Composition and cured product

Abstract

To provide a composition that can form a cured product with high gloss and high flexibility. [Solution] A composition comprising fine fibrous cellulose and a radical polymerizable compound, characterized in that the fine fibrous cellulose satisfies the following conditions (A), (B), (C), and (D), and also satisfies one or more of the following conditions (E) and (F). (A) The number-average fiber diameter is between 1 nm and 100 nm. (B) The number-average fiber length is between 50 nm and 1000 nm. (C) Having anionic functional groups (D) The above anionic functional group is bonded to an organonium ion. (E) Having an acyl group (F) The above organic onium ion is a quaternary ammonium compound.

Description

[Technical Field]

[0001] This invention relates to a composition and its cured product. [Background technology]

[0002] Due to the need to replace petroleum resources and growing environmental awareness, attention is being drawn to the application of renewable natural fibers. Among natural fibers, cellulose fibers, particularly wood-derived cellulose fibers (pulp), are widely used mainly in paper products. In addition, fine fibrous cellulose with a fiber diameter of 1000 nm or less is also known, and various applications for fine fibrous cellulose are being investigated. Patent document 1 describes an ionizing radiation-curable resin composition containing an acrylic material and quaternary alkylamine-modified cellulose nanofibers. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2015-200815 [Overview of the initiative] [Problems that the invention aims to solve]

[0004] Challenges of using fine fibrous cellulose include the low gloss and poor flexibility of the cured product when incorporated into resins. Therefore, the problem that the present invention aims to solve is to provide a composition that can form a cured product with high gloss and high flexibility. [Means for solving the problem]

[0005] As a result of diligent research, the inventors have found that a composition containing a specific fine fibrous cellulose and a radically polymerizable compound can solve the above problem. That is, the present invention relates to a composition comprising fine fibrous cellulose and a radical polymerizable compound, The composition is characterized in that the fine fibrous cellulose satisfies the following conditions (A), (B), (C) and (D) and satisfies one or more of the following conditions (E) and (F). (A) The number-average fiber diameter is 1 nm or more and 100 nm or less. (B) The number-average fiber length is 50 nm or more and 1000 nm or less. (C) It has an anionic functional group. (D) An organic onium ion is bonded to the anionic functional group. (E) It has an acyl group. (F) The organic onium ion is a quaternary ammonium represented by the following general formula (1).

[0006]

Chemical formula

[0007] (In the general formula (1), R 1 ~R 4 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an arene group, an allyl group or a group having an alkylene oxide structure, and R 1 ~R 4 at least one of which is a group having an alkylene oxide structure.)

Advantages of the invention

[0008] According to the present invention, it is possible to provide a composition capable of forming a cured product having a high gloss and high flexural resistance, that is, a cured product excellent in gloss and flexural resistance.

Embodiments for carrying out the invention

[0009] A. Composition The composition of the present disclosure comprises fine fibrous cellulose and a radical polymerizable compound, wherein the fine fibrous cellulose satisfies the following conditions (A), (B), (C), and (D), and also satisfies one or more of the following conditions (E) and (F). From the viewpoint of obtaining a cured product with superior gloss and flexibility, it is preferable that the composition of the present disclosure satisfies all of the following conditions (A), (B), (C), (D), (E), and (F). (A) The number-average fiber diameter is between 1 nm and 100 nm. (B) The number-average fiber length is between 50 nm and 1000 nm. (C) Having anionic functional groups (D) The above anionic functional group is bonded to an organonium ion. (E) Having an acyl group (F) The above organic onium ion is a quaternary ammonium represented by the following general formula (1).

[0010] [ka]

[0011] In general formula (1), R 1 ~R 4 Each of these is independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an arene group, an allyl group, or a group having an alkylene oxide structure, R 1 ~R 4 At least one of them is a group having an alkylene oxide structure.

[0012] (1) Microfiber Cellulose The composition of this disclosure contains fine fibrous cellulose.

[0013] (1-1) Number-average fiber diameter and number-average fiber length In this disclosure, the number-average fiber diameter of the fine fibrous cellulose is 1 nm or more and 100 nm or less. In this disclosure, the number-average fiber diameter of the fine fibrous cellulose is preferably 1 nm or more and 50 nm or less, more preferably 2 nm or more and 30 nm or less, and even more preferably 2 nm or more and 10 nm or less. This is because by setting the fiber diameter within the above range, the composition of this disclosure can form a cured product with excellent gloss and flexibility. In this disclosure, the number-average fiber length of the fine fibrous cellulose is 50 nm to 1000 nm. Preferably, the number-average fiber length of the fine fibrous cellulose is 100 nm to 500 nm, and more preferably 250 nm to 500 nm. This is because the composition of this disclosure can form a cured product with superior gloss and flexibility. In this disclosure, the number-average fiber diameter and number-average fiber length can be determined by the following method: After preparing an aqueous dispersion of fine fibrous cellulose with a solid content of 0.01 to 0.05% by mass, the aqueous dispersion is dropped onto a mica plate and dried. The dispersion is then observed with a scanning probe microscope (SPM), and the diameter and length of at least 50 fibers are measured. The average values ​​of these measurements are taken as the number-average fiber diameter and number-average fiber length.

[0014] (1-2) Anionic functional groups The microfiber cellulose in this disclosure has an anionic functional group. In this disclosure, the anionic functional group is not particularly limited, but examples include a carboxyl group, a phosphate group, a sulfate group, etc. As the anionic functional group, a carboxyl group is preferred because it is easy to introduce the anionic functional group into the microfiber cellulose.

[0015] There are no particular limitations on the method for introducing carboxyl groups into microfiber cellulose, but examples include (i) a method of converting hydroxyl groups of microfiber cellulose into carboxyl groups by oxidation, and (ii) a method of reacting the hydroxyl groups of microfiber cellulose with at least one selected from the group consisting of compounds having carboxyl groups, acid anhydrides of compounds having carboxyl groups, and derivatives thereof.

[0016] The method for oxidizing the hydroxyl groups of fine fibrous cellulose is not particularly limited, but examples include using an N-oxyl compound as an oxidation catalyst and applying an oxidizing agent.

[0017] The compounds having the carboxyl group mentioned above are not particularly limited, but examples include halogenated acetic acid. Examples of halogenated acetic acid include chloroacetic acid, bromoacetic acid, and iodoacetic acid.

[0018] The acid anhydrides of the compounds having the carboxyl group described above are not particularly limited, but include, for example, cyclic acid anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride, and cyclic acid anhydrides of compounds having the carboxyl group in which at least some of the hydrogen atoms are substituted with substituents (e.g., alkyl groups, phenyl groups, etc.). The derivatives of the acid anhydrides of compounds having the carboxyl group are not particularly limited, but include, for example, dimethyl maleic anhydride, diethyl maleic anhydride, and diphenyl maleic anhydride.

[0019] The amount of anionic functional groups per gram of fine fibrous cellulose (amount of anionic functional groups [mmol] / amount of fine fibrous cellulose [g]) is not particularly limited, but from the viewpoint of excellent dispersibility of fine fibrous cellulose when reacted with organo-onium ions, it is preferably 1.0 mmol / g to 3.0 mmol / g, and more preferably 1.0 mmol / g to 2.0 mmol / g. By setting it within the above range, the composition of this disclosure can produce a cured product with better gloss and flexibility. The amount of anionic functional groups can be measured by neutralization titration using electrical conductivity.

[0020] (1-3) Organic onium ions In the microfibrillar cellulose of the present disclosure, an organic onium ion is bonded to the anionic functional group. Examples of the organic onium ion include ammonium such as primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium, phosphonium, and sulfonium. The microfibrillar cellulose in the present disclosure may have two or more kinds of organic onium ions.

[0021] In the present disclosure, the organic onium ion is preferably selected from the group consisting of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium, and more preferably is quaternary ammonium.

[0022] Examples of the quaternary ammonium include those represented by the following general formula (1), symmetric quaternary ammonium having a symmetric structure such as tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraheptylammonium, tetraoctylammonium; asymmetric quaternary ammonium having an asymmetric structure such as tributylpropylammonium, tributylpentylammonium, tripentylpropylammonium, tripentylbutylammonium, trihexylpropylammonium, trihexylbutylammonium, distearyldimethylammonium, behenyltrimethylammonium, and the like.

[0023]

Chemical formula

[0024] (In general formula (1), R 1 ~R 4 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an arene group, an allyl group, or a group having an alkylene oxide structure, and at least one of R 1 ~R 4 is a group having an alkylene oxide structure.)

[0025] Among quaternary ammonium compounds, from the viewpoint of obtaining a cured product with superior gloss and flexibility, a quaternary ammonium compound with a symmetric structure or a quaternary ammonium compound represented by general formula (1) is preferred, tetraoctylammonium compound or a quaternary ammonium compound represented by general formula (1) is preferred, and a quaternary ammonium compound represented by general formula (1) is more preferred.

[0026] In general formula (1), from the viewpoint of obtaining a cured product with superior gloss and flexibility, R 1 ~R 4 Each of these is independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or an alkylene oxide structure, and R 1 ~R 4 At least one of them is preferably a group having an alkylene oxide structure, R 1 ~R 4 Each of these is independently a group having a linear or branched alkyl or alkylene oxide structure with 1 to 10 carbon atoms, and R 1 ~R 4 At least one of them is more preferably a group having an alkylene oxide structure, R 1 ~R 4 Each of these is independently a group having a linear or branched alkyl or alkylene oxide structure with 1 to 5 carbon atoms, and R 1 ~R 4 At least one of them is more preferably a group having an alkylene oxide structure, R 1 ~R 4 Each of these is independently a group having a linear or branched alkyl or alkylene oxide structure with 1 to 3 carbon atoms, and R 1 ~R 4 Most preferably, at least one of the groups is a group having an alkylene oxide structure.

[0027] In general formula (1), from the viewpoint of obtaining a cured product with superior gloss and flexibility, R 1 ~R 3Each is independently a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and R 4 It is preferable that R is a group having an alkylene oxide structure. 1 ~R 3 Each of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, and R 4 It is more preferable that the group has an alkylene oxide structure, R 1 ~R 3 Each of these is independently a linear or branched alkyl group having 1 to 5 carbon atoms, and R 4 It is more preferably a group having an alkylene oxide structure, R 1 ~R 3 Each of these is independently a linear alkyl group having 1 to 3 carbon atoms, and R 4 It is most preferable that the group has an alkylene oxide structure.

[0028] In this disclosure, the group having an alkylene oxide structure is preferably a group represented by the following general formula (2) from the viewpoint of obtaining a cured product with superior gloss and flexibility.

[0029] [ka]

[0030] (In general formula (2), R 21 (where n is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an arene group, or an allyl group; n is a number between 1 and 100; and * represents a bonding site.)

[0031] In general formula (2), R 21From the viewpoint of obtaining a cured product with superior gloss and flexibility, it is preferable that the group is a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, even more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

[0032] In this disclosure, the group having an alkylene oxide structure is preferably a group represented by the following general formula (2-1) or the following general formula (2-2) from the viewpoint of obtaining a cured product with superior gloss and flexibility.

[0033] [ka]

[0034] (In general formulas (2-1) and (2-2), n represents a number between 1 and 100, and * represents a joining point.)

[0035] In this disclosure, there are no particular limitations on the method for bonding an organic onium ions to an anionic functional group, but examples include a method of mixing a fine fibrous cellulose having an anionic functional group with an organic onium salt in a solvent.

[0036] (1-4) Acyl group The fine fibrous cellulose in this disclosure preferably has an acyl group. In this disclosure, the acyl group is represented by the following general formula (3). RC(=O)- (3) (In general formula (3), R is a monovalent hydrocarbon group having 1 to 20 carbon atoms. The monovalent hydrocarbon group may be linear, branched, or cyclic.)

[0037] The fine fibrous cellulose having acyl groups in this disclosure is obtained by substituting some of the hydroxyl groups of fine fibrous cellulose with acyl groups, wherein the number of carbon atoms in the acyl group is in the range of 1 to 20, preferably in the range of 1 to 10, and more preferably in the range of 1 to 4. This range allows the composition of this disclosure to form a cured product with superior gloss and flexibility. The number of carbon atoms mentioned above refers to the number of carbon atoms in the hydrocarbon group represented by R in general formula (3). For example, the acetyl group has 1 carbon atom, and the propionyl group has 2 carbon atoms.

[0038] There are no particular limitations on the method for introducing acyl groups into fine fibrous cellulose, but examples include reacting at least one selected from the group consisting of linear acid anhydrides and acid halides with the hydroxyl groups of the fine fibrous cellulose. The linear acid anhydride is not particularly limited, but examples include acetic anhydride and propionic anhydride. The acid halide is not particularly limited, but examples include acetyl chloride and propionic acid chloride.

[0039] In this disclosure, acyl groups and anionic functional groups in microfiber cellulose can be introduced simultaneously.

[0040] (1-5) Amount of fine cellulose In the compositions of this disclosure, the content of fine fibrous cellulose is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the radical polymerizable compound. This is because by setting the content within the above range, the compositions of this disclosure can produce cured products with superior gloss and flexibility.

[0041] In the compositions of this disclosure, the amount of the cellulose skeleton portion excluding the modified portion in the fine fibrous cellulose is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 8 parts by mass or less, per 100 parts by mass of the radical polymerizable compound. This is because by setting the amount within the above range, the compositions of this disclosure can produce cured products with superior gloss and flexibility. The modified portion refers to anionic functional groups bonded to the fine fibrous cellulose, organo-onium ions bonded to the anionic functional groups, and, if acyl groups are bonded to the fine fibrous cellulose, the acyl groups.

[0042] (2) Radical polymerizable compounds A radical polymerizable compound is a compound that has a radical polymerizable group and can be polymerized by radical polymerization. Examples of radical polymerizable groups include ethylenically unsaturated double bond groups such as methacrylic groups, acrylic groups, and allyl groups. The radical polymerizable group is preferably a methacrylic group or an acrylic group, and more preferably an acrylic group, i.e., the radical polymerizable compound is an acrylate. By using a radical polymerizable compound in which the radical polymerizable group is a methacrylic group or an acrylic group, the composition of this disclosure has a fast curing rate and excellent workability.

[0043] In one embodiment of the composition of this disclosure, the number of radical polymerizable groups in the radical polymerizable compound can be appropriately set according to the desired adhesion, etc. The number of radical polymerizable groups may be 1 or more per molecule of the radical polymerizable compound, but it is preferable to be between 2 and 50. This is because by setting the number within the above range, the composition of this disclosure can produce a cured product with superior gloss and flexibility.

[0044] As the radical polymerizable compound, either a monofunctional compound having one radical polymerizable group or a polyfunctional compound having two or more radical polymerizable groups can be used.

[0045] Examples of monofunctional compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, and stearyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, polyoxyalkylene-modified (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydro (meth)acrylate. Examples include hydroxyalkyl esters of (meth)acrylates such as hydroxypropyl, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; acrylamides such as acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; NN-dimethyl(meth)acrylamide, NN-diethyl(meth)acrylamide, N-(meth)acryloylmorpholine, and NN-diethylaminoethyl (meth)acrylate; and ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.

[0046] As monofunctional compounds, compounds having a cyclic ether group, such as tetrahydrofurfuryl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether, can also be used. In one embodiment of the composition of this disclosure, the monofunctional compound may consist of only one type, or two or more types may be used in combination.

[0047] Examples of polyfunctional compounds include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, di(acryloxyethyl) isocyanurate, allylated cyclohexyl di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and propionic acid-modified dipentaerythritol. Examples include di(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, bis(acryloxyethyl)hydroxyethyl isocyanurate, ethylene oxide-modified diacrylate, ethylene oxide-modified triacrylate, ε-caprolactone-modified tris(acryloxyethyl) isocyanurate, diglycerin tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. These polyfunctional compounds may consist of only one type, or two or more types may be used in combination.

[0048] The radical polymerizable compound may contain at least one of a compound having a urethane bond and a compound not having a urethane bond (the monofunctional compound and polyfunctional compound described above). In the compositions of this disclosure, the radical polymerizable compound preferably contains a compound having a urethane bond, and more preferably contains both a compound having a urethane bond and a compound not having a urethane bond. This is because such compositions can produce cured products with superior gloss and flexibility.

[0049] Examples of compounds having a urethane bond include urethane (meth)acrylates such as polycarbonate-based urethane (meth)acrylate, polyester-based urethane (meth)acrylate, polyether-based urethane (meth)acrylate, and caprolactone-based urethane (meth)acrylate. These can be obtained by reacting an isocyanate compound, which is obtained by reacting a polyol with a diisocyanate, with a (meth)acrylate monomer having a hydroxyl group.

[0050] Examples of the polyols mentioned above include polycarbonate diols, polyester polyols, polyether polyols, and polycaprolactone polyols.

[0051] Examples of (meth)acrylate monomers having the hydroxyl group mentioned above include hydroxyethyl (meth)acrylate. Note that (meth)acrylate encompasses both acrylate and methacrylate. Similarly, (meth)acrylic also encompasses both acrylic and methacrylic.

[0052] Examples of commercially available compounds containing urethane bonds include Artresin UN-320HA, UN-333, UN-350, UN-352, UN-353, UN-1255, UN-2600, UN-2700, UN-5500, UN-5590, UN-5507, UN-6060PTM, UN-6200, UN-6202, UN-6303, UN-6304, UN-6305, UN-7600, UN-7700, UN-9000PEP, UN-9200A, UN-3320HA, UN-3320HC, UN-3320HS, UN-904, UN-906S, UN-901T, Examples include UN-905, UN-952 (manufactured by Negami Kogyo Co., Ltd.); EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8807, EBECRYL9260, EBECRYL9270 (manufactured by Daicel Ornex Co., Ltd.); U-4HA, U-6HA, U-6LPA, UA-1100H, UA-200PA, UA-4200, UA-122P, UA-53H, NK ester ABE-300, A9300, A-LEN-10, NK ester AMP-10G, A-TMM-3LM-N, A-DPH, A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0053] The compounds that do not have urethane bonds are not particularly limited as long as the desired adhesion properties can be obtained. For example, monofunctional compounds having one radical polymerizable functional group without a urethane bond, or polyfunctional compounds having two or more radical polymerizable functional groups without a urethane bond can be used.

[0054] In the compositions of this disclosure, it is preferable that the compound without a urethane bond contains the above-mentioned monofunctional compound without a urethane bond. This is because such compositions can yield cured products with superior gloss and flexibility.

[0055] In the compositions of this disclosure, the monofunctional compound without a urethane bond is preferably tetrahydrofurfuryl (meth)acrylate or N-(meth)acryloylmorpholine. This is because such compositions can yield cured products with superior gloss and flexibility.

[0056] (3) Others The compositions of this disclosure may further contain, as appropriate, radical polymerization initiators, solvents, stress reducers, antioxidants, flame retardants, leveling agents, and various additives to improve various properties such as compatibility with other resins, stability, and workability. From the viewpoint of obtaining a cured product with superior gloss and flexibility, the composition of this disclosure preferably further contains a radical polymerization initiator.

[0057] (3-1) Radical polymerization initiators The radical polymerization initiator in this disclosure can be any compound that can initiate radical polymerization upon irradiation with energy rays. For example, ketone compounds such as acetophenone compounds, benzyl compounds, and thioxanthone compounds are preferred examples.

[0058] Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, and benzoin isobutyl ether.

[0059] Examples of benzyl compounds include benzyl and anisyl.

[0060] Examples of benzophenone compounds include benzophenone, o-methyl benzoylbenzoate, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0061] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0062] Examples of commercially available radical polymerization initiators include ADEKA Optomer N-1414, N-1717, N-1919, ADEKA Arcles NCI-831, NCI-930 (manufactured by ADEKA Corporation); Omnirad 651, 184, 1173, 2959, 127D, 907, 369, 369E, 369EG, TPO, 819, TPO-L, TP, MBF, 754, 3644 (manufactured by IGM Resins BV); Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF Japan); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (manufactured by Tronly).

[0063] (3-2) Solvent The solvent used may be the same solvent used in the production of the fine fibrous cellulose, or it may be a solvent that has been added separately. The solvents used in this disclosure are not particularly limited, and well-known organic solvents such as ethanol, acetone, N-methyl-2-pyrrolidone, and methyl ethyl ketone can be used.

[0064] B. Cured product The cured products of this disclosure are obtained by curing the compositions of this disclosure described above. The cured products of this disclosure can be molded into any shape and are provided, for example, as thin materials such as films, coatings, and sheets, block-shaped materials such as rectangular parallelepipeds and cubes, and other three-dimensional shapes.

[0065] Next, a method for producing the cured product of this disclosure will be described. The method for producing the cured product of the present disclosure includes a step of curing the composition of the present disclosure by irradiating it with active energy rays. The method for producing the cured product of the present disclosure may also include a step of removing the solvent by drying the composition, if necessary, before the step of irradiating it with active energy rays.

[0066] In this process, the light source for the active energy rays used to cure the composition can be electromagnetic wave energy with wavelengths of 2000 angstroms to 7000 angstroms obtained from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc., or high-energy rays such as electron beams, X-rays, and radiation. Preferably, ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, light-emitting diodes, etc. that emit light with wavelengths of 300 to 450 nm are used.

[0067] The irradiation dose of the active energy rays is not particularly limited and can be appropriately determined depending on the composition of the composition. When irradiating the composition with light of a wavelength of 365 nm, the irradiation dose should be 100 mJ / cm² from the viewpoint of preventing degradation of the components in the composition. 2 ~2000 mJ / cm 2 It is preferable that this be the case.

[0068] C. Others The following aspects are included in this disclosure: [1] A composition comprising fine fibrous cellulose and a radical polymerizable compound, A composition characterized in that the above-mentioned fine fibrous cellulose satisfies the following conditions (A), (B), (C), and (D), and also satisfies one or more of the following conditions (E) and (F). (A) The number-average fiber diameter is between 1 nm and 100 nm. (B) The number-average fiber length is between 50 nm and 1000 nm. (C) Having anionic functional groups (D) The above anionic functional group is bonded to an organonium ion. (E) Having an acyl group (F) The above organic onium ion is a quaternary ammonium represented by the following general formula (1). [ka] (In general formula (1), R 1 ~R 4 Each of these is independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an arene group, an allyl group, or a group having an alkylene oxide structure, R 1 ~R 4 At least one of them is a group having an alkylene oxide structure.

[0069] [2] The composition according to [1], characterized in that the organic onium ion is a quaternary ammonium compound, and the fine fibrous cellulose satisfies condition (E).

[0070] [3] The composition according to [1] or [2], characterized in that the anionic functional group is a carboxyl group.

[0071] [4] The composition according to any one of [1] to [3], characterized in that the fine fibrous cellulose satisfies the conditions (E) and (F).

[0072] [5] The composition according to any one of [1] to [4], further comprising a radical polymerization initiator.

[0073] [6] The composition according to any one of [1] to [5], characterized in that the fine fibrous cellulose is contained in 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the radical polymerizable compound.

[0074] [7] A cured product of any of the compositions described in [1] to [6]. [Examples]

[0075] The present disclosure will be described in further detail below with reference to examples and comparative examples. However, the present disclosure is not limited in any way by the following examples. In the examples, "parts" and "%" refer to mass unless otherwise specified.

[0076] (Manufacturing Example 1) 10 g of cellulose (Nacalai Tesque) was added to 990 g of deionized water, and then 0.16 g of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) and 1 g of sodium bromide were added and dissolved while stirring. 38 mL of 1.33 mol / L sodium hypochlorite aqueous solution was added dropwise, while checking that the pH did not exceed 11. When the pH fell below 10, 0.5 M sodium hydroxide aqueous solution was added dropwise to maintain a pH of 10. When it was no longer necessary to add sodium hydroxide aqueous solution, the reaction was terminated, and 0.1 g of sodium borohydride was added and stirred for 2 hours, after which 1 M hydrochloric acid was added to adjust the pH to 2. After that, the mixture was washed with water by suction filtration to obtain 10.2 g of TEMPO-oxidized cellulose having carboxyl groups as anionic functional groups. The amount of carboxyl groups in the obtained TEMPO-oxidized cellulose was measured by neutralization titration using electrical conductivity and was found to be 1.4 mmol / g.

[0077] (Manufacturing example 2) 4.08 g of TEMPO-oxidized cellulose obtained in Production Example 1 was mixed with acetone and subjected to repeated suction filtration to replace the solvent. Subsequently, 400 g of a dispersion of TEMPO-oxidized cellulose was prepared by adding N-methyl-2-pyrrolidone (NMP) and performing solvent replacement again. The solid content of this dispersion was 1% by mass. 49.2 g of propionic anhydride was added to this and the mixture was reacted at 80°C with stirring for 5 hours. Subsequently, methyl ethyl ketone (MEK) was added and solvent replacement was performed by repeated suction filtration to prepare a MEK dispersion of cellulose having a carboxyl group as an anionic functional group and a propionyl group as an acyl group. The solid content of this dispersion was 1.29% by mass.

[0078] (Manufacturing Example 3) 4.08 g of TEMPO-oxidized cellulose obtained in Production Example 1 was subjected to solvent replacement by adding acetone and repeatedly suction filtration. Subsequently, 400 g of a dispersion of TEMPO-oxidized cellulose was prepared by adding N-methyl-2-pyrrolidone (NMP) and performing solvent replacement. The solid content of this dispersion was 1% by mass. 37.6 g of acetic anhydride was added to this and the mixture was reacted at 80°C with stirring for 5 hours. Subsequently, methyl ethyl ketone (MEK) was added and solvent replacement was performed by repeatedly suction filtration to prepare a MEK dispersion of cellulose having a carboxyl group as an anionic functional group and an acetyl group as an acyl group. The solid content of this dispersion was 1.22% by mass.

[0079] (Manufacturing example 4) 2 g of cellulose (manufactured by Nacalai Tesque) was added to acetone and solvent replacement was performed by repeated suction filtration. Subsequently, N-methyl-2-pyrrolidone (NMP) was added and solvent replacement was performed again to prepare 200 g of a dispersion with a solid content of 1% by mass. 16.8 g of propionic anhydride and 5.8 g of succinic anhydride were added to this dispersion and the mixture was heated to 80°C with stirring and reacted for 5 hours. Then, methyl ethyl ketone (MEK) was added and solvent replacement was performed by repeated suction filtration to prepare a MEK dispersion of cellulose having carboxyl groups as anionic functional groups and propionyl groups as acyl groups. The solid content of this dispersion was 1.43% by mass. The amount of carboxyl groups in the obtained cellulose was measured by neutralization titration using electrical conductivity and was found to be 1.3 mmol / g.

[0080] (Manufacturing example 5) 20 g of the compound represented by the following general formula (3) was dissolved in 20 g of ethanol, and 20 mL of ion exchange resin (Amberlite® IRN78 OH hydroxide foam) was added. After stirring overnight at room temperature, the ion exchange resin was removed by filtration to obtain a 50% ethanol solution of the compound represented by the general formula (4).

[0081] [ka]

[0082] (Manufacturing example 6) 100 g of a MEK dispersion of TEMPO-oxidized cellulose was prepared by adding acetone to 1.02 g of TEMPO-oxidized cellulose obtained in Production Example 1 and repeatedly performing solvent replacement by suction filtration, followed by adding methyl ethyl ketone (MEK) and repeatedly performing solvent replacement by suction filtration. The solid content of this dispersion was 1.02% by mass. 4.4 g of a 50% ethanol solution of the compound represented by general formula (4), prepared in Production Example 5, was added and stirred overnight at room temperature. The resulting liquid was defibrated six times at a pressure of 180 MPa using a wet-type ultra-high-pressure atomizer (product name: NanoVeta C-ES, manufactured by Yoshida Machinery Industry Co., Ltd.) to obtain a dispersion containing fine fibrous cellulose B-1. The solid content of this dispersion was 3.2% by mass. The properties of fine fibrous cellulose B-1 are shown in Table 1.

[0083] (Manufacturing example 7) 100 g of a MEK dispersion of TEMPO-oxidized cellulose was prepared by adding acetone to 1.02 g of TEMPO-oxidized cellulose obtained in Production Example 1 and repeatedly performing solvent replacement by suction filtration, and then adding methyl ethyl ketone (MEK) and repeatedly performing solvent replacement by suction filtration. The solid content of this dispersion was 1.02% by mass. 3.5 g of a 20% methanol solution of tetraoctylammonium hydroxide (Sigma-Aldrich) was added to this and stirred overnight at room temperature. The resulting liquid was defibrated six times at a pressure of 180 MPa using a wet-type ultra-high-pressure atomizer (product name: NanoVeta C-ES, Yoshida Machinery Industry Co., Ltd.) to obtain a dispersion containing fine fibrous cellulose b-1. The solid content of this dispersion was 3.2% by mass. The properties of fine fibrous cellulose b-1 are shown in Table 1.

[0084] (Manufacturing example 8) 100 g of the MEK dispersion of cellulose obtained in Production Example 2 was defibrated six times at a pressure of 180 MPa using a wet-type ultra-high-pressure atomization device (product name: NanoVeta C-ES, manufactured by Yoshida Machinery Industry Co., Ltd.) to obtain a dispersion containing fine fibrous cellulose b-2. The solid content of this dispersion was 1.3% by mass. The properties of fine fibrous cellulose b-2 are shown in Table 1.

[0085] (Manufacturing example 9) 100 g of the MEK dispersion of cellulose obtained in Production Example 2 was mixed with 4.4 g of a 50% ethanol solution of the compound represented by general formula (4), prepared in Production Example 5, and stirred overnight at room temperature. The resulting liquid was defibrated six times at a pressure of 180 MPa using a wet-type ultra-high-pressure atomizer (product name: NanoVeta C-ES, manufactured by Yoshida Machinery Industry Co., Ltd.) to obtain a dispersion containing fine fibrous cellulose B-2. The solid content of the dispersion was 3.5% by mass. The properties of fine fibrous cellulose B-2 are shown in Table 1.

[0086] (Manufacturing example 10) 100 g of the MEK dispersion of cellulose obtained in Production Example 2 was mixed with 3.4 g of a 20% methanol solution of tetraoctylammonium hydroxide (Sigma-Aldrich) and stirred overnight at room temperature. The resulting liquid was defibrated six times at a pressure of 180 MPa using a wet-type ultra-high-pressure atomizer (product name: NanoVeta C-ES, Yoshida Machinery Industry Co., Ltd.) to obtain a dispersion containing fine fibrous cellulose B-3. The solid content of the dispersion was 2.0% by mass. The properties of fine fibrous cellulose B-3 are shown in Table 1.

[0087] (Manufacturing Example 11) To 100 g of the MEK dispersion of cellulose obtained in Production Example 3, 4.4 g of a 50% ethanol solution of the compound represented by general formula (4), prepared in Production Example 5, was added and stirred overnight at room temperature. The resulting liquid was defibrated six times at a pressure of 180 MPa using a wet-type ultra-high-pressure atomizer (product name: NanoVeta C-ES, manufactured by Yoshida Machinery Industry Co., Ltd.) to obtain a dispersion containing fine fibrous cellulose B-4. The solid content of the dispersion was 3.5% by mass. The properties of fine fibrous cellulose B-4 are shown in Table 1.

[0088] (Manufacturing Example 12) 100 g of the MEK dispersion of cellulose obtained in Production Example 3 was mixed with 3.4 g of a 20% methanol solution of tetraoctylammonium hydroxide (Sigma-Aldrich) and stirred overnight at room temperature. The resulting liquid was defibrated six times at a pressure of 180 MPa using a wet-type ultra-high-pressure atomization apparatus (product name: NanoVeta C-ES, Yoshida Machinery Industry Co., Ltd.) to obtain a dispersion containing fine fibrous cellulose B-5. The solid content of the dispersion was 1.9% by mass. The properties of fine fibrous cellulose B-5 are shown in Table 1.

[0089] (Manufacturing Example 13) 100 g of the MEK dispersion of cellulose obtained in Production Example 4 was mixed with 5.8 g of a 50% ethanol solution of the compound represented by general formula (4), prepared in Production Example 5, and stirred overnight at room temperature. The resulting liquid was defibrated six times at a pressure of 180 MPa using a wet-type ultra-high-pressure atomizer (product name: NanoVeta C-ES, manufactured by Yoshida Machinery Industry Co., Ltd.) to obtain a dispersion containing fine fibrous cellulose B-6. The solid content of the dispersion was 4.3% by mass. The properties of fine fibrous cellulose B-6 are shown in Table 1.

[0090] (Manufacturing Example 14) We attempted to defibrillate the resulting liquid using a wet-type, ultra-high-pressure atomizer (product name: NanoVector C-ES, manufactured by Yoshida Machinery Industry Co., Ltd.) by adding MEK and repeatedly performing suction filtration to replace the solvent, adjusting the solid content to 1%. However, the device became clogged and defibrillation was not possible.

[0091] (Manufacturing example 15) In the TEMPO-oxidized cellulose obtained in Production Example 1, MEK was added and solvent replacement was performed by repeated suction filtration to adjust the solid content to 1%. Attempts were made to defibrillate the resulting liquid using a wet-type, ultra-high-pressure atomizing device (product name: NanoVeta C-ES, manufactured by Yoshida Machinery Industry Co., Ltd.), but the device became clogged and defibrillation was not possible.

[0092] [Measurement of number-average fiber diameter and number-average fiber length] After preparing aqueous dispersions of various fine fibrous celluloses with a solid content of 0.01 to 0.05% by mass, these dispersions were dropped onto a mica plate and dried. The dispersions were then observed using a scanning probe microscope (Bruker, model: MultiMode8), and the diameter and length of at least 50 fibers were measured. The average values ​​were defined as the number-average fiber diameter and number-average fiber length. The number-average fiber diameter and number-average fiber length are shown in Table 1.

[0093] [Table 1]

[0094] [ka]

[0095] (Examples and Comparative Examples) Compositions were prepared by blending each component according to the compositions shown in Tables 2 and 3. The content of fine fibrous cellulose is based on solid content. The prepared compositions were applied to an easily adhesive treated PET film (Toyobo A-4360, 100 microns thick) using a bar coater, dried at 80°C for 1 minute, and then cured with an electrodeless UV lamp (H bulb, manufactured by Excelitas Snowblelight) at 1000 mJ / cm². 2 The cured material (coating film) was prepared by irradiating it with ultraviolet light. Although the solid content differed depending on the composition, the grit of the bar coater was adjusted so that the coating film thickness was 4 to 6 microns.

[0096] (Radical polymerizable compounds) A-1: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., product name: Art Resin UN-904) A-2: Urethane acrylate (manufactured by Negami Kogyo Co., Ltd., product name: Art Resin UN-320HA) A-3: Tetrahydrofurfurylacrylate (manufactured by Aldrich) A-4: N-Acryloylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0097] (Fine fibrous cellulose) B-1: Fine fibrous cellulose B-1 obtained in Production Example 6 B-2: Fine fibrous cellulose B-2 obtained in Production Example 9 B-3: Fine fibrous cellulose B-3 obtained in Production Example 10 B-4: Fine fibrous cellulose B-4 obtained in Production Example 11 B-5: Fine fibrous cellulose B-5 obtained in Production Example 12 B-6: Fine fibrous cellulose B-6 obtained in Production Example 13 b-1: Fine fibrous cellulose b-1 obtained in Production Example 7 b-2: Fine fibrous cellulose b-2 obtained in Production Example 8

[0098] (Radical polymerization initiator) C-1: 1-Hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV, trade name: Omnirad 184)

[0099] [Measurement of gloss level] The 60° gloss of the coating film was measured using a VG 7000 gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.). The gloss of the coating films prepared in the examples and comparative examples was measured using a VG 7000 gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.). A higher gloss value indicates a higher gloss and a more glossy coating film. The results are shown in Tables 2 and 3.

[0100] [Evaluation of flexural resistance] The coatings prepared in the examples and comparative examples were cut into 25mm x 150mm rectangles, and the samples were fixed to the jig of a Yuasa System Equipment desktop durability tester (desktop durability tester DMLHB main unit + surface material unloaded U-shaped expansion test jig DMX-FS) by attaching the short side of the sample with double-sided tape so that the coating surface was facing inward when folded. A bending test was conducted 100,000 times under the conditions of a bending radius of 1.5 mm and a bending speed of 60 cycles / minute. After the test, the bent portion of the sample was visually inspected. A sample with no cracks or fractures in the bent portion was marked with ◎, a sample with cracks or fractures only at the ends of the bent portion was marked with ○, and a sample with cracks or fractures throughout the entire bent portion was marked with ×. The results are shown in Tables 2 and 3.

[0101] [Table 2]

[0102] [Table 3]

Claims

1. A composition comprising fine fibrous cellulose and a radical polymerizable compound, A composition characterized in that the above-mentioned fine fibrous cellulose satisfies the following conditions (A), (B), (C), and (D), and also satisfies one or more of the following conditions (E) and (F). (A) The number-average fiber diameter is between 1 nm and 100 nm. (B) The number-average fiber length is between 50 nm and 1000 nm. (C) Having anionic functional groups (D) An organonium ion is bonded to the above anionic functional group. (E) Having an acyl group (F) The above organic onium ion is a quaternary ammonium represented by the following general formula (1). 【Chemistry 1】 (In general formula (1), R １ ~R ４ Each of these is independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an arene group, an allyl group, or a group having an alkylene oxide structure, R １ ~R ４ At least one of them is a group having an alkylene oxide structure.

2. The composition according to claim 1, characterized in that the organic onium ion is a quaternary ammonium compound, and the fine fibrous cellulose satisfies condition (E).

3. The composition according to claim 1, characterized in that the anionic functional group is a carboxyl group.

4. The composition according to claim 1, characterized in that the fine fibrous cellulose satisfies the conditions (E) and (F).

5. The composition according to claim 1, further comprising a radical polymerization initiator.

6. The composition according to claim 1, characterized in that the fine fibrous cellulose is contained in 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the radical polymerizable compound.

7. A cured product of the composition according to any one of claims 1 to 6.

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