / Kα-radiation, tube voltage: 15kv, tube current: 30mA Peak splitting conditions: After removing background noise, the peaks were fitted with a Gaussian function so that the error between 2θ = 13 and 23° was within 5%. The crystalline structures of various celluloses were confirmed by measurements using the above-mentioned diffractometer under the above-mentioned conditions. The crystallinity of the cellulose type I crystal structure was calculated based on the following formula (A) using the area of ​​the X-ray diffraction peak obtained by the above-mentioned peak division. Cellulose type I crystallinity (%) = [I cr / (I cr +I am )]×100 (A) [In the formula, I cr is the area of ​​the diffraction peak of the lattice plane (002 plane) (diffraction angle 2θ = 22-23°) in X-ray diffraction, I am indicates the area of ​​the diffraction peak of the amorphous part (diffraction angle 2θ = 18.5°).

[0073] [Anionic Group Content of Anion-Modified Cellulose Fiber] A dry mass of 0.5 g of the cellulose fiber to be measured was placed in a beaker and mixed with deionized water or a 2:1 (volume ratio) methanol / deionized water mixture to a total volume of 55 mL. 5 mL of 0.01 M aqueous sodium chloride solution was added to prepare a dispersion. The dispersion was stirred until the cellulose fiber to be measured was fully dispersed. 0.1 M hydrochloric acid was added to the dispersion to adjust the pH to 2.5-3. Using an automatic titrator (DKK-TOA Corporation, AUT-701), 0.05 M aqueous sodium hydroxide solution was added dropwise to the dispersion with a waiting time of 60 seconds, and the electrical conductivity and pH were measured every minute. Measurements were continued until the pH reached approximately 11, and a conductivity curve was obtained. The sodium hydroxide titration volume was determined from this conductivity curve, and the anionic group content of the cellulose fiber to be measured was 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)]

[0074] [Content of each ingredient] The content of each component other than water was calculated from the blend amount of each component. The water content in the dispersion or suspension was measured by Karl Fischer titration using a CA-200 manufactured by Mitsubishi Analytech Co., Ltd. The solid content of various cellulose fibers was calculated by measuring the moisture content of the sample using an infrared moisture meter (Shimadzu Corporation, MOC-120H) and calculating the difference from 100% by mass. The moisture content was measured every 30 seconds at a constant temperature of 150°C for 1 g of sample, and the value displayed when the mass loss over 30 seconds was 0.1% or less was used.

[0075] [Measurement of electrical conductivity of filtrate] The electrical conductivity of the filtrate was measured using a compact electrical conductivity meter (LAQUAtwin EC-33B, manufactured by Horiba, Ltd.).

[0076] [Measurement of the average degree of polymerization of anion-modified cellulose fibers] The average degree of polymerization of the anion-modified cellulose fiber was measured as follows. (1) Preparation of the measurement solution 0.06 g of the anion-modified cellulose fiber to be measured (dry mass) was weighed out and placed in a 50 mL beaker. Water was added to adjust the solids concentration to 1% by mass. 0.006 g of sodium borohydride was added and stirred at room temperature for 2 hours. 18 g of acetone was then added. The mixture was then centrifuged at 10°C, 10,000 G, and 1 minute using a high-speed refrigerated centrifuge (Koki Holdings Co., Ltd., CR21G III) to remove the supernatant. 18 g of ethanol was added to the residue, and the same process of centrifuging and removing the supernatant was repeated three times to obtain a precipitate that was washed with ethanol. The resulting precipitate was vacuum-dried at 40°C for 12 hours to obtain reduced pulp in which the aldehyde groups in the anion-modified cellulose fiber had been reduced. 0.06 g of the resulting reduced pulp was added to 15 mL of deionized water and 15 mL of 1 M copper ethylenediamine solution and stirred at room temperature for 1 hour to obtain the measurement solution.

[0077] (2) Measurement of average degree of polymerization The measurement solution obtained in (1) above was placed in an Ubbelohde viscometer and allowed to stand in a thermostatic bath (20±0.1)°C for 1 hour. The flow time of the solution (t (seconds)) and the flow time of the copper ethylenediamine solution without cellulose (t0 (seconds)) were then measured, and the intrinsic viscosity [η] (dL / g) was calculated using the following formula:

[0078] [η]=[(t / t0-1) / c] / [1+0.28×(t / t0-1)] (c: cellulose concentration (g / dL))

[0079] From the obtained intrinsic viscosity [η], the average degree of polymerization (DP) of the anion-modified cellulose fiber was calculated using the following formula: v ) was calculated.

[0080] [η] = 0.094 × 162 × DP v 0.67

[0081] [Component (A)] Anion-modified cellulose fiber 1 or anion-modified cellulose fiber 2 having the physical property values ​​shown in Table 1 was used as the raw material for component (A).

[0082] [Table 1]

[0083] Anion-modified cellulose fiber 1 can be prepared, for example, by the following TEMPO oxidation treatment and alkaline hydrolysis treatment. Anion-modified cellulose fiber 2 can be prepared, for example, by the following TEMPO oxidation treatment.

[0084] [TEMPO oxidation treatment] 20 g of bleached softwood kraft pulp fiber (as the raw natural cellulose fiber) and 1980 g of deionized water were weighed into a 2-L polypropylene beaker equipped with a mechanical stirrer and impeller, and the mixture was stirred at 25°C and 100 rpm for 30 minutes. Next, 0.26 g of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO), 2.6 g of sodium bromide, and 70.0 g of a 10.5% by weight aqueous solution of sodium hypochlorite were added to the 20 g of pulp fiber, in that order. pH stat titration was then performed using an automatic titrator, and 0.5 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10.5. The reaction was continued at 25°C for 120 minutes, stirring at 100 rpm. While stirring, 0.01 M hydrochloric acid was added to adjust the pH of the suspension to 2. The solids were then filtered off by suction filtration. The solids are dispersed in deionized water and filtered off by suction. This procedure is repeated until the electrical conductivity of the filtrate reaches 200 μS / cm or less. The resulting solids are then dehydrated to obtain anion-modified cellulose fibers 2.

[0085] [Alkaline hydrolysis treatment] A suspension of anion-modified cellulose fiber 2 (solid content: 14.5 g) obtained by the TEMPO oxidation treatment was diluted with 100 g of deionized water, to which 0.14 g of 35% hydrogen peroxide solution (1 part by mass of hydrogen peroxide per 100 parts by mass of the solid content of the raw cellulose fiber) was added, and the pH was adjusted to 12 with 1 M aqueous sodium hydroxide. This was then subjected to alkaline hydrolysis at 80°C for 2 hours (solid content concentration of the anion-modified cellulose fiber suspension: 4.3% by mass). After cooling the suspension to room temperature, 0.01 M hydrochloric acid was added to adjust the pH of the suspension to 2. The solid content of the suspension was separated by suction filtration. This process of dispersing the solid content in deionized water and separating the solid content by suction filtration was repeated until the electrical conductivity of the filtrate reached 200 μS / cm or less. The resulting solid content was then dehydrated to obtain anion-modified cellulose fiber 1.

[0086] [Preparation of short anion-modified cellulose fibers] Anion-modified cellulose fibers 1 and 2 having the physical properties shown in Table 1 were each subjected to a fiber shortening treatment to obtain shortened anion-modified cellulose fibers 1 or 2 having the physical properties shown in Table 2. Such shortened anion-modified cellulose fibers were designated as component (A). Specifically, a cake of anion-modified cellulose fiber was collected, and deionized water was added until the solids concentration reached 5% by mass. The resulting mixture was stirred at the temperature and for the time shown in Table 2 to obtain an aqueous suspension of shortened anion-modified cellulose fiber. The resulting suspension was centrifuged at 25°C, 10,000 G, and for 1 minute using a high-speed refrigerated centrifuge (Koki Holdings Co., Ltd., CR21G III) to obtain a precipitate of shortened anion-modified cellulose fiber having the physical properties shown in Table 2.

[0087] [Table 2]

[0088] [Preparation of Dispersion] A dispersion liquid was prepared using the shortened anion-modified cellulose fibers as follows. Shortened anion-modified cellulose fibers were placed in a beaker, and component (B) and an organic solvent (methyl ethyl ketone (MEK) or ethanol) were added so that the blending amounts of each component other than water were as shown in Table 3. The mixture was then stirred at room temperature for 2 hours to obtain a suspension. Note that the water in Table 3 is the water that was mixed in with shortened anion-modified cellulose fibers 1 or 2, respectively. The resulting suspension was subjected to a micronization treatment 10 times at 150 MPa using a high-pressure homogenizer (NanoVeita L-ES, manufactured by Yoshida Kikai Kogyo Co., Ltd.), to obtain dispersions 1 to 3 shown in Table 3.

[0089] [Table 3]

[0090] Examples 1 to 3 [Preparation of Thickening Composition] Using the above dispersion, a thickening composition was prepared as follows. To the resulting dispersion, component (C) was added so as to obtain the composition shown in Table 4, and the mixture was stirred at room temperature for 1 hour. The dispersion was then transferred to a recovery flask, and the volatile components, the organic solvent and water, were distilled off using a rotary evaporator (manufactured by BUCHI) under the conditions shown below, to obtain the composition shown in Table 4.

[0091] Evaporator conditions Water bath temperature: 40℃ Degree of decompression (absolute pressure): 2 to 5 kPa Judgment that distillation is complete: Judgment was made when there was a mass loss equivalent to the blended amounts of water and organic solvent.

[0092] Comparative Example 1 10 g of bleached softwood kraft pulp (Hinton, manufactured by West Fraser Corporation) was thoroughly stirred with 990 g of deionized water, and then 0.13 g of TEMPO, 1.3 g of sodium bromide, and 27 g of a 10.5% by mass aqueous solution of sodium hypochlorite were added to the pulp in this order. The resulting mixture was stirred for 120 minutes while maintaining the pH at 10.5 by adding 0.5 M aqueous sodium hydroxide dropwise using an automatic titrator (AUT-701, manufactured by DKK-TOA Corporation) at 20°C. The stirring and addition of the aqueous sodium hydroxide solution were then stopped, yielding a suspension.

[0093] The resulting suspension was adjusted to a pH of 2 with 0.01 M hydrochloric acid, and the solids were then filtered off under suction. The solids were dispersed in deionized water and filtered off under suction. This procedure was repeated until the electrical conductivity of the filtrate reached 200 μS / cm or less, as measured using a conductivity meter (HORIBA, Ltd., LAQUAtwin EC-33B). The solids were then filtered off under suction to obtain a cake of anion-modified cellulose fibers.

[0094] The anion-modified cellulose fiber cake was collected, and deionized water was added until the solids concentration reached 5% by mass to obtain a suspension. The resulting suspension was stirred at 95°C for 3 hours to obtain an aqueous suspension of shortened anion-modified cellulose fiber. The resulting suspension was centrifuged using a high-speed refrigerated centrifuge (Koki Holdings Co., Ltd., CR21G III) at 25°C, 10,000G, and for 1 minute to obtain shortened anion-modified cellulose fiber as a precipitate.

[0095] The shortened anion-modified cellulose fiber dispersion was washed three times with 1-methoxy-2-propanol (PGME) to perform solvent substitution. 7.0 g of the resulting gel (solids concentration: 14.6% by mass) was placed in a beaker and mixed with 3.1 g of methoxypoly(oxyethylene / oxypropylene)-2-propylamine (MPAA) (equivalent to 1 equivalent of the carboxyl groups of the anion-modified cellulose fiber). 33.0 g of PGME was added to the mixture to make a total of 43 g. This solution was stirred with a mechanical stirrer for 1 hour at room temperature and then subjected to five passes at 150 MPa in a high-pressure homogenizer (Yoshida Kikai Co., Ltd., Nanovaita L-ES) to obtain the composition listed in Table 4. The anion-modified cellulose fibers contained in the composition of Comparative Example 1 had an average fiber diameter of 4.0 nm and an average fiber length of 600 nm.

[0096] [Evaluation method] The viscosity of each composition was measured and the effect was evaluated as follows. [Viscosity measurement] The viscosity of the composition was measured using a rheometer (MARS40, manufactured by Thermo Fisher Scientific) and a measuring jig ((top) P20 / Ti, (bottom) TMP20) according to the following program. Step 1: 0°C, shear rate 0 s -1 From 100s -1 The shear rate was increased at a constant rate over 30 seconds until Step 2: 0°C, shear rate 100 s -1 From 0s -1 The shear rate was reduced at a constant rate over 30 seconds until Step 3: The temperature was increased from 0 to 150 °C at a rate of 10 °C / min, while the shear rate was 0.1 s -1 The viscosity was measured. In step 3, shear viscosity readings were taken at 0° C., 25° C., 80° C. and 100° C. The results are shown in Table 4.

[0097] [Table 4]

[0098] In Table 4, in the items "Total amount of component (A), component (B), and component (C)," "Amount of component (B) per 100 parts by mass of component (A)," and "Amount of component (A) per 100 parts by mass of component (C)," for convenience, the amount of component (B) corresponds to the amount of component (B) and the amount of non-component (B), and the amount of component (C) corresponds to the amount of component (C) and the amount of non-component (C).

[0099] Table 4 shows that the viscosity of the composition increased significantly when heated (Examples 1 to 3). On the other hand, the viscosity of the composition containing the primary amine MPAA instead of component (B) decreased (Comparative Example 1). Generally, the viscosity decreases as the temperature increases, so it was surprising that the viscosity of the composition of the present invention increased upon heating. By utilizing this property, it is possible to provide a composition that is easy to handle due to its low viscosity before application, and that can be prevented from dripping by heating after application.

[0100] In the above examples, the following reagents and compounds were used without any special purification. [Component (B) and non-component (B) for comparison] Trihexylamine: Tri-n-hexylamine (Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 269.52, tertiary amine) EOPO-added ethylenediamine: ADEKA (registered trademark) Pluronic TR-913R (manufactured by ADEKA Corporation, number average molecular weight 5,900, tertiary amine) Polyoxyethylene stearylamine: Brownon S-230 (manufactured by Aoki Oil & Fat Industries, number average molecular weight 1,590, tertiary amine) MPAA: Methoxypoly(oxyethylene / oxypropylene)-2-propylamine (Huntsman, Jeffamine M2070, number average molecular weight 2,000, primary amine) [Component (C) and non-component (C) for comparison] Squalane: Squalane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point is 350°C at 1 atmosphere and is liquid at 25°C) PEG200: Polyethylene glycol 200 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point: 250°C at 1 atmosphere; liquid at 25°C) 4HBA: 4-hydroxybutyl acrylate (Tokyo Chemical Industry Co., Ltd.; boiling point: 230°C at 1 atmosphere; liquid at 25°C) PGME: 1-methoxy-2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point is 120°C at 1 atmosphere and is liquid at 25°C) [Solvents, etc.] Ethanol: Ethanol (Fujifilm Wako Pure Chemical Industries, Ltd.) Methyl ethyl ketone: Methyl ethyl ketone (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0101] Composition example 1 [Preparation of Anion-Modified Cellulose Fiber 3] Even if anion-modified cellulose fiber into which a phosphate group has been introduced is used instead of anion-modified cellulose fiber 1 and 2 into which a carboxy group has been introduced by TEMPO oxidation treatment, a thickening composition similar to that of Examples 1 to 3 can be obtained. Such anion-modified cellulose fiber 3 can be prepared by the following phosphorylation treatment.

[0102] [Phosphorylation] 100 parts by weight of solids of bleached softwood kraft pulp fiber (the raw natural cellulose fiber) is impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea, and then pressed to obtain 56 parts by weight of ammonium dihydrogen phosphate and 150 parts by weight of urea, yielding chemical-impregnated fiber. The chemical-impregnated fiber is dried in a dryer at 105°C to evaporate the water, and the evaporated fiber is heated for 4 minutes in a blower dryer set at 140°C. To 100 parts by mass of the obtained fiber, 10,000 parts by mass of deionized water is added, and the mixture is stirred to disperse the fiber, and then the solids are filtered off by suction filtration. To 100 parts by mass of the solids in the filtered cake, 10,000 parts by mass of deionized water is added, and the mixture is stirred to disperse the fiber, and then the solids are filtered off by suction filtration. To the resulting cake, 10,000 parts by mass of deionized water is added, and a 1N aqueous solution of sodium hydroxide is added dropwise with stirring to obtain a slurry with a pH of 12 to 13. Next, 0.01M hydrochloric acid is added to the mixture with stirring to adjust the pH of the suspension to 2. The solid content is then filtered off by suction filtration. The cake is dispersed in deionized water and filtered off by suction. This procedure is repeated until the electrical conductivity of the filtrate reaches 200 μS / cm or less. The resulting solid is then dehydrated to obtain anion-modified cellulose fibers 3. [Industrial Applicability]

[0103] The composition of the present invention is expected to be prevented from dripping because it thickens when heated, and is therefore suitable for use in various coating agents, adhesives, and paints.

Claims

1. A thickening composition comprising the following components (A), (B) and (C): Component (A): Anion-modified cellulose fiber Component (B): a tertiary amine, and Component (C): A compound that has a boiling point of 160°C or higher at 1 atmosphere and is liquid at 25°C

2. 10. The thickened composition of claim 1, wherein the thickened composition is for use at temperatures above 50°C.

3. The thickening composition according to claim 1, wherein the total amount of the components (A), (B) and (C) in the thickening composition is 90 mass% or more.

4. 2. The thickening composition according to claim 1, wherein the blending amount of component (B) is 1 part by mass or more and 5,000 parts by mass or less per 100 parts by mass of component (A).

5. 2. The thickening composition according to claim 1, wherein the blending amount of the component (A) is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the component (C).

6. The thickening composition according to claim 1, wherein the amount of component (A) in the thickening composition is 0.1% by mass or more and 10% by mass or less.

7. 2. The thickening composition according to claim 1, wherein the molecular weight of component (B) is 50 or more and 10,000 or less.

8. The thickening composition according to claim 1, wherein the amount of component (C) is 50% by mass or more of the amount of the thickening composition.

9. A method for producing a laminate, comprising the step of applying a thickening composition comprising the following components (A), (B), and (C) onto a substrate at 50°C or higher: Component (A): Anion-modified cellulose fiber Component (B): a tertiary amine, and Component (C): A compound that has a boiling point of 160°C or higher at 1 atmosphere and is liquid at 25°C

10. A method for thickening a composition, comprising a step of heating a thickening composition comprising the following components (A), (B), and (C): Component (A): Anion-modified cellulose fiber Component (B): a tertiary amine, and Component (C): A compound that has a boiling point of 160°C or higher at 1 atmosphere and is liquid at 25°C

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