Molding material

Abstract

To provide a molding material containing cellulose fibers that can be suitably used for producing molded articles excellent in strength and impact resistance, and that exhibits excellent moldability during the production of molded articles.SOLUTION: The molding material comprises cellulose fibers and a specific cellulose derivative in which some of the hydrogen atoms constituting the hydroxyl groups of cellulose are substituted with a first chemical structure that is a chemical structure of the general formula of at least one of formulas (A) and (B) in the figure, and others of the hydrogen atoms are substituted with a second chemical structure that is a chemical structure of the general formula of formula (C) in the figure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a molding material. [Background technology]

[0002] As a measure to combat oil depletion and global warming, attempts are being considered to replace conventional plastic materials with molding materials made from cellulose, a plant-derived, abundant natural material.

[0003] For example, a molded article containing natural cellulose fibers and cellulose esters such as cellulose acetate butyrate and cellulose acetate propionate has been proposed as a nonwoven web or composite structure that can be disposed of in a composting landfill (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2005-504184 Summary of the Invention [Problem to be solved by the invention]

[0005] However, such molded articles have problems in that they are inferior in strength and impact resistance, and are poor in moldability during production. [Means for solving the problem]

[0006] The present invention has been made to solve the above-mentioned problems, and can be realized as the following application examples.

[0007] A molding material according to an application example of the present invention comprises cellulose fibers and a specific cellulose derivative in which some of the hydrogen atoms constituting the hydroxyl groups of the cellulose are substituted with a first chemical structure having a general chemical structure of at least one of the following formulas (A) and (B), and other hydrogen atoms are substituted with a second chemical structure having a general chemical structure of the following formula (C): [ka] (In formula (A), R A is a monovalent hydrocarbon group having 1 to 8 carbon atoms.) [ka] (In formula (B), RB is a monovalent hydrocarbon group having 1 to 8 carbon atoms.) [ka] (In formula (C), RC is a divalent hydrocarbon group having 1 to 8 carbon atoms, and X - is an anionic chemical structure, and Y + is a cationic chemical structure.) [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a table showing the types and amounts of Compounds X and Y used in Synthesis Examples 1 to 9. [Figure 2] FIG. 2 is a table summarizing the conditions under which the cellulose derivatives were synthesized in each synthesis example. [Figure 3] FIG. 3 is a table summarizing the compositions of the molding materials, molding methods, and evaluation results of Examples 1 to 13. [Figure 4] FIG. 4 is a table summarizing the compositions of the molding materials, molding methods, and evaluation results of Examples 14 to 22 and Comparative Examples 1 to 3. DETAILED DESCRIPTION OF THE INVENTION

[0009] Preferred embodiments of the present invention will be described in detail below. [1] Molding material First, the molding material of the present invention will be described.

[0010] The molding material of the present invention contains cellulose fibers and a specific cellulose derivative in which some of the hydrogen atoms constituting the hydroxyl groups of the cellulose are substituted with a first chemical structure which is a chemical structure of at least one of the following general formulas (A) and (B), and other some of the hydrogen atoms are substituted with a second chemical structure which is a chemical structure of the following general formula (C).

[0011] [ka] (In formula (A), R A is a monovalent hydrocarbon group having 1 to 8 carbon atoms.)

[0012] [ka] (In formula (B), RB is a monovalent hydrocarbon group having 1 to 8 carbon atoms.)

[0013] [ka] (In formula (C), RC is a divalent hydrocarbon group having 1 to 8 carbon atoms, and X - is an anionic chemical structure, and Y + is a cationic chemical structure.)

[0014] With this configuration, it is possible to provide a molding material that can be suitably used to produce molded articles that are excellent in strength and impact resistance, and that has excellent moldability when producing molded articles.

[0015] The reasons for such excellent effects are believed to be as follows. Specifically, by including a specific cellulose derivative that has excellent compatibility and affinity with cellulose fibers, excellent heat resistance and toughness, and excellent fluidity when melted, in addition to cellulose, which has high theoretical strength and excellent shape stability, the functions of these components can be prevented or suppressed from canceling out, allowing these components to fully exhibit their functions. More specifically, during the production of a molded article using the molding material, or in a molded article produced using the molding material, the functions of the cellulose fibers and the specific cellulose derivative can be fully exhibited, while the wettability of the specific cellulose derivative with the cellulose fibers can be increased, and interfacial delamination between the different components constituting the molded article can be suitably prevented or suppressed. As a result, the above-mentioned excellent effects are believed to be obtained. In particular, the specific cellulose derivative having a first chemical structure improves the strength of the molded article produced using the molding material, and the specific cellulose derivative having a second chemical structure improves the compatibility between the specific cellulose derivative and cellulose fibers, resulting in excellent impact resistance of the molded article produced using the molding material.

[0016] Furthermore, since interfacial peeling between different components constituting the molded body can be suitably prevented or suppressed, a molded body can be obtained in which problems such as dust generation are effectively prevented.

[0017] Furthermore, the inclusion of cellulose fiber, which is a plant-derived, abundant natural material, makes it possible to appropriately address environmental issues and conserve buried resources, etc., and is also advantageous from the viewpoints of stable supply of molding materials and molded articles produced using the same, cost reduction, etc. Furthermore, cellulose fiber is a component that is contained in large amounts not only in virgin pulp but also in waste paper, used cloth, etc., and is therefore advantageous from the viewpoint of promoting effective reuse of resources.

[0018] Furthermore, the specific cellulose derivatives can be suitably obtained from the above-mentioned cellulose as a raw material and are generally components with excellent biodegradability, which allows the molding material as a whole and the molded article produced using the molding material as a whole to suitably address environmental issues, etc.

[0019] On the other hand, if the above conditions are not met, satisfactory results will not be obtained.

[0020] For example, even if a molding material contains cellulose fibers, if it does not contain a specific cellulose derivative, the molded article produced using the molding material will have significantly poorer impact resistance, etc., and will also have poor moldability during production.

[0021] Furthermore, if other cellulose derivatives are used in place of the specific cellulose derivatives and the specific cellulose derivatives are not included, the strength and impact resistance of the molded body produced using the molding material may be inferior, and the moldability during production of the molded body may be inferior.

[0022] For example, if a cellulose derivative having a first chemical structure but not a second chemical structure is used instead of the specific cellulose derivative, the impact resistance of the molded body produced using the molding material will be inferior.

[0023] Furthermore, if a cellulose derivative having the second chemical structure but not the first chemical structure is used instead of the specific cellulose derivative, the heat resistance and flexural modulus of the molded body produced using the molding material will be inferior.

[0024] Furthermore, if a cellulose derivative having a second chemical structure but not a first chemical structure, and having a chemical structure in which the hydrocarbon group in the above formula (A) or formula (B) has 9 or more carbon atoms, is used instead of the specific cellulose derivative, the flexural modulus of the molded body produced using the molding material will be inferior.

[0025] Furthermore, if a cellulose derivative having a first chemical structure but not a second chemical structure, and having a chemical structure in which the hydrocarbon group in the above formula (C) has 9 or more carbon atoms, is used instead of the specific cellulose derivative, the flexural impact resistance of the molded body produced using the molding material will be poor.

[0026] [1-1] Cellulose fiber The molding material of the present invention contains cellulose fibers.

[0027] Cellulose fiber is the main component of the molding material of the present invention, and is a component that greatly contributes to maintaining the shape of the molded body produced using the molding material of the present invention, as well as having a significant impact on the properties of the molded body, such as its strength.

[0028] Cellulose is a naturally occurring material derived from plants and is abundant in nature. Therefore, the use of cellulose fibers can effectively address environmental issues and conserve buried resources, and is also preferable from the viewpoints of stable supply of molding materials and molded articles produced using the same, cost reduction, etc. Furthermore, among various fibers, cellulose fibers have particularly high theoretical strength, and are advantageous from the viewpoint of improving the strength of molded articles.

[0029] As the cellulose fiber, virgin pulp may be used, or recycled waste paper, waste cloth, etc. may be used.

[0030] Cellulose fibers are generally composed mainly of cellulose, but may contain components other than cellulose, such as hemicellulose and lignin.

[0031] Furthermore, the cellulose fibers used may be those that have been subjected to a treatment such as bleaching. Examples of cellulose fibers include cotton, hemp, rayon, and cupra.

[0032] The content of cellulose fibers in the molding material is not particularly limited, but is preferably 40% by mass or more and 80% by mass or less, more preferably 45% by mass or more and 78% by mass or less, and even more preferably 50% by mass or more and 75% by mass or less.

[0033] This results in the material containing a larger amount of cellulose fiber, which is a plant-derived, abundant natural material, which can more appropriately address environmental issues and conserve buried resources, and is more preferable from the standpoint of stable supply of molding materials and molded articles produced using them, cost reduction, etc. It is also more preferable from the standpoint of improving the strength of molded articles, and the molding material will have better plasticity and moldability.

[0034] When the molding material contains a cellulose derivative having an acetyl group but not having a second chemical structure, as described below, the value of [XF / (XF+XD1+XD2)] × 100, where XF is the content of cellulose fiber in the molding material (mass%), XD1 is the content of the specific cellulose derivative (mass%), and XD2 is the content of the cellulose derivative having an acetyl group but not having a second chemical structure (mass%), is preferably 50 or more and 80 or less, more preferably 55 or more and 78 or less, and even more preferably 60 or more and 75 or less.

[0035] This results in the material containing a larger amount of cellulose fiber, which is a plant-derived, abundant natural material, which can more appropriately address environmental issues and conserve buried resources, and is more preferable from the standpoint of stable supply of molding materials and molded articles produced using them, cost reduction, etc. It is also more preferable from the standpoint of improving the strength of molded articles, and the molding material will have better plasticity and moldability.

[0036] The average length of the cellulose fibers is not particularly limited, but is preferably 500 μm or less, more preferably 1 μm or more and 400 μm or less, and even more preferably 1 μm or more and 50 μm or less.

[0037] This improves the affinity and compatibility of the cellulose fibers with specific cellulose derivatives and cellulose derivatives having an acetyl group but not a second chemical structure, as described below, and improves the shape stability and strength of molded articles produced using the molding material. Furthermore, dust generation in molded articles produced using the molding material can be more effectively prevented and suppressed. Furthermore, the occurrence of undesired irregularities on the surface of molded articles produced using the molding material can be more effectively prevented. The fiber length of the cellulose fibers is determined by a method conforming to ISO 16065-2:2007.

[0038] The average thickness of the cellulose fibers is not particularly limited, but is preferably 0.1 μm or more and 100 μm or less, and more preferably 0.2 μm or more and 20 μm or less.

[0039] This makes it possible to improve the shape stability, strength, etc. of a molded article produced using the molding material, and also makes it possible to more effectively prevent the occurrence of undesired irregularities on the surface of a molded article produced using the molding material.

[0040] The average aspect ratio of the cellulose fibers, that is, the average length to the average thickness, is not particularly limited, but is preferably 10 or more and 1,000 or less, and more preferably 15 or more and 100 or less.

[0041] This makes it possible to improve the shape stability, strength, etc. of a molded article produced using the molding material. Also, dust generation in a molded article produced using the molding material can be more effectively prevented or suppressed. Also, it is possible to more effectively prevent the occurrence of undesired irregularities on the surface of a molded article produced using the molding material.

[0042] [1-2] Specific cellulose derivatives The molding material of the present invention contains a specific cellulose derivative.

[0043] The specific cellulose derivative is a compound in which some of the hydrogen atoms constituting the hydroxyl groups of cellulose are substituted with a first chemical structure which is a chemical structure of at least one of the general formulas (A) and (B) above, and other hydrogen atoms are substituted with a second chemical structure which is a chemical structure of the general formula (C) above.

[0044] In the above formula (A), R A may be a monovalent hydrocarbon group having 1 to 8 carbon atoms, but is preferably an alkyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 3 to 5 carbon atoms.

[0045] This makes it possible to improve the strength and impact resistance of a molded article produced using the molding material, and to improve the moldability during production of the molded article.

[0046] When the specific cellulose derivative has a chemical structure represented by the above formula (A), the specific cellulose derivative may have two or more chemical structures with different conditions as the chemical structure represented by the above formula (A).

[0047] In the above formula (B), RB may be a monovalent hydrocarbon group having 1 to 8 carbon atoms, but is preferably an alkyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 3 to 5 carbon atoms.

[0048] This makes it possible to improve the strength and impact resistance of a molded article produced using the molding material, and to improve the moldability during production of the molded article.

[0049] When the specific cellulose derivative has a chemical structure represented by the above formula (B), the specific cellulose derivative may have two or more chemical structures with different conditions as the chemical structure represented by the above formula (B).

[0050] In the specific cellulose derivative, the DS value of the first chemical structure, i.e., the degree of substitution, which is the value corresponding to the number of hydrogen atoms of all hydroxyl groups in cellulose that are substituted with the first chemical structure divided by the number of glucose atoms that constitute the cellulose, is preferably 1.2 or more and 2.6 or less, more preferably 1.4 or more and 2.4 or less, and even more preferably 1.6 or more and 2.2 or less.

[0051] This makes it possible to improve the strength and impact resistance of a molded article produced using the molding material, and to improve the moldability during production of the molded article.

[0052] R C in the above formula (C) may be a divalent hydrocarbon group having 1 to 8 carbon atoms, but is preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an alkylene group having 3 to 5 carbon atoms.

[0053] This makes it possible to improve the strength and impact resistance of a molded article produced using the molding material, and to improve the moldability during production of the molded article.

[0054] X in the above formula (C) - is not particularly limited as long as it has an anionic chemical structure, but is preferably at least one of the following formulas (1) to (5).

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] This allows the shape stability, strength, etc. of a molded article produced using the molding material to be improved.

[0061] Y in the above formula (C) + is not particularly limited as long as it has a cationic chemical structure, but is preferably at least one of the following formulas (6) to (11).

[0062] [ka] (In formula (6), n is an integer of 1 or more and 18 or less.)

[0063] [ka] (In formula (7), n is an integer of 1 or more and 18 or less.)

[0064] [ka] (In formula (8), n is an integer of 1 or more and 18 or less.)

[0065] [ka] (In formula (9), n is an integer of 1 or more and 18 or less.)

[0066] [ka] (In formula (10), n is an integer of 1 or more and 18 or less.)

[0067] [ka] (In formula (11), n is an integer of 1 or more and 18 or less.)

[0068] This allows the shape stability, strength, etc. of the molded article produced using the molding material to be improved.

[0069] In the above formula (6), n may be an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 15 or less, and more preferably an integer of 2 or more and 12 or less. This makes the above-mentioned effects more pronounced.

[0070] In the above formula (7), n may be an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 15 or less, and more preferably an integer of 2 or more and 12 or less. This makes the above-mentioned effects more pronounced.

[0071] In the above formula (8), n may be an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 15 or less, and more preferably an integer of 2 or more and 12 or less. This makes the above-mentioned effects more pronounced.

[0072] In the above formula (9), n may be an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 15 or less, and more preferably an integer of 2 or more and 12 or less. This makes the above-mentioned effects more pronounced.

[0073] In the above formula (10), n may be an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 15 or less, and more preferably an integer of 2 or more and 12 or less. This makes the above-mentioned effects more pronounced.

[0074] In the above formula (11), n may be an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 15 or less, and more preferably an integer of 2 or more and 12 or less.

[0075] This more significantly exhibits the above-mentioned effects, specifically, the specific cellulose derivative is more effectively prevented from separating, the dispersibility of the specific cellulose derivative in the surrounding resin forming the matrix is improved, and the mechanical properties are also improved.

[0076] In particular, in the second chemical structure, X - is at least one of the above formulas (1) to (5), and Y + is preferably at least one of the above formulas (6) to (11).

[0077] This allows the shape stability, strength, etc. of a molded article produced using the molding material to be improved.

[0078] The specific cellulose derivative may have the chemical structure represented by the above formula (C), that is, two or more chemical structures with different conditions as the second chemical structure.

[0079] The DS value of the second chemical structure in the specific cellulose derivative, i.e., the degree of substitution, which is the value corresponding to the number of hydrogen atoms of all hydroxyl groups in cellulose that are substituted with the second chemical structure divided by the number of glucose atoms that constitute the cellulose, is preferably 0.1 or more and 0.8 or less, more preferably 0.15 or more and 0.7 or less, and even more preferably 0.2 or more and 0.6 or less.

[0080] This makes it possible to improve the strength and impact resistance of a molded article produced using the molding material, and to improve the moldability during production of the molded article.

[0081] In particular, when the DS value of the first chemical structure and the DS value of the second chemical structure in the specific cellulose derivative both satisfy the above-mentioned conditions, the above-mentioned effects are more significantly exhibited.

[0082] In the specific cellulose derivative, the total DS value of all the substituents is preferably 1.6 or more and 3.0 or less, more preferably 1.8 or more and 2.9 or less, and even more preferably 2.0 or more and 2.8 or less.

[0083] This makes it possible to further improve the strength and impact resistance of a molded article produced using the molding material, and to further improve the moldability during production of the molded article.

[0084] The number average molecular weight of the specific cellulose derivative is preferably 10,000 or more and 400,000 or less, more preferably 20,000 or more and 300,000 or less, and even more preferably 35,000 or more and 200,000 or less.

[0085] This makes it possible to improve the affinity and compatibility of the specific cellulose derivative with cellulose fibers, thereby improving the strength and impact resistance of molded bodies produced using the molding material and improving the moldability during production of the molded bodies.

[0086] The glass transition temperature of the specific cellulose derivative is preferably 80°C or higher and 200°C or lower, more preferably 90°C or higher and 180°C or lower, and even more preferably 100°C or higher and 170°C or lower.

[0087] This makes it possible to improve the affinity and compatibility of the specific cellulose derivative with cellulose fibers, thereby improving the strength and impact resistance of molded bodies produced using the molding material and improving the moldability during production of the molded bodies.

[0088] The content of the specific cellulose derivative in the molding material is preferably 10% by mass or more and 40% by mass or less, more preferably 13% by mass or more and 30% by mass or less, and even more preferably 15% by mass or more and 25% by mass or less.

[0089] This makes it possible to improve the strength and impact resistance of a molded article produced using the molding material, and to improve the moldability during production of the molded article.

[0090] When the molding material contains a cellulose derivative having an acetyl group but not having a second chemical structure, as described below, the value of [XD1 / (XF+XD1+XD2)] × 100, where XF is the content of cellulose fiber in the molding material (mass%), XD1 is the content of the specific cellulose derivative (mass%), and XD2 is the content of the cellulose derivative having an acetyl group but not having a second chemical structure (mass%), is preferably 10 or more and 50 or less, more preferably 12 or more and 45 or less, and even more preferably 15 or more and 40 or less.

[0091] This makes it possible to more effectively prevent an increase in the cost of the molding material, while improving the plasticity and moldability of the molding material.

[0092] When the content of cellulose fiber in the molding material is XC [% by mass] and the content of the specific cellulose derivative is XD1 [% by mass], it is preferable to satisfy the relationship 0.14≦XD1 / XC≦0.80, more preferably the relationship 0.19≦XD1 / XC≦0.60, and even more preferably the relationship 0.22≦XD1 / XC≦0.50.

[0093] This makes it possible to improve the strength and impact resistance of a molded article produced using the molding material, and to improve the moldability during production of the molded article.

[0094] [1-3] Cellulose derivatives having an acetyl group but no second chemical structure The molding material of the present invention preferably contains, in addition to the cellulose fibers and specific cellulose derivative described above, a cellulose derivative that has an acetyl group but does not have the second chemical structure described above.

[0095] Such cellulose derivatives having an acetyl group but not having a second chemical structure have excellent affinity and compatibility with the specific cellulose derivatives described above, and by including such cellulose derivatives having an acetyl group but not having a second chemical structure, the strength, flexural modulus, and impact resistance of molded bodies produced using the molding material can be improved, and the moldability during production of the molded bodies can be improved.

[0096] The cellulose derivative having an acetyl group but not a second chemical structure preferably has at least one alkyl group having 1 to 18 carbon atoms as a modifying group and has a DS value in the range of 1.0 to 2.5.

[0097] This allows a molded article produced using the molding material to have a particularly excellent flexural modulus.

[0098] As described above, a cellulose derivative having an acetyl group but not a second chemical structure preferably has at least one alkyl group having 1 to 18 carbon atoms as a modifying group, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms. This makes the above-mentioned effects more pronounced.

[0099] Furthermore, as described above, the DS value of a cellulose derivative having an acetyl group but not having a second chemical structure is preferably 1.0 or more and 2.5 or less, more preferably 1.2 or more and 2.3 or less, and even more preferably 1.5 or more and 2.0 or less. This makes the above-mentioned effects more pronounced.

[0100] The cellulose derivative having an acetyl group but not having a second chemical structure is preferably at least one selected from the group consisting of cellulose acetate propionate, cellulose acetate butyrate, and cellulose diacetate.

[0101] This makes it possible to improve the flexural modulus, flexural strength and impact resistance of a molded article produced using the molding material, and to improve the moldability during production of the molded article.

[0102] When the molding material contains a cellulose derivative that has an acetyl group but does not have a second chemical structure, the value of [XD2 / (XF+XD1+XD2)] × 100, where XF [mass%] is the content of cellulose fiber in the molding material, XD1 [mass%] is the content of the specific cellulose derivative, and XD2 [mass%] is the content of the cellulose derivative that has an acetyl group but does not have the second chemical structure, is preferably 10 or more and 40 or less, more preferably 12 or more and 36 or less, and even more preferably 14 or more and 32 or less.

[0103] This makes it possible to more significantly exert the effect of including a cellulose derivative having an acetyl group but not having a second chemical structure as described above, while also improving the moldability during the production of molded bodies.

[0104] The content of the cellulose derivative having an acetyl group but not having a second chemical structure in the molding material is preferably 8% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 36% by mass or less, and even more preferably 12% by mass or more and 32% by mass or less.

[0105] This makes it possible to improve the strength and impact resistance of a molded article produced using the molding material, and to improve the moldability during production of the molded article.

[0106] [1-4] Flame retardants The molding material of the present invention may further contain a flame retardant.

[0107] This makes it possible to improve the flame retardancy of a molded article produced using the molding material.

[0108] Examples of the flame retardant include bromine-based flame retardants, chlorine-based flame retardants, phosphorus-containing flame retardants, silicon-containing flame retardants, nitrogen compound-based flame retardants, and inorganic flame retardants.

[0109] Among these, phosphorus-containing flame retardants and silicon-containing flame retardants are preferred because they do not generate hydrogen halides through thermal decomposition during mixing / kneading with other components or during molding processing, which may corrode processing machinery or molds or worsen the working environment, and they are less likely to have adverse effects on the environment through the release of halogens or the generation of dioxins and other compounds through decomposition when incinerated.

[0110] Examples of phosphorus-containing flame retardants include organic phosphorus compounds such as phosphate esters, phosphate condensed esters, and polyphosphates.

[0111] Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, tris(phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl(2-ethylhexyl) phosphate, di(isopropylphenyl) phosphate, Examples of suitable acryloyloxyethyl phosphate include diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, and diethyl phenylphosphonate.

[0112] Examples of the phosphoric acid condensed ester include aromatic phosphoric acid condensed esters such as resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly(2,6-xylyl) phosphate, and condensates thereof.

[0113] Further examples include polyphosphates formed from salts of phosphoric acid or polyphosphoric acid with metals of Groups 1 to 14 of the periodic table, ammonia, aliphatic amines, and aromatic amines. Representative polyphosphate salts include metal salts such as lithium salt, sodium salt, calcium salt, barium salt, iron (II) salt, iron (III) salt, and aluminum salt; aliphatic amine salts such as methylamine salt, ethylamine salt, diethylamine salt, triethylamine salt, ethylenediamine salt, and piperazine salt; and aromatic amine salts such as pyridine salt and triazine salt.

[0114] In addition to the above, examples include halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, and tris(β-chloropropyl) phosphate, phosphazene compounds having a structure in which a phosphorus atom and a nitrogen atom are linked by a double bond, and phosphate ester amides.

[0115] Examples of silicon-containing flame retardants include organosilicon compounds with a two-dimensional or three-dimensional structure, polydimethylsiloxanes, and polydimethylsiloxanes in which the methyl groups on the side chains or ends are substituted or modified with hydrogen atoms, substituted or unsubstituted aliphatic hydrocarbon groups, or aromatic hydrocarbon groups, so-called silicone oils or modified silicone oils.

[0116] Examples of substituted or unsubstituted aliphatic hydrocarbon groups and aromatic hydrocarbon groups include alkyl groups, cycloalkyl groups, phenyl groups, benzyl groups, amino groups, epoxy groups, polyether groups, carboxyl groups, mercapto groups, chloroalkyl groups, alkyl higher alcohol ester groups, alcohol groups, aralkyl groups, vinyl groups, and trifluoromethyl groups.

[0117] Furthermore, as flame retardants other than the phosphorus-containing flame retardants and silicon-containing flame retardants, for example, inorganic flame retardants such as magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, tin oxide salts, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, metal salts of tungstic acid, composite oxides of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium-based compounds, guanidine-based compounds, fluorine-based compounds, graphite, and expandable graphite can be used.

[0118] When the molding material contains a flame retardant, the content of the flame retardant can be 1 part by mass or more and 30 parts by mass or less, when the total content of the cellulose fiber and the specific cellulose derivative is 100 parts by mass.

[0119] This makes it possible to more effectively exhibit the effects of the present invention described above, while also making it possible to improve the flame retardancy of a molded article produced using the molding material of the present invention.

[0120] When the molding material contains a cellulose derivative having an acetyl group but not having a second chemical structure, as described below, and a flame retardant, the value of [XR / (XF+XD1+XD2)] × 100, where XF is the content of the cellulose fiber in the molding material (mass%), XD1 is the content of the specific cellulose derivative, XD2 is the content of the cellulose derivative having the acetyl group and not having the second chemical structure (mass%), and XR is the content of the flame retardant (mass%), is preferably 1 or more and 20 or less, more preferably 2 or more and 18 or less, and even more preferably 3 or more and 16 or less.

[0121] This makes it possible to improve the flame retardancy of a molded article produced using the molding material, and also to improve the toughness and Charpy impact strength of a molded article produced using the molding material.

[0122] [1-5] Antioxidants The molding material of the present invention may further contain an antioxidant. This improves the resin's stability against heating during the kneading and molding processes.

[0123] Examples of antioxidants include phosphorus-based antioxidants and hindered phenol-based antioxidants (e.g., "Irganox 1010," "Irganox 1076," and "Irganox 3114" manufactured by Ciba Specialty Chemicals, and "Sumilizer GP" manufactured by Sumitomo Chemical Co., Ltd.).

[0124] When the molding material contains an antioxidant, the content of the antioxidant can be 0.05 parts by mass or more and 2.0 parts by mass or less when the total content of the cellulose fiber and the specific cellulose derivative is 100 parts by mass.

[0125] This makes it possible to more suitably improve scratch resistance and stain resistance while more suitably suppressing the deterioration of the impact resistance, moldability, rigidity, bending strength, heat resistance, etc., which are inherent to the specific cellulose derivative.

[0126] [1-6] Other ingredients The molding material of the present invention may contain components other than those described above. Hereinafter, in this section, such components will also be referred to as "other components."

[0127] Examples of other components include colorants, insect repellents, mildew inhibitors, antibacterial agents, antistatic agents, flame retardant assistants, ultraviolet absorbers, aggregation inhibitors, release agents, processing aids, anti-drip agents, cellulose derivatives other than those mentioned above, resin materials, and plasticizers.

[0128] However, the content of other components in the molding material of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0129] [2] Manufacturing method of molding material Next, a method for producing the molding material of the present invention will be described.

[0130] The molding material of the present invention can be produced, for example, by mixing the above-mentioned components. In this case, the timing of mixing the components may be the same or different.

[0131] The molding material of the present invention may be produced by kneading the above-mentioned components, for example. The components can be kneaded using, for example, a single-screw kneader, a twin-screw kneader, a multi-screw kneader, a mixer, or a roll Banbury mixer.

[0132] The strand-shaped molding material obtained by kneading may be pelletized using a pelletizer such as a strand type or a watering hot cut type to form a pellet-shaped molding material.

[0133] The following method may also be used as a method for producing a molding material. That is, a kneaded mixture of the above-mentioned components may be formed into a sheet, and then cut into a desired shape using, for example, a shredder to produce pellets of molding material. The method for forming the kneaded mixture into a sheet is not particularly limited, but examples include a method in which the kneaded mixture is first deposited in air to form a sheet-like deposit, the deposit is compressed using a calendar device to remove air and increase density, and then heated in a heating furnace without contact, and then hot-pressed using a heat press. The shape and size of the pellets obtained by cutting are not particularly limited, but they can be, for example, approximately rectangular parallelepipeds with a side length of 2 mm to 5 mm.

[0134] The cellulose fibers used in the production of the molding material of the present invention may be those that have been previously subjected to a defibration treatment. In particular, cellulose fiber sources containing cellulose fibers, such as waste paper, may be defibrated.

[0135] [3] Molded body Next, a molded article produced using the molding material of the present invention will be described.

[0136] The molded body of the present invention comprises cellulose fibers and a specific cellulose derivative in which some of the hydrogen atoms constituting the hydroxyl groups of the cellulose are substituted with a first chemical structure which is a chemical structure of at least one of the general formulas (A) and (B) above, and other hydrogen atoms are substituted with a second chemical structure which is a chemical structure of the general formula (C) above.

[0137] The molded article according to the present invention can be produced using the molding material described above. This makes it possible to provide a molded article having excellent strength and impact resistance.

[0138] Furthermore, since interfacial peeling between different components constituting the molded body can be suitably prevented or suppressed, problems such as dust generation can be effectively prevented.

[0139] Furthermore, the inclusion of cellulose fibers, which are naturally abundant and plant-derived materials, makes it possible to appropriately address environmental issues and conserve buried resources, and is also advantageous from the viewpoints of stable supply of molded products, cost reduction, etc. Furthermore, cellulose fibers are a component that is contained in large amounts not only in virgin pulp but also in waste paper, used cloth, etc., and is therefore advantageous from the viewpoint of promoting effective reuse of resources.

[0140] Furthermore, the specific cellulose derivatives can be suitably obtained from the above-mentioned cellulose as a raw material and are generally components with excellent biodegradability, which allows the molded article as a whole to suitably address environmental issues and the like.

[0141] Each component constituting the molded body preferably satisfies the conditions described above in [1-1] to [1-6].

[0142] The shape of the molded product is not particularly limited, and may be any shape, such as a sheet, a block, a sphere, or a three-dimensional shape.

[0143] The molded article may be used for any purpose, and examples thereof include various housings such as housings for printers, ink cartridges, various containers, and the like.

[0144] In particular, the molded body of the present invention has a high affinity between the cellulose fibers and the specific cellulose derivative, and dust generation is effectively prevented, making it suitable for use in ink cartridges and the like where dust generation is a particular problem.

[0145] The molded article according to the present invention may be produced by any method, but can be suitably produced, for example, by injection molding, press molding, or the like using the molding material according to the present invention as described above.

[0146] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these. [Example]

[0147] Next, specific examples of the present invention will be described. [4] Synthesis of cellulose derivatives (Synthesis Example 1) A mixture of 238 g (1000 mmol) of triethyl 3-phosphonopropionate and 1000 mL of a 30% by weight solution of hydrogen bromide in acetic acid (approximately 5.1 mol / L) was heated at 90°C overnight with stirring, and then diethyl ether was added. The resulting solid oil was then washed with diethyl ether (1000 mL x 3) to obtain a slightly yellow, viscous oil. This slightly yellow, viscous oil was dried under vacuum overnight to obtain 154 g (1000 mmol) of 3-[(hydroxyphosphinyl)oxy]propanoic acid as compound X.

[0148] Also, propionic acid was prepared as compound Y. Cellulose (KC Flock W50, manufactured by Nippon Paper Industries Co., Ltd.): 1.90 g (11.76 mmol) was placed in a 200 mL three-neck flask, and 25.4 mL of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) and 3 g of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as solvents, followed by mechanical stirring at 300 rpm for 4 hours.

[0149] The internal temperature was then cooled to -4°C, and 2.1 g (14 mmol) of compound X and 2.61 g (35.27 mmol) of compound Y were added dropwise thereto, followed by a reaction for 12 hours at an internal temperature of 90°C. The internal temperature was then cooled to 65°C, and 50 mL of methanol was added to terminate the reaction.

[0150] 10 mL of pure water was added thereto and filtered under reduced pressure, and then the residue was dispersed in 25 mL of methanol, stirred, and filtered under reduced pressure. This procedure was repeated five times, and the mixture was dried in vacuo for 12 hours.

[0151] The obtained solid was mixed with 12.3 g of 1-methylimidazole (Tokyo Chemical Industry Co., Ltd.) at room temperature (25°C), and the mixture was reacted at 100°C for 4 hours.

[0152] This reaction solution was poured into a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), vigorously stirred for 5 minutes, and then allowed to stand. The upper layer, which separated into two layers, was then removed by decantation. This procedure was repeated two more times, and the remaining lower layer was heated and vacuum dried at 100°C for 1 hour while stirring, yielding a wine-colored liquid cellulose derivative at room temperature (25°C; the same applies below).

[0153] (Synthesis Examples 2 to 9) A cellulose derivative was synthesized in the same manner as in Synthesis Example 1, except that the type of compound Y and the amounts of compound X and compound Y used were changed as shown in FIG. 1 to give the structure of the cellulose derivative as shown in FIG. 1.

[0154] In FIG. 1, 3-[(Hydroxyphosphinyl)oxy]propanoic acid is shown as "X1."

[0155] (Synthesis Example 10) Cellulose (KC Flock W50, manufactured by Nippon Paper Industries Co., Ltd.): 1.90 g (11.76 mmol) was placed in a 200 mL three-neck flask, and 25.4 mL of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) and 3 g of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as solvents, followed by mechanical stirring at 300 rpm for 4 hours.

[0156] Thereafter, the internal temperature was cooled to -4°C, and 2.61 g (35.27 mmol) of propionic acid (Kanto Chemical Co., Ltd.) was added dropwise thereto, followed by a reaction for 12 hours at an internal temperature of 90°C. Thereafter, the internal temperature was cooled to 65°C, and 50 mL of methanol was added to terminate the reaction.

[0157] 10 mL of pure water was added thereto and filtered under reduced pressure, and then the residue was dispersed in 25 mL of methanol, stirred, and filtered under reduced pressure. This procedure was repeated five times, and the mixture was dried in vacuo for 12 hours.

[0158] The obtained solid was mixed with 12.3 g of 1-methylimidazole (Tokyo Chemical Industry Co., Ltd.) at room temperature, and the mixture was reacted at 100° C. for 4 hours.

[0159] This reaction solution was poured into a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), vigorously stirred for 5 minutes, and then allowed to stand. The upper layer, which separated into two layers, was then removed by decantation. This procedure was repeated two more times, and the remaining lower layer was heated and vacuum dried at 100°C for 1 hour while stirring, yielding a wine-colored liquid cellulose derivative at room temperature.

[0160] (Synthesis Example 11) A mixture of 238 g (1000 mmol) of triethyl 3-phosphonopropionate and 1000 mL of a 30% by weight solution of hydrogen bromide in acetic acid (approximately 5.1 mol / L) was heated at 90°C overnight with stirring, and then diethyl ether was added. The resulting solid oil was then washed with diethyl ether (1000 mL x 3) to obtain a slightly yellow, viscous oil. This slightly yellow, viscous oil was dried under vacuum overnight to obtain 154 g of 3-[(hydroxyphosphinyl)oxy]propanoic acid.

[0161] Cellulose (KC Flock W50, manufactured by Nippon Paper Industries Co., Ltd.): 1.90 g (11.76 mmol) was placed in a 200 mL three-neck flask, and 25.4 mL of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) and 3 g of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as solvents, followed by mechanical stirring at 300 rpm for 4 hours.

[0162] Thereafter, the internal temperature was cooled to −4° C., and 2.1 g of 3-[(hydroxyphosphinyl)oxy]propanoic acid was added dropwise thereto, followed by a reaction for 12 hours at an internal temperature of 90° C. Thereafter, the internal temperature was cooled to 65° C., and 50 mL of methanol was added to terminate the reaction.

[0163] 10 mL of pure water was added thereto and filtered under reduced pressure, and then the residue was dispersed in 25 mL of methanol, stirred, and filtered under reduced pressure. This procedure was repeated five times, and the mixture was dried in vacuo for 12 hours.

[0164] The obtained solid was mixed with 12.3 g of 1-methylimidazole (Tokyo Chemical Industry Co., Ltd.) at room temperature, and the mixture was reacted at 100° C. for 4 hours.

[0165] This reaction solution was poured into a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), vigorously stirred for 5 minutes, and then allowed to stand. The upper layer, which separated into two layers, was then removed by decantation. This procedure was repeated two more times, and the remaining lower layer was heated and vacuum dried at 100°C for 1 hour while stirring, yielding a wine-colored liquid cellulose derivative at room temperature.

[0166] (Synthesis Example 12) A mixture of 238 g (1000 mmol) of triethyl 3-phosphonopropionate and 1000 mL of a 30% by weight solution of hydrogen bromide in acetic acid (approximately 5.1 mol / L) was heated at 90°C overnight with stirring, and then diethyl ether was added. The resulting solid oil was then washed with diethyl ether (1000 mL x 3) to obtain a slightly yellow, viscous oil. This slightly yellow, viscous oil was dried under vacuum overnight to obtain 154 g of 3-[(hydroxyphosphinyl)oxy]propanoic acid.

[0167] Cellulose (KC Flock W50, manufactured by Nippon Paper Industries Co., Ltd.): 1.90 g (11.76 mmol) was placed in a 200 mL three-neck flask, and 25.4 mL of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) and 3 g of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as solvents, followed by mechanical stirring at 300 rpm for 4 hours.

[0168] The internal temperature was then cooled to -4°C, and 4.2 g of 3-[(hydroxyphosphinyl)oxy]propanoic acid and 2.61 g (35.27 mmol) of propionic acid (Kanto Chemical Co., Ltd.) were added dropwise thereto, followed by a reaction for 12 hours at an internal temperature of 90°C. The internal temperature was then cooled to 65°C, and 50 mL of methanol was added to terminate the reaction.

[0169] 10 mL of pure water was added thereto and filtered under reduced pressure, and then the residue was dispersed in 25 mL of methanol, stirred, and filtered under reduced pressure. This procedure was repeated five times, and the mixture was dried in vacuo for 12 hours.

[0170] The obtained solid was mixed with 12.3 g of 1-methylimidazole (Tokyo Chemical Industry Co., Ltd.) at room temperature, and the mixture was reacted at 100° C. for 4 hours.

[0171] This reaction solution was poured into a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), vigorously stirred for 5 minutes, and then allowed to stand. The upper layer, which separated into two layers, was then removed by decantation. This procedure was repeated two more times, and the remaining lower layer was heated and vacuum dried at 100°C for 1 hour while stirring, yielding a wine-colored liquid cellulose derivative at room temperature.

[0172] (Synthesis Example 13) A cellulose derivative was synthesized in the same manner as in Synthesis Example 12, except that 14.4 g of 1-ethylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 12.3 g of 1-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0173] (Synthesis Example 14) Cellulose (KC Flock W50, manufactured by Nippon Paper Industries Co., Ltd.): 1.90 g (11.76 mmol) was placed in a 200 mL three-neck flask, and 25.4 mL of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) and 3 g of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as solvents, followed by mechanical stirring at 300 rpm for 4 hours.

[0174] Thereafter, the internal temperature was cooled to -4°C, and 3.05 g (27 mmol) of chloroacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.61 g (35.27 mmol) of propionic acid (manufactured by Kanto Chemical Co., Ltd.) were added dropwise thereto, and the reaction was carried out for 12 hours at an internal temperature of 90°C. Thereafter, the internal temperature was cooled to 65°C, and 50 mL of methanol was added to stop the reaction.

[0175] 10 mL of pure water was added thereto and filtered under reduced pressure, and then the residue was dispersed in 25 mL of methanol, stirred, and filtered under reduced pressure. This procedure was repeated five times, and the mixture was dried in vacuo for 12 hours.

[0176] The obtained solid was mixed with 10.78 g (27 mmol) of triethylsulfonium bis(trifluoromethylsulfonyl)imide (Merck) at room temperature, and the mixture was reacted at 100° C. for 4 hours.

[0177] This reaction solution was poured into a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), vigorously stirred for 5 minutes, and then allowed to stand. The upper layer, which separated into two layers, was then removed by decantation. This procedure was repeated two more times, and the remaining lower layer was heated and vacuum dried at 100°C for 1 hour while stirring, yielding a wine-colored liquid cellulose derivative at room temperature.

[0178] (Synthesis Example 15) Cellulose (KC Flock W50, manufactured by Nippon Paper Industries Co., Ltd.): 1.90 g (11.76 mmol) was placed in a 200 mL three-neck flask, and 25.4 mL of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) and 3 g of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as solvents, followed by mechanical stirring at 300 rpm for 4 hours.

[0179] Thereafter, the internal temperature was cooled to -4°C, and 3.05 g (27 mmol) of chloroacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.61 g (35.27 mmol) of propionic acid (manufactured by Kanto Chemical Co., Ltd.) were added dropwise thereto, and the reaction was carried out for 12 hours at an internal temperature of 90°C. Thereafter, the internal temperature was cooled to 65°C, and 50 mL of methanol was added to stop the reaction.

[0180] 10 mL of pure water was added thereto and filtered under reduced pressure, and then the residue was dispersed in 25 mL of methanol, stirred, and filtered under reduced pressure. This procedure was repeated five times, and the mixture was dried in vacuo for 12 hours.

[0181] The obtained solid was mixed with 5.919 g (27 mmol) of potassium bis(fluorosulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 12.3 g of 1-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) at room temperature, and the mixture was reacted at 100° C. for 4 hours.

[0182] This reaction solution was poured into a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), vigorously stirred for 5 minutes, and then allowed to stand. The upper layer, which separated into two layers, was then removed by decantation. This procedure was repeated two more times, and the remaining lower layer was heated and vacuum dried at 100°C for 1 hour while stirring, yielding a wine-colored liquid cellulose derivative at room temperature.

[0183] (Synthesis Example 16) Cellulose (KC Flock W50, manufactured by Nippon Paper Industries Co., Ltd.): 1.90 g (11.76 mmol) was placed in a 200 mL three-neck flask, and 25.4 mL of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) and 3 g of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as solvents, followed by mechanical stirring at 300 rpm for 4 hours.

[0184] Thereafter, the internal temperature was cooled to -4°C, and 3.05 g (27 mmol) of chloroacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.61 g (35.27 mmol) of propionic acid (manufactured by Kanto Chemical Co., Ltd.) were added dropwise thereto, and the reaction was carried out for 12 hours at an internal temperature of 90°C. Thereafter, the internal temperature was cooled to 65°C, and 50 mL of methanol was added to stop the reaction.

[0185] 10 mL of pure water was added thereto and filtered under reduced pressure, and then the residue was dispersed in 25 mL of methanol, stirred, and filtered under reduced pressure. This procedure was repeated five times, and the mixture was dried in vacuo for 12 hours.

[0186] The obtained solid was mixed with 6.18 g (27 mmol) of 1-butyl-1-methylpyrrolidinium tetrafluoroborate (manufactured by Tokyo Chemical Industry Co., Ltd.) at room temperature, and the mixture was reacted at 100° C. for 4 hours.

[0187] This reaction solution was poured into a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), vigorously stirred for 5 minutes, and then allowed to stand. The upper layer, which separated into two layers, was then removed by decantation. This procedure was repeated two more times, and the remaining lower layer was heated and vacuum dried at 100°C for 1 hour while stirring, yielding a wine-colored liquid cellulose derivative at room temperature.

[0188] (Synthesis Example 17) Cellulose (KC Flock W50, manufactured by Nippon Paper Industries Co., Ltd.): 1.90 g (11.76 mmol) was placed in a 200 mL three-neck flask, and 25.4 mL of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) and 3 g of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as solvents, followed by mechanical stirring at 300 rpm for 4 hours.

[0189] Thereafter, the internal temperature was cooled to -4°C, and 3.05 g (27 mmol) of chloroacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.61 g (35.27 mmol) of propionic acid (manufactured by Kanto Chemical Co., Ltd.) were added dropwise thereto, and the reaction was carried out for 12 hours at an internal temperature of 90°C. Thereafter, the internal temperature was cooled to 65°C, and 50 mL of methanol was added to stop the reaction.

[0190] 10 mL of pure water was added thereto and filtered under reduced pressure, and then the residue was dispersed in 25 mL of methanol, stirred, and filtered under reduced pressure. This procedure was repeated five times, and the mixture was dried in vacuo for 12 hours.

[0191] The obtained solid was mixed with 7.69 g (27 mmol) of 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) at room temperature, and the mixture was reacted at 100° C. for 4 hours.

[0192] This reaction solution was poured into a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), vigorously stirred for 5 minutes, and then allowed to stand. The upper layer, which separated into two layers, was then removed by decantation. This procedure was repeated two more times, and the remaining lower layer was heated and vacuum dried at 100°C for 1 hour while stirring, yielding a wine-colored liquid cellulose derivative at room temperature.

[0193] (Synthesis Example 18) A mixture of 238 g (1000 mmol) of triethyl 3-phosphonopropionate and 1000 mL of a 30% by weight solution of hydrogen bromide in acetic acid (approximately 5.1 mol / L) was heated at 90°C overnight with stirring, and then diethyl ether was added. The resulting solid oil was then washed with diethyl ether (1000 mL x 3) to obtain a slightly yellow, viscous oil. This slightly yellow, viscous oil was dried under vacuum overnight to obtain 154 g (1000 mmol) of 3-[(hydroxyphosphinyl)oxy]propanoic acid as compound X.

[0194] Also, propionic acid was prepared as compound Y. Compound Z was also obtained as follows.

[0195] That is, first, 68.08 g (1000 mmol) of imidazole (Tokyo Chemical Industry Co., Ltd.) and 108.97 g (1000 mmol) of bromoethane (Tokyo Chemical Industry Co., Ltd.) were heated and stirred at 60°C for 2 hours in 500 mL of tetrahydrofuran (Wako Pure Chemical Industries, Ltd.), and the solvent was removed by filtration under reduced pressure. Then, the mixture was heated and refluxed in a large amount of tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) for 24 hours, and the solvent and impurities were removed by filtration under reduced pressure to obtain solid compound Z.

[0196] Cellulose (KC Flock W50, manufactured by Nippon Paper Industries Co., Ltd.): 1.90 g (11.76 mmol) was placed in a 200 mL three-neck flask, and 25.4 mL of N-methyl-2-pyrrolidinone (manufactured by Kanto Chemical Co., Ltd.) and 3 g of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as solvents, followed by mechanical stirring at 300 rpm for 4 hours.

[0197] The internal temperature was then cooled to -4°C, and 2.1 g (14 mmol) of compound X and 2.61 g (35.27 mmol) of compound Y were added dropwise thereto, followed by a reaction for 12 hours at an internal temperature of 90°C. The internal temperature was then cooled to 65°C, and 50 mL of methanol was added to terminate the reaction.

[0198] 10 mL of pure water was added thereto and filtered under reduced pressure, and then the residue was dispersed in 25 mL of methanol, stirred, and filtered under reduced pressure. This procedure was repeated five times, and the mixture was dried in vacuo for 12 hours.

[0199] The obtained solid was mixed with the above compound Z at room temperature (25°C), and the mixture was reacted at 100°C for 4 hours.

[0200] This reaction solution was poured into a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), vigorously stirred for 5 minutes, and then allowed to stand. The upper layer, which separated into two layers, was then removed by decantation. This procedure was repeated two more times, and the remaining lower layer was heated and vacuum dried at 100°C for 1 hour while stirring, yielding a wine-colored liquid cellulose derivative at room temperature (25°C; the same applies below).

[0201] (Synthesis Example 19) A liquid cellulose derivative was obtained in the same manner as in Synthesis Example 18, except that the compound Z was a compound synthesized as follows.

[0202] That is, the compound Z used in this synthesis example was synthesized as follows. First, 68.08 g (1000 mmol) of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 249.24 g (1000 mmol) of 1-bromododecane (manufactured by Tokyo Chemical Industry Co., Ltd.) were heated and stirred at 60°C for 2 hours in 500 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and the solvent was removed by filtration under reduced pressure. Then, the mixture was heated and refluxed in a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) for 24 hours, and the solvent and impurities were removed by filtration under reduced pressure to obtain solid compound Z.

[0203] (Synthesis Example 20) A liquid cellulose derivative was obtained in the same manner as in Synthesis Example 18, except that the compound Z was a compound synthesized as follows.

[0204] That is, the compound Z used in this synthesis example was synthesized as follows. First, 68.08 g (1000 mmol) of imidazole (Tokyo Chemical Industry Co., Ltd.) and 333.40 g (1000 mmol) of 1-bromooctadecane (Tokyo Chemical Industry Co., Ltd.) were heated and stirred at 60°C for 2 hours in 500 mL of tetrahydrofuran (Wako Pure Chemical Industries, Ltd.), and the solvent was removed by filtration under reduced pressure. Then, the mixture was heated and refluxed in a large amount of tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) for 24 hours, and the solvent and impurities were removed by filtration under reduced pressure to obtain solid compound Z.

[0205] The conditions for synthesizing the cellulose derivatives in each synthesis example are summarized in Figure 2. The cellulose derivatives obtained in each synthesis example all had a number average molecular weight in the range of 10,000 to 400,000 and a glass transition temperature in the range of 80°C to 200°C.

[0206] [5] Preparation of molding material Example 1 Cellulose fiber (manufactured by CMPC, Guaiba BEKP): 60 parts by mass, the cellulose derivative synthesized in Synthesis Example 1: 20 parts by mass, and cellulose acetate propionate (manufactured by Eastman Chemical Co., CAP-482-20): 20 parts by mass were weighed. These were then charged into a twin-screw kneader (manufactured by Technovel Co., KZW15TW-45MG) and kneaded. The kneading conditions were a maximum heating temperature of 180°C and an extrusion discharge rate of 1 kg / hr. Next, the strands were processed into a strand-like material and then pelletized using a pelletizer to produce a molding material in the form of pellets.

[0207] Examples 2 to 22 Pellets of molding material were prepared in the same manner as in Example 1, except that the types of components to be kneaded and the compounding ratio of each component were changed as shown in FIGS.

[0208] (Comparative Examples 1 to 3) A pellet-shaped molding material was prepared in the same manner as in Example 1, except that the types of components to be kneaded and the compounding ratio of each component were changed as shown in FIG.

[0209] [6] Manufacturing of molded bodies The molding materials of each of the examples and comparative examples were injection molded using an injection molding machine (THX40-5V, manufactured by Nissei Plastic Industrial Co., Ltd.) to produce molded articles for evaluating flexural modulus, flexural strength, and Charpy impact strength, as described below. The heating temperature of the molding materials during injection molding was 200°C. The molded articles for evaluating flexural modulus and flexural strength were rectangular plate-shaped molded articles with long sides of 80 mm ± 2 mm, short sides of 10.0 mm ± 0.2 mm, and thicknesses of 4.0 mm ± 0.2 mm. The molded article for evaluating Charpy impact strength was a rectangular plate-shaped molded article with long sides of 80 mm ± 2 mm, short sides of 4.0 mm ± 0.2 mm, and thicknesses of 10.0 mm ± 0.2 mm.

[0210] [7] Evaluation The molded articles according to the above-mentioned Examples and Comparative Examples were evaluated as follows.

[0211] [7-1] Flexural modulus The flexural modulus of each molded article for evaluating the flexural modulus of each of the Examples and Comparative Examples, which was produced as described in [6] above, was measured using an Instron 68TM-30 in accordance with ISO 178 (JIS K7171), and evaluated according to the following criteria: The distance between supports was 64 mm in the measurement of the flexural modulus.

[0212] A: The flexural modulus is 2.0 GPa or more. B: The flexural modulus is 1.5 GPa or more and less than 2.0 GPa. C: The flexural modulus is 1.0 GPa or more and less than 1.5 GPa. D: The flexural modulus is less than 1.0 GPa.

[0213] [7-2] Bending strength The flexural strength of each molded article for evaluation of flexural strength according to each of the Examples and Comparative Examples, which was produced as described in [6] above, was measured using an Instron 68TM-30 in accordance with ISO 178 (JIS K7171), and evaluated according to the following criteria: The flexural strength was measured with a support distance of 64 mm.

[0214] A: The bending strength is 60 MPa or more. B: The bending strength is 40 MPa or more and less than 60 MPa. C: The bending strength is 20 MPa or more and less than 40 MPa. D: The bending strength is less than 20 MPa.

[0215] [7-3] Charpy impact strength The Charpy impact strength of each of the molded articles for Charpy impact strength evaluation according to each of the Examples and Comparative Examples, which were produced as described in [6] above, was measured in accordance with ISO 179 (JIS K7111) using an Impact Tester IT manufactured by Toyo Seiki Seisaku-sho, Ltd., and evaluated according to the following criteria: The hammer weight was 4J (WR 2.14 N / m), the lifting angle was 150°, the notch remaining width was 8.0 mm ± 0.2 mm, and the notch angle was 45°.

[0216] A: Charpy impact strength is 10kJ / m 2 That's all. B: Charpy impact strength is 8kJ / m 2 More than 10kJ / m 2 is less than. C: Charpy impact strength is 6kJ / m 2 More than 8kJ / m 2 is less than. D: Charpy impact strength is 6kJ / m 2 is less than.

[0217] [7-4] Melt flow rate The melt flow rate of each molding material in each of the Examples and Comparative Examples was determined by measuring at 190°C and a load of 21.2 N in accordance with ISO 1133, and evaluated according to the following criteria: The higher the melt flow rate, the better the moldability.

[0218] A: The melt flow rate is 20g / 10min or more. B: The melt flow rate is 10 g / 10 min or more and less than 20 g / 10 min. C: The melt flow rate is 5 g / 10 min or more and less than 10 g / 10 min. D: The melt flow rate is less than 5 g / 10 min.

[0219] These results are shown together in FIGS. 3 and 4, along with the compositions of the molding materials obtained in the respective Examples and Comparative Examples, and the methods for molding molded articles using the molding materials.

[0220] In Figures 3 and 4, cellulose fiber (Guaiba BEKP, manufactured by CMPC) is referred to as "cellulose fiber," cellulose acetate propionate (CAP-482-20, manufactured by Eastman Chemical Co.) is referred to as "CAP," cellulose acetate butyrate (CAB-381-20, manufactured by Eastman Chemical Co.) is referred to as "CAB," diacetate cellulose (DAC:L-70, manufactured by Daicel Millize Co.) is referred to as "DAC," and melt flow rate is referred to as "MFR." The numerical values for each component in Figures 3 and 4 indicate the content in mass%.

[0221] As is clear from Figures 3 and 4, excellent results were obtained in each of the Examples, whereas satisfactory results were not obtained in each of the Comparative Examples.

[0222] In addition, molding materials were produced in the same manner as in each of the above examples, except that triphenyl phosphate was added as a flame retardant so that the content ratio of the cellulose fiber, the specific cellulose derivative, and the cellulose derivative having an acetyl group but not having a second chemical structure to the total content was 1 mass% or more and 20 mass% or less, and the same evaluations as above were performed on these materials, and the same results as above were obtained.

[0223] In addition, molding materials were produced in the same manner as in each of the above examples, except that the cation structure of the chemical structure having an acetyl group and not having a second chemical structure was changed to that represented by the above formula (8), formula (10), or formula (11).These materials were evaluated in the same manner as above, and the same results as above were obtained.

Claims

1. A molding material comprising cellulose fibers and a specific cellulose derivative in which some of the hydrogen atoms constituting hydroxyl groups of the cellulose are substituted with a first chemical structure which is a chemical structure of at least one of the following general formulas (A) and (B), and other hydrogen atoms are substituted with a second chemical structure which is a chemical structure of the following general formula (C). 【Chemical 1】 (In formula (A), RA is a monovalent hydrocarbon group having 1 to 8 carbon atoms.) 【Chemistry 2】 (In formula (B), RB is a monovalent hydrocarbon group having 1 to 8 carbon atoms.) 【Chemistry 3】 (In formula (C), R represents a divalent hydrocarbon group having 1 to 8 carbon atoms, and X － is an anionic chemical structure, and Y ＋ is a cationic chemical structure.)

2. The X － is at least one of the following formulas (1) to (5), The Y ＋ The molding material according to claim 1, wherein is at least one of the following formulas (6) to (11): 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 (In formula (6), n is an integer of 1 or more and 18 or less.) 【Chemistry 10】 (In formula (7), n is an integer of 1 or more and 18 or less.) 【Chemistry 11】 (In formula (8), n is an integer of 1 or more and 18 or less.) 【Chemistry 12】 (In formula (9), n is an integer of 1 or more and 18 or less.) 【Chemistry 13】 (In formula (10), n is an integer of 1 or more and 18 or less.) 【Chemistry 14】 (In formula (11), n is an integer of 1 or more and 18 or less.)

3. The molding material according to claim 1 or 2, further comprising a cellulose derivative having an acetyl group and not having the second chemical structure.

4. 4. The molding material according to claim 3, wherein the cellulose derivative having the acetyl group and not having the second chemical structure has at least one alkyl group having 1 to 18 carbon atoms as a modifying group, and the DS value of the acetyl group is a value in the range of 1.0 to 2.

5.

5. 4. The molding material according to claim 3, wherein the cellulose derivative having an acetyl group and not having the second chemical structure is at least one selected from the group consisting of cellulose acetate propionate, cellulose acetate butyrate, and diacetate cellulose.

6. 4. The molding material according to claim 3, wherein the content of the cellulose fiber in the molding material is XF [mass%], the content of the specific cellulose derivative is XD1 [mass%], and the content of the cellulose derivative having the acetyl group and not having the second chemical structure is XD2 [mass%]. The value of [XF / (XF + XD1 + XD2)] × 100 is 50 or more and 80 or less.

7. 4. The molding material according to claim 3, wherein the content of the cellulose fiber in the molding material is XF [mass%], the content of the specific cellulose derivative is XD1 [mass%], and the content of the cellulose derivative having the acetyl group and not having the second chemical structure is XD2 [mass%]. The value of [XD1 / (XF + XD1 + XD2)] × 100 is 10 or more and 50 or less.

8. The molding material according to claim 3, wherein the content of the cellulose fiber in the molding material is XF [mass%], the content of the specific cellulose derivative is XD1 [mass%], and the content of the cellulose derivative having the acetyl group and not having the second chemical structure is XD2 [mass%], the value of [XD2 / (XF + XD1 + XD2)] × 100 is 10 or more and 40 or less.

9. The molding material according to claim 1 or 2, further comprising a flame retardant.

10. The molding material further includes a cellulose derivative having an acetyl group and not having the second chemical structure, and a flame retardant, In the molding material, the content of the cellulose fiber is XF [% by mass], the content of the specific cellulose derivative is XD1 [% by mass], the content of the cellulose derivative having the acetyl group and not having the second chemical structure is XD2 [% by mass], and the content of the flame retardant is XR [% by mass], and the value of [XR / (XF+XD1+XD2)]×100 is The molding material according to claim 1 or 2, wherein the molecular weight is 1 or more and 20 or less.

11. The molding material according to claim 1 or 2, wherein the DS value of the first chemical structure in the specific cellulose derivative is 1.2 or more and 2.6 or less.

12. The molding material according to claim 1 or 2, wherein the DS value of the second chemical structure in the specific cellulose derivative is 0.1 or more and 0.8 or less.

13. The molding material according to claim 1 or 2, wherein the cellulose fibers have an average length of 500 μm or less.

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