JP2014162804A - Cellulose-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cellulose-based resin composition improved in impact resistance.SOLUTION: There is provided a cellulose-based resin composition which contains the following cellulose-based resin (X) and the following polar group-containing rubber (Y), in which the following cellulose-based resin (X) and the following polar group-containing rubber (Y) are chemically unbonded to each other. (X) A cellulose-based resin in which at least one selected from the group consisting of a carboxylic acid having 1 to 32 carbon atoms, an alcohol and a derivative thereof is bonded to at least one of a cellulose and a derivative thereof, (Y) A polar group-containing rubber has at least one polar group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, a nitrile group, an ester group, a hydroxyl group, an amino group, a formyl group and an epoxy group in the structure.

Description

  The present invention relates to a cellulose resin composition and its use.

  Bioplastics made from plant materials can contribute to environmental measures, and therefore are being used in various fields. Among the bioplastics, various bioplastics using cellulose, which is a main component of wood and vegetation, have already been developed and commercialized as bioplastics made from non-edible parts. Specifically, for example, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate and the like are used in many fields as cellulose esters which are cellulose derivatives.

  Cellulose is a polymer in which β-glucose is polymerized, but has high crystallinity, so it is hard and brittle and has no thermoplasticity. Furthermore, since cellulose contains many hydroxy groups, its water absorption is high and its water resistance is low. Therefore, various studies for improving the characteristics of cellulose have been conducted.

  For example, Patent Document 1 discloses a biodegradable graft polymer having thermoplasticity obtained by ring-opening graft polymerization of ε-caprolactone to cellulose acetate having a hydroxy group.

  On the other hand, materials using non-edible part components other than cellulose are also being developed. For example, cardanol derived from cashew nut shell has been applied to various uses because it has a stable molecular output and is excellent in functionality from a characteristic molecular structure. As an example using cardanol, Patent Document 2 discloses a brake substrate formed by using a fiber base material made of aramid pulp and cellulose fiber, a filler made of calcium carbonate and cashew dust, and a binder made of phenol resin. A friction material is disclosed. Patent Document 3 discloses a cellulose resin in which cardanol or a derivative thereof and further a reactive rubber are bonded to mercerized cellulose. In Patent Document 4, as a method for improving the impact resistance of a cellulose derivative, a cellulose derivative in which both an ether structure and an ester structure are introduced into cellulose is used, and the cellulose derivative and an aliphatic polyester elastomer are used. The containing molding material is disclosed.

Non-Patent Document 1 describes that the water resistance of paper can be improved by immersing the paper sheet in cardanol and performing a grafting reaction in which cardanol is bonded to cellulose constituting the paper sheet. In the grafting reaction, it is described that a terminal double bond of cardanol and a hydroxy group of cellulose are bonded in the presence of boron trifluoride diethyl ether (BF ₃ -OEt ₂ ).

  Cellulosic bioplastics are inferior in strength, heat resistance, water resistance, thermoplasticity, and impact resistance compared to petroleum plastics. In particular, these characteristics are improved when applied to durable products such as exteriors for electronic devices. is necessary. However, when a plasticizer obtained from petroleum raw materials is added in order to improve thermoplasticity, the plant utilization rate (plantiness) is reduced, heat resistance and strength (particularly rigidity) are reduced, uniformity is reduced, and There is a problem that bleed out of the plasticizer (seepage of the plasticizer to the surface of the molded body) occurs. In addition, when a normal soft component is added to improve impact resistance, the soft component may bleed out during molding of the bioplastic, which may hinder moldability.

JP-A-11-255801 Japanese Patent Laid-Open No. 10-8035 JP 2012-219112 A JP2011-148975

George John et al. Polymer Bulletin, 22, p.89-94 (1989)

  Therefore, an object of the present invention is to provide a cellulose resin composition having improved impact resistance.

The cellulose resin composition of the present invention includes the following cellulose resin (X) and the following polar group-containing rubber (Y),
The cellulose resin (X) and the polar group-containing rubber (Y) are chemically unbonded.
(X) Cellulose-based resin (Y) having at least one selected from the group consisting of carboxylic acids having 1 to 32 carbon atoms, alcohols and derivatives thereof to at least one of cellulose and derivatives thereof (Y) carboxyl group, carboxylic acid anhydride Polar group-containing rubber having in its structure at least one polar group selected from the group consisting of physical groups, nitrile groups, ester groups, hydroxyl groups, amino groups, halogens, nitro groups, formyl groups and epoxy groups

  The molding material of the present invention comprises the cellulose resin composition of the present invention.

  The molded product of the present invention is characterized by including the cellulose resin composition of the present invention.

  The cellulose resin composition of the present invention can improve impact resistance.

  As described above, the present inventors include the polar group to the cellulose resin by including the cellulose resin (X) and the polar group-containing rubber (Y) in a chemically unbonded state. It has been found that the dispersibility of rubber can be improved. The cellulose-based resin (X) in the present invention has an acyl group or an ether group in its structure due to the binding of the carboxylic acid or the alcohol to the hydroxy group of cellulose or a derivative thereof. Thus, by using the cellulose resin (X) having an acyl group or an ether group and the polar group-containing rubber (Y), the former acyl group or ether group and the latter polar group It is considered that the dispersibility is improved as described above by the synergistic effect. And by containing the said cellulose resin (X) and the said polar group containing rubber (Y) in a chemically unbonded state, while improving impact resistance about a cellulose resin composition, it is mechanical characteristics. (Especially toughness), water resistance and plasticity can be improved. For this reason, for example, the amount of the plasticizer added to the cellulose resin composition can be reduced, or the plasticizer can be not added, and the heat resistance of the cellulose resin composition due to the addition of the plasticizer can be reduced. In addition to suppressing a decrease in property and strength (particularly rigidity), the bleeding out of the additive in the molded article can also be suppressed. Furthermore, in the present invention, it is not necessary to bond the cellulose resin (X) and the polar group-containing rubber (Y) by a chemical reaction. For this reason, it was possible to produce easily, and it became possible to improve the bending strength as compared with the case where the cellulose resin (X) and the polar group-containing rubber (Y) were chemically bonded.

1. Cellulose-based resin composition The cellulose-based resin composition of the present invention includes, as described above, the following cellulose-based resin (X) and the following polar group-containing rubber (Y), and the cellulose-based resin (X) and the above-mentioned The polar group-containing rubber (Y) is chemically unbonded.
(X) Cellulose-based resin (Y) having at least one selected from the group consisting of carboxylic acids having 1 to 32 carbon atoms, alcohols and derivatives thereof to at least one of cellulose and derivatives thereof (Y) carboxyl group, carboxylic acid anhydride Polar group-containing rubber having in its structure at least one polar group selected from the group consisting of physical groups, nitrile groups, ester groups, hydroxyl groups, amino groups, halogens, nitro groups, formyl groups and epoxy groups

In the present invention, the cellulose resin (X) can also be referred to as a cellulose resin having at least one of an acyl group and an ether group. Specifically, examples of the cellulose resin (X) include a resin in which at least one of the following (X1) and (X2) is bonded to at least one of cellulose and a derivative thereof.
(X1) at least one of carboxylic acids having 1 to 32 carbon atoms and derivatives thereof (X2) at least one of alcohols having 1 to 32 carbon atoms and derivatives thereof

  Hereinafter, unless otherwise indicated, the description of “cellulose” can be replaced with a cellulose derivative.

  In the cellulose resin composition, the cellulose resin (X) may be, for example, one in which the (X1) or (X2) is bonded to cellulose, or the (X1) or (X2) is bonded to a cellulose derivative. Or may include both. In the cellulose resin (X), for example, it is preferable that the hydrogen atom H of the hydroxyl group contained in the cellulose is not substituted with a hydrocarbon group.

  In the cellulose-based resin composition, the cellulose-based resin (X) may be, for example, one in which any one of the (X1) and (X2) is bonded to one of cellulose and a derivative thereof. Two types may be combined.

Among the cellulose-based resins (X), the resin in which the (X1) is bonded to at least one of cellulose and its derivatives can be referred to as a resin in which the following (X1 ′) is added, for example.
(X1) at least one of carboxylic acid having 1 to 32 carbon atoms (R—CO—OH) and derivatives thereof (X1 ′) at least one of acyl group having 1 to 32 carbon atoms (R—CO—) and derivatives thereof

  The resin to which the (X1) is bonded is obtained by reacting, for example, a cellulose hydroxy group or a substituent thereof with a carboxyl group (—COOH) of a carboxylic acid having 1 to 32 carbon atoms or a substituent thereof into the cellulose. An acyl group having 1 to 32 carbon atoms (R—CO—) or a derivative thereof is added. Specifically, for example, the hydrogen atom H of the hydroxy group (—OH) of the cellulose is substituted with the acyl group (R—CO—) or a derivative thereof, and the carbon of the cellulose has a carboxyl group (R—CO). -O-) is bonded (added). The reaction of the hydroxy group of the cellulose or a substituent thereof and the carboxyl group or the substituent thereof is, for example, a dehydration reaction and forms an ester bond. In the carboxyl group or a substituent thereof, the hydroxy group or the substituent thereof, for example, the hydrogen may be substituted with a halogen (X) such as Cl, F, Br, or I. In this case, for example, a de-HOX bond occurs between —COOX and —OH or between —COOH and —OX.

Among the cellulose-based resins (X), the resin in which the (X2) is bonded to at least one of cellulose and its derivatives can be referred to as a resin in which the following (X2 ′) is added, for example.
(X2) C1-C32 alcohol (ROH) and / or its derivative (X2 ′) C1-C32 ether group (RO—) and / or its derivative

  The resin to which the (X2) is bonded is, for example, obtained by reacting the cellulose hydroxy group or a substituent thereof with the hydroxy group (—OH) of a C 1 to C 32 alcohol or the substituent thereof into the cellulose. The ether group (RO-) of 1 to 32 or a derivative thereof is added. Specifically, for example, the hydrogen atom H of the hydroxy group (—OH) of the cellulose is substituted with a hydrocarbon group (R—) having 1 to 32 carbon atoms or a derivative thereof, and an ether group is added to the carbon of the cellulose. (RO-) or a derivative thereof is bound (added). The reaction between the hydroxy group of the cellulose or a substituent thereof and the hydroxy group of the alcohol or the substituent thereof is, for example, a dehydration reaction and forms an ether bond. In the hydroxy group or a substituent thereof, for example, the hydrogen may be substituted with halogen (X) such as Cl, F, Br, or I. In this case, for example, a de-HOX bond occurs between -OX and -OH.

  Specific examples of the cellulose resin (X) include cellulose acetate propionate and cellulose acetate butyrate.

  In the cellulose resin (X), for example, at least one of cardanol and a derivative thereof may be bonded as the alcohol. Examples of the bond include grafting of cardanol or a derivative thereof. Specific examples of the cellulose resin (X) include cardanol grafted cellulose acetate propionate and cardanol grafted cellulose acetate butyrate.

  In the cellulose resin composition of the present invention, the cellulose resin (X) may be, for example, any one kind or a combination of two or more kinds. The resin component in the cellulose resin composition of the present invention may be, for example, only the cellulose resin (X) or may contain other resins.

  In the cellulose resin composition of the present invention, the polar group-containing rubber (Y) may be a rubber having the polar group. Examples of the polar group include a carboxyl group, a carboxylic anhydride group, a nitrile group, an ester group, a hydroxyl group, an amino group, a halogen, a nitro group, a formyl group, and an epoxy group as described above. The polar group-containing rubber (Y) may have, for example, any one type of polar group or two or more types of polar groups. The polar group-containing rubber (Y) is preferably a polar group-containing rubber having no isocyanate group.

  The carboxylic anhydride group can be represented, for example, by the general formula —R—CO—O—CO—R ′. In the above formula, R and R ′ may be bonded to form a cyclic structure, for example. R and R ′ may be the same or different. Examples of R and R ′ include a hydrocarbon group having 1 to 6 carbon atoms and a benzene ring. Examples of the carboxylic anhydride group include groups such as maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, sebacic anhydride, and phthalic anhydride. When the polar group-containing rubber (Y) has the carboxylic acid unique group, it can also be referred to as, for example, a rubber to which a carboxylic acid anhydride group has been added or a rubber modified with a carboxylic acid anhydride.

  In the cellulose resin composition of the present invention, the polar group-containing rubber (Y) may be any one kind, or two or more kinds may be used in combination.

  Examples of the polar group-containing rubber (Y) include butadiene rubber, nitrile rubber, isoprene rubber, urethane rubber, ethylene propylene rubber, and silicone rubber. When the polar group-containing rubber (Y) has a carboxyl group, examples thereof include a carboxylic acid-terminated rubber having a carboxyl group at at least one end or both ends. Specific examples include, for example, a carboxylic acid-terminated butadiene rubber, a carboxylic acid-terminated nitrile rubber, a carboxylic acid-terminated isoprene rubber, a carboxylic acid-terminated urethane rubber, a carboxylic acid-terminated ethylene-propylene rubber, and a carboxyl group-terminated butadiene rubber having a carboxyl group at at least one end or both ends. Examples thereof include carboxylic acid-terminated silicone rubber.

  In the cellulose resin composition of the present invention, the addition ratio of the cellulose resin (X) and the polar group-containing rubber (Y) is not particularly limited. For example, the weight ratio of the cellulose resin (X) and the polar group-containing rubber (Y) is preferably 80:20 to 99: 1, more preferably 90:10 to 99: 1, more preferably 93: 7 to 97: 3.

  The cellulose resin composition of the present invention may be composed only of the cellulose resin (X) and the polar group-containing rubber (Y), and may further contain other additives.

  The present invention will be specifically described below. In addition, the following description is an illustration and this invention is not restrict | limited to these illustrations.

(1) Cellulose or a derivative thereof Cellulose is a linear polymer of β-glucose represented by the following formula (1), and each glucose unit has three hydroxy groups. The cellulose resin (X) can be synthesized, for example, by combining at least one of (X1) and (X2) using these hydroxy groups. In addition, when cardanol or a derivative thereof is bonded, for example, it is preferable to graft onto the cellulose or the derivative thereof.

  The cellulose is a main component of vegetation, and can be obtained by, for example, separating other components such as lignin from vegetation. In the present invention, for example, in addition to the cellulose thus obtained, cotton and pulp having a high cellulose content can be purified or used as they are.

  The polymerization degree of cellulose and its derivatives is not particularly limited, and for example, the glucose polymerization degree is preferably in the range of 50 to 5000, more preferably 100 to 3000. By setting the degree of polymerization within the above range, for example, a cellulose resin, a cellulose resin composition and a molded body obtained therefrom, sufficient strength and heat resistance can be obtained, and the melt viscosity of the resin is increased. It is possible to suppress the hindrance to molding.

  Examples of the cellulose derivative include those in which a substituent is introduced using cellulose as a raw material by a biological method or a chemical synthesis method. Specific examples of the cellulose derivative include those obtained by acylating, etherifying, or grafting part or all of the hydroxy groups of cellulose. Specific examples of the cellulose derivative include, for example, organic acid esters such as cellulose acetate, cellulose butyrate, and cellulose propionate; inorganic acid esters such as cellulose nitrate, cellulose sulfate, and cellulose phosphate; cellulose acetate propionate and cellulose acetate. Examples thereof include hybrid esters such as butyrate, cellulose acetate phthalate, and cellulose nitrate acetate; etherified celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose. Examples of the cellulose derivative include grafted cellulose in which a polymer such as styrene, (meth) acrylic acid, (meth) acrylic ester, ε-caprolactone, lactide, glycolide, or the like is bonded to cellulose.

  Above all, the cellulose derivative is preferably at least one acylated cellulose selected from the group consisting of cellulose acetate, cellulose propionate and cellulose butyrate in which a part of the hydroxy group of cellulose is acylated.

In the cellulose derivative, for example, the degree of substitution of hydroxy groups per glucose unit is not particularly limited. As a specific example, the average value of the number of substituents such as an acyl group introduced by reaction with a hydroxy group per glucose unit, that is, the hydroxyl group substitution degree (DS _XX ) is, for example, water resistance, mechanical properties, and From the viewpoint of heat resistance and the like, 2.0 or more and 2.8 or less are more preferable. In the cellulose derivative, for example, the average value of the number of remaining hydroxy groups per glucose unit, that is, the hydroxyl group residual degree (DS _OH ) is, for example, 0.9 or less from the viewpoint of sufficiently securing water resistance. Preferably, it is 0.7 or less.

  In the present invention, for the cellulose and the cellulose derivative, for example, any one kind may be used, or two or more kinds may be used in combination. Moreover, as for the said cellulose derivative, any one type may be used independently, and two or more types may be used together, for example.

  In the cellulose of the present invention and the cellulose derivative, as an analog of cellulose, for example, a normal non-edible polysaccharide, that is, chitin, chitosan, hemicellulose, glucomannan, β-1,3-glucan, curdlan, etc. Applicable.

  In the cellulose resin (X), for example, a hydroxy group of cellulose or a derivative thereof reacts with a carboxyl group of the carboxylic acid or a hydroxy group of an alcohol to form a glycosidic bond. Here, the reaction of the cellulose or its derivative with the carboxyl group of the carboxylic acid or the hydroxy group of the alcohol to form a glycosidic bond is also referred to as grafting of cellulose or its derivative.

  When the carboxylic acid or the alcohol has at least one of an aromatic group and an alicyclic group, the grafting of cellulose or a derivative thereof using these, for example, the bending strength of the molded product finally obtained, Effective for improving rigidity and heat resistance. Further, when the carboxylic acid or the alcohol has an aliphatic group, grafting of cellulose or a derivative thereof using these is effective for improving the toughness of the finally obtained molded article.

  As shown in said (X1) and (X2), the said carboxylic acid, the said alcohol, or these derivatives are C1-C32, Preferably it is C1-C20. When the carbon number is within this range, for example, steric hindrance can be suppressed and the grafting rate of the hydroxy group of cellulose can be increased.

  The carboxylic acid of (X1) is not particularly limited, and examples thereof include chain carboxylic acid (aliphatic carboxylic acid) and cyclic carboxylic acid. Examples of the aliphatic carboxylic acid include linear and branched aliphatic carboxylic acids, and aliphatic monocarboxylic acids are particularly preferable. Examples of the cyclic carboxylic acid include alicyclic carboxylic acids and aromatic carboxylic acids, and alicyclic monocarboxylic acids are particularly preferable. In the cyclic monocarboxylic acid, the carboxyl group may be directly bonded to, for example, an alicyclic group or an aromatic ring, or may be bonded to a substituent of the alicyclic group or the aromatic ring. The carboxylic acid may be, for example, a carboxylic acid anhydride.

  Examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated monocarboxylic acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid; butenoic acid And unsaturated monocarboxylic acids such as pentenoic acid, hexenoic acid, octenoic acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid. Examples of the alicyclic carboxylic acid include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, cyclohexyl acetic acid, and the like. Examples of the aromatic carboxylic acid include benzoic acid, toluic acid, and phenyl acetic acid. Phenylpropionic acid, biphenylcarboxylic acid, biphenylacetic acid, naphthalenecarboxylic acid, tetralincarboxylic acid and the like. Among these carboxylic acids, for example, acetic acid, propionic acid, and butyric acid are preferable.

  The derivative of the carboxylic acid has, for example, a substituent on the carboxylic acid. As the substituent, for example, a functional group having reactivity with a hydroxy group of cellulose is preferable, and specific examples include, for example, a carboxylic acid halide group such as a carboxylic acid chloride group, a carboxylic acid anhydride group, and the like. Examples thereof include an epoxy group, an isocyanate group, and a halogen atom such as a chlorine atom. Among these, for example, carboxylic acid halide groups such as carboxylic acid chloride and isocyanate groups are preferable.

  The alcohol (X2) is not particularly limited, and examples thereof include aliphatic alcohols and cyclic alcohols. Examples of the aliphatic alcohol include methanol, ethanol, propanol and the like. Examples of the cyclic alcohol include alicyclic alcohols and aromatic alcohols. Examples of the alicyclic alcohol include cyclohexylol, cycloheptalol, and the like, and examples of the aromatic alcohol include phenol.

When the alcohol of (X2) is at least one of phenol having 1 to 32 carbon atoms (C ₆ H ₅ OH) and derivatives thereof, the cellulose resin (X) is, for example, phenoxy having 1 to 32 carbon atoms. It can be said that a resin to which at least one of a group (C ₆ H ₅ O—) and a derivative thereof is added. The resin to which phenol or a derivative thereof is bonded is, for example, a cellulose having a carbon number of 1 to 1 by reacting with a hydroxy group of cellulose or a substituent thereof and a phenolic hydroxy group (—OH) of the phenol or a substituent thereof. 32 phenoxy groups (C ₆ H ₅ O—) or derivatives thereof are added. Specifically, for example, the hydrogen atom H of the hydroxy group (—OH) of the cellulose is substituted with the phenyl group (C ₆ H ₅ —) or a derivative thereof, and the phenoxy group (C ₆ H ₅ O—) or a derivative thereof is bound (added). The reaction between the hydroxy group of the cellulose or a substituent thereof and the phenolic hydroxy group or the substituent thereof is, for example, a dehydration reaction and forms an ether bond. In the hydroxy group or a substituent thereof, for example, the hydrogen may be substituted with halogen (X) such as Cl, F, Br, or I. In this case, for example, a de-HOX bond occurs between -OX and -OH.

The aromatic alcohol is preferably cardanol or a derivative thereof. Cardanol is a component contained in the shell of cashew nut, and is an organic compound having a phenol moiety and a linear hydrocarbon moiety R as shown by the following formula (2). Cardanol has four types of different unsaturated bonds in the straight-chain hydrocarbon group R, and is usually a mixture of these four types of isomers. That is, in the formula (2), the compound 3-pentadecylphenol having a pentadecyl group of R ¹ , the compound 3-pentadecylphenol monoene having an 8-pentadecenyl group of R ² , and the pentadecyl 8,11-diene group of R ³ And a mixture of compound 3-pentadecylphenoltriene having a pentadecyl 8,11,14-triene group of R ⁴ . As the cardanol, for example, a cardanol component obtained by extraction and purification from cashew nut shell liquid can be used.

In the formula (2), R is the following R ¹ , R ² , R ³ or R ⁴ , and the hydrogen of the hydroxy group (OH) may be substituted.
R ¹ : — (CH ₂ ) ₁₄ CH _{3
^{R 2: - (CH 2)}} 7 CH = CH (CH 2) 5 CH 3
_{^{R 3: - (CH 2)}} 7 CH = CHCH 2 CH = CH (CH 2) 2 CH 3
_{^{R 4: - (CH 2)}} 7 CH = CHCH 2 CH = CHCH 2 CH = CH 2

  In cardanol, the linear hydrocarbon group (R) contributes to, for example, improvement in flexibility and hydrophobicity of the resin, and the phenol moiety is, for example, a highly reactive phenolic hydroxy group used for grafting. And the hydroxy group forms, for example, a glucoside bond with cellulose or a derivative thereof. When the cardanol or a derivative thereof is bonded to cellulose or a derivative thereof, for example, a cellulose-based resin in which the cardanol component is bonded in a brush shape is formed. As a result, interaction between cardanols glycosidically bonded to cellulose or a derivative thereof is formed. For example, mechanical properties, particularly toughness can be improved, thermoplasticity can be imparted, and water resistance can be improved by the hydrophobicity of cardanol. When the glycoside bond between cardanol and cellulose or a derivative thereof is formed, a dehydration catalyst such as sulfuric acid, toluenesulfonic acid, hydrogen chloride or the like may be added.

  In cardanol, for example, the unsaturated bond (double bond) in the linear hydrocarbon group (R) portion of cardanol is preferably converted to a saturated bond by hydrogenation. By using a cardanol derivative in which the unsaturated bond of the linear hydrocarbon group is sufficiently converted to a saturated bond by hydrogenation, for example, side reactions are suppressed, and the bond between cellulose and cardanol can be efficiently performed. It can be performed, and a decrease in solubility of the product in the solvent can be suppressed. The unsaturated bond conversion rate (hydrogenation rate) by hydrogenation is, for example, preferably 90 mol% or more, and more preferably 95 mol% or more. The residual ratio of unsaturated bonds in cardanol after hydrogenation, that is, the number of unsaturated bonds per cardanol molecule is, for example, preferably 0.2 or less, more preferably 0.1 or less. It is.

The method for hydrogenating cardanol is not particularly limited, and a normal method can be used. Examples of the catalyst used in the hydrogenation reaction include noble metals such as palladium, ruthenium and rhodium, and metals such as nickel. As the catalyst, for example, a catalyst in which the various metals are supported on a support such as activated carbon, activated alumina, or diatomaceous earth can be used. As the hydrogenation reaction system, for example, a batch system in which a reaction is performed while suspending and stirring a powdered catalyst, a continuous system using a reaction tower filled with a molded catalyst, or the like can be adopted. The solvent used for the hydrogenation is not particularly limited, and may be used or may not be used depending on the reaction method, for example. When using the said solvent, normally, solvents, such as alcohol, ethers, ester, saturated hydrocarbons, are mention | raise | lifted, for example. The reaction temperature at the time of hydrogenation is not particularly limited. For example, in order to appropriately adjust the hydrogenation rate, it can be usually set to 20 to 250 ° C., preferably 50 to 200 ° C. The hydrogen pressure at the time of hydrogenation is not particularly limited, and is typically 10 to 80 kgf / cm ² (9.8 × 10 ^{5 to} 78.4 × 10 ⁵ Pa), preferably 20 to 50 kgf / cm ² ( 19.6 × 10 ^{5 to} 49.0 × 10 ⁵ Pa).

  Hydrogenation of cardanol may be performed, for example, before forming the cardanol derivative, after forming the cardanol derivative and before bonding with cellulose, or after bonding between the cardanol derivative and cellulose. Among these, from the viewpoint of, for example, hydrogenation and grafting reaction efficiency, the bonding between the cardanol derivative and cellulose is preferable, and more preferably before the formation of the cardanol derivative.

  Grafting of cellulose or a derivative thereof with the alcohol (X2) or a derivative thereof can be performed using, for example, a polyfunctional compound having a functional group that binds to both of these hydroxy groups. Then, cellulose or a derivative thereof is grafted. What the said polyfunctional compound couple | bonded with the said cellulose is a derivative | guide_body of a cellulose, for example, What the said polyfunctional compound couple | bonded with the hydroxy group of the said alcohol is a derivative | guide_body of alcohol, for example. By using the polyfunctional compound, for example, one functional group of the polyfunctional compound is bonded to a hydroxy group of an alcohol such as phenol to form a cardanol derivative, and the functional group of the cardanol derivative is bonded to cellulose. According to the coupling | bonding by the said polyfunctional compound, the reaction efficiency of the hydroxyl group of a cellulose can be improved and a side reaction can be suppressed, for example.

  The polyfunctional compound is preferably, for example, one in which a functional group that binds to a hydroxyl group of cellulose and the alcohol is bonded to a hydrocarbon group. The number of carbon atoms of the hydrocarbon group is not particularly limited, and the lower limit is preferably, for example, 1 or more, more preferably 2 or more, and the upper limit is, for example, preferably 20 or less, more preferably 14 or less, More preferably, it is 8 or less. By setting the carbon number within this range, for example, a decrease in reactivity can be suppressed and the efficiency of grafting can be improved. For example, the hydrocarbon group is preferably a divalent group, and specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a decamethylene group, Divalent linear aliphatic hydrocarbon groups such as dodecamethylene group and hexadecamethylene group; cycloheptane ring, cyclohexane ring, cyclooctane ring, bicyclopentane ring, tricyclohexane ring, bicyclooctane ring, bicyclononane ring, tricyclo And divalent alicyclic hydrocarbon groups such as a decane ring; divalent aromatic hydrocarbon groups such as a benzene ring, a naphthalene ring and a biphenylene group; Of these, for example, a chain alkylene group is preferred.

  When the hydrocarbon group is the aromatic hydrocarbon group or the alicyclic hydrocarbon group, for example, the rigidity of the resin can be improved due to their rigidity. Moreover, when the said hydrocarbon group is a linear aliphatic hydrocarbon group, the toughness of resin can be improved from the softness | flexibility, for example.

  The functional group of the polyfunctional compound is not particularly limited, and is preferably, for example, a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid halide group such as carboxylic acid chloride, an epoxy group, an isocyanate group, or a halogen atom. Among these, for example, a carboxyl group, a carboxylic acid anhydride group, a halogen atom such as a chlorine atom, and an isocyanate group are preferable. The functional group to be reacted with the hydroxy group of the alcohol is preferably a carboxylic acid anhydride group, a halogen atom such as a chlorine atom, or an isocyanate group, and the functional group to be reacted with the hydroxy group of cellulose or a derivative thereof is, for example, a carboxylic acid Carboxylic acid halide groups such as chloride groups and isocyanate groups are preferred. The carboxylic acid halide group can be formed, for example, by converting a carboxyl group into an acid halide.

  Specific examples of the polyfunctional compound include dicarboxylic acid, carboxylic acid anhydride, dicarboxylic acid halide, monochlorocarboxylic acid, diisocyanate and the like. Examples of the dicarboxylic acid include malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, and the like. Examples of the carboxylic acid anhydride include the listed anhydrides of the dicarboxylic acid, and examples of the dicarboxylic acid halide include the listed acid halides of the dicarboxylic acid. Monochlorocarboxylic acid is, for example, monochloroacetic acid, 3-chloropropionic acid, 3-fluoropropionic acid, 4-chlorobutyric acid, 4-fluorobutyric acid, 5-chlorovaleric acid, 5-fluorovaleric acid, 6-chlorohexanoic acid, Examples include 6-fluorohexanoic acid, 8-chlorooctanoic acid, 8-fluorooctanoic acid, 12-chlorododecanoic acid, 12-fluorododecanoic acid, 18-chlorostearic acid, and 18-fluorostearic acid. Diisocyanates are, for example, tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate, 1,6-hexamethylene diisocyanate (HDI). , Isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated XDI, triisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, 1,8-diisocyanate methyloctane, lysine ester tri Isocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, dicyclohexylmethane diisocyanate (HMDI: hydrogenated MDI) And the like. Among these, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI) and the like are more preferable.

  When grafting cellulose or a derivative thereof with the alcohol via the polyfunctional compound, for example, grafting via at least one of an ester bond, an ether bond, and a urethane bond is performed.

  The carboxylic acid, the alcohol, or a derivative thereof may have, for example, a group derived from an organic silicon compound, an organic fluorine compound, or the like in the structure in order to obtain an effect of improving water resistance.

The grafting rate of the carboxylic acid, alcohol or derivative thereof on cellulose or its derivative is not particularly limited. The grafting rate is represented by, for example, an average value of the number of hydroxy groups contained in the glucose unit of cellulose or a derivative thereof reacted with the carboxylic acid, alcohol or a derivative thereof, that is, a hydroxyl group substitution degree (DS _XX ). It is. The hydroxyl group substitution degree is preferably 0.1 or more and 2.9 or less, more preferably 1.0 or more and 2.8 or less, for example, from the viewpoint of water resistance, mechanical properties, heat resistance, and the like. Further, the average value of the number of hydroxy groups remaining in the glucose unit of cellulose or its derivative, that is, the hydroxyl group residual degree (DS _OH ) is, for example, 0 from the viewpoint of sufficiently ensuring water resistance, mechanical strength and plasticity. .9 or less is preferable, and 0.7 or less is more preferable.

The grafting rate of the cardanol to cellulose or its derivative is not particularly limited. The grafting rate is represented by, for example, the average value of the number of hydroxy groups contained in the glucose unit of cellulose or its derivative bonded to cardanol, that is, the degree of hydroxyl group substitution (DS _CD ). The hydroxyl group substitution degree (DS _CD ) is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.4 from the viewpoint of, for example, improvement in water resistance, mechanical properties, and heat resistance. That's it.

The maximum value of the DS _CD is theoretically “3”, but is preferably 2.5 or less, more preferably 2 or less, and still more preferably 1.5 or less, for example, in order to perform efficient bonding. It is. The DS _CD may be 1 or less, for example, and in this case, a sufficient improvement effect can be obtained. The DS _CD can be appropriately set according to desired characteristics, for example. For example, by setting the DS _CD to be equal to or less than the upper limit value, for example, the tensile fracture strain and the bending fracture strain (toughness) are sufficiently suppressed, and the maximum strength (tensile strength and bending strength) is also reduced. It can be suppressed sufficiently. Further, the average value of the number of hydroxy groups remaining in the glucose unit of cellulose or its derivative bound with cardanol, that is, the hydroxyl group residual degree (DS _OH ), for example, sufficiently ensures water resistance, mechanical strength, and plasticity. From the point of view, 0.9 or less is preferable, and 0.7 or less is more preferable.

  Grafting of cellulose and its derivatives with the carboxylic acid, the alcohol or derivatives thereof can be carried out in a solvent, for example. The solvent is preferably a solvent that can dissolve, for example, cellulose or a derivative thereof, the carboxylic acid, the alcohol, or a derivative thereof. Moreover, it is preferable to heat the grafting reaction at an appropriate temperature, for example. Examples of the solvent for dissolving cellulose or a derivative thereof include dimethyl sulfoxide-amine solvents, dimethylformamide-chloral-pyridine solvents, dimethylacetamide-lithium chloride solvents, imidazolium ionic liquids, and the like. In addition, since the solubility in a general solvent can be improved, when the grafting reaction is performed, the carboxylic acid, the alcohol, or a derivative thereof is bonded to a part of the hydroxyl group of cellulose or a derivative thereof in advance to form a molecule. You may use the acylated cellulose derivative which improved the solubility by the fall of interstitial force. Examples of the solvent include dioxane, chloroform, methylene chloride, acetone and the like. Specific examples of the cellulose derivative include acylated celluloses such as acetyl cellulose, propionyl cellulose, and butyryl cellulose. Among them, acetyl cellulose is particularly preferable.

The acylation rate in the acylated cellulose is represented, for example, by the average value of the number of acylated hydroxy groups contained in the glucose unit of cellulose or its derivative, that is, the degree of hydroxyl substitution (DS _AC ). The hydroxyl group substitution degree (DS _AC ) is, for example, preferably 0.5 or more, more preferably 1.0 or more, still more preferably 1.5 or more, in order to increase the solubility of cellulose. For example, in order to perform grafting of cellulose or a derivative thereof with high efficiency, 2.9 or less is preferable, and 2.8 or less is more preferable.

  And the grafting of a cellulose or its derivative (s) can be performed by reaction of the hydroxy group of the acylated cellulose and the hydroxy group of alcohol such as cardanol and phenol.

(2) Polar group-containing rubber (Y)
As described above, the polar group-containing rubber (Y) comprises a carboxyl group, a carboxylic acid anhydride group, a nitrile group such as acrylonitrile, an ester group, a hydroxyl group, an amino group, a halogen, a nitro group, a formyl group, and an epoxy group. A polar group-containing rubber having in its structure at least one polar group selected from the group. The polar group-containing rubber (Y) is preferably a polar group-containing rubber having no isocyanate group.

  In the polar group-containing rubber (Y), the rubber that becomes the skeleton having the polar group is not particularly limited, and examples thereof include isoprene rubber such as butadiene rubber, nitrile rubber, and isoprene polymer, urethane rubber, ethylene propylene rubber, and silicone. Rubber. The polar group-containing rubber (Y) has a structure in which the rubber serving as the skeleton further has the polar group. The polar group-containing rubber (Y) may have, for example, one type of the polar group or two or more types. Moreover, the cellulose resin composition of the present invention may contain one type of the polar group-containing rubber (Y) or two or more types of the polar group-containing rubber (Y).

  Examples of the polar group-containing rubber (Y) include acrylonitrile / butadiene copolymers having carboxyl groups at both ends, maleic anhydride adducts of isoprene polymers, maleic acid-modified polybutadiene, and epoxy-modified polybutadiene.

  Examples of the acrylonitrile / butadiene copolymer having carboxyl groups at both ends include commercially available Hypro (trademark) (formerly Hycar (registered trademark)) CTB, CTBN, and CTBNX (CVC Thermoset Specialties (USA) or PTI Japan Co., Ltd.). Etc. can be used.

  As the maleic anhydride adduct, for example, trade name LIR-403 (manufactured by Kuraray Co., Ltd.) can be used.

  The number average molecular weight of the polar group-containing rubber (Y) is not particularly limited, and the lower limit thereof is preferably 1,000 or more, more preferably 2,000 or more, and the upper limit thereof is 20,000 or less. Is more preferable, and 10,000 or less is more preferable. For example, the polar group-containing rubber (Y) is set to an appropriate molecular weight such as the range of the number average molecular weight, whereby a more uniform molded product can be obtained with better dispersibility. . The number average molecular weight can be measured using, for example, gel permeation chromatography (GPC). Specifically, for example, a measurement value by GPC (calibrated with a polystyrene standard sample) regarding a 0.1% chloroform solution of a sample is used. Can be adopted.

  In the cellulose resin composition of the present invention, the content of the polar group-containing rubber (Y) is not particularly limited. The addition ratio of the polar group-containing rubber (Y) is, for example, 0.1% by mass or more with respect to the whole cellulose resin composition, for example, from the point of sufficiently improving the impact resistance of the obtained molded body. Is more preferable, and more preferably 1% by mass or more. Further, for example, from the viewpoint of sufficiently securing properties such as strength of the cellulose resin composition, for example, 20% by mass or less is preferable, and more preferably 10% by mass or less, with respect to the entire cellulose resin composition. It is.

(3) Cellulose-based resin composition The cellulose-based resin composition of the present invention is obtained by melt-mixing the polar group-containing rubber (Y) into the cellulose-based resin (X) as described above. The mixing is preferably, for example, melt mixing. By mixing the two, for example, the prepolar group-containing rubber (Y) can be appropriately dispersed in the cellulose resin (X). And, for example, at the time of breaking, stress concentrates on the low-elasticity polar group-containing rubber (Y), so that many crazes are generated and energy is absorbed, so that the impact resistance of the cellulose resin composition is reduced. It can be improved.

  The cellulose resin composition may contain additives such as a colorant, an antioxidant, a heat stabilizer, a plasticizer, and a flame retardant as necessary.

  The manufacturing method of the said cellulose resin composition is not restrict | limited except using the said cellulose resin (X) and the said polar group containing rubber (Y), and mixing on the conditions from which the both are not chemically couple | bonded. As a condition that the two are not chemically bonded, for example, as the polar group-containing rubber (Y), a mode in which a polar functional group-containing rubber (Y) having no highly reactive functional group, for example, an isocyanate group is used. Can be given. As the production method, for example, a known method can be adopted, and as a specific example, various additives, the cellulose resin, and the polar group-containing rubber (Y) are hand-mixed or mixed (for example, a tumbler mixer, It can be manufactured by melting and mixing with a ribbon blender, a single-shaft or multi-shaft mixing extruder, a compounding device such as a kneading kneader, a kneading roll, etc., and granulating into an appropriate shape if necessary. In addition, as another preferred production method, for example, it is dispersed in a solvent such as an organic solvent, and various additives, the cellulose resin, and the polar group-containing rubber (Y) are mixed. Thus, there is a method of adding a coagulation solvent to obtain a mixed composition thereof, and then evaporating the solvent.

  The form of the cellulose resin composition of the present invention is not particularly limited, and may be, for example, a solution or a solid such as a pellet, powder, particle, or block.

  The cellulose resin composition can be used as a molding material, for example. A molding material using the cellulose-based resin composition is suitable for a molded body such as a casing of an exterior for an electronic device, for example.

2. Molding material Next, the molding material of the present invention is characterized in that it contains the cellulose resin composition of the present invention. The molding material of the present invention contains, for example, the cellulose-based resin composition as a base resin, and is useful as a raw material for various molded articles such as a casing for an electronic equipment exterior.

  The base resin means, for example, a main component in the molding material, and means that other components are allowed to be contained within a range that does not hinder the function of the main component. In the molding material of the present invention, the content ratio of the base resin (that is, the cellulose resin composition of the present invention) which is a main component is not particularly limited, and is preferably, for example, 30% by mass or more, more preferably It is 50 mass% or more, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.

  The molding material of the present invention may contain, for example, a binder, a solvent and the like in addition to the cellulose resin composition of the present invention.

  The form of the molding material of the present invention is not particularly limited, and may be, for example, a solution or a solid such as a pellet, powder, particle, or block.

3. Moldings Then, the molded body of the present invention is characterized by comprising a cellulose-based resin composition of the present invention. The molded object of this invention should just use the cellulose resin composition of the said this invention, and another structure is not restrict | limited at all. Examples of the molded body include housings such as exteriors for electronic devices, internal parts of electronic devices, sheets, films, packaging containers, and the like.

Hereinafter, the present invention will be described in more detail with specific examples.

[Cellulosic resin]
As the cellulose resin, the following cellulose resins 1, 3 and 4 were prepared.

(1) Cellulosic resin 1
As the cellulose resin 1, cellulose acetate propionate (CAP482-20: manufactured by Eastman Chemical Co., Ltd.) having the following characteristics (DS _Ace and DS _Pro ) was used.
Acetylation rate of hydroxy group per glucose unit of cellulose: DS _Ace = 0.18
Propionylation rate of hydroxy group per glucose unit of cellulose: DS _Pro = 2.49)

(2) Cellulosic resin 3
Cardanol-grafted cellulose acetate propionate was produced as cellulose resin 3 by Synthesis Examples 1 to 4 shown below.

(2-1) Synthesis Example 1: Hydrogenated Cardanol The 3-pentadecylphenol represented by the formula (2) was hydrogenated to prepare 3-pentadecylcyclohexanol as the hydrogenated cardanol. First, 20 g of cardanol obtained by distillation purification from heat-treated cashew nut oil, 2 g of ruthenium / carbon catalyst (Ru: 5% by mass), and 20 ml of tetrahydrofuran were charged into a batch-type autoclave having an internal volume of 1.0 liter at room temperature. Hydrogenation reaction was performed by injecting 20 kgf / cm ² (1.96 × 10 6 Pa) of hydrogen and stirring at 80 ° C. for 3 hours. Thereafter, the ruthenium / carbon catalyst was removed by filtering the reaction solution taken out of the autoclave using a fluororesin membrane filter having an average pore size of 0.2 μm. Tetrahydrofuran was distilled off by reducing the pressure of the obtained filtrate under heating. As a result, 20.6 g of hydrogenated cardanol which was a white solid at room temperature was obtained.

When the purity of the obtained hydrogenated cardanol was measured with a liquid chromatograph (LC-10ADVP: manufactured by Shimadzu Corporation), the purity was 99% by mass. Moreover, when the obtained hydrogenated cardanol was measured by ¹ H-NMR (AV-400, 400 MHz: manufactured by Bruker), hydrogenation rate (conversion rate of double bond of hydrocarbon portion and double bond of aromatic ring) ) Was 99 mol% or more.

(2-2) Synthesis Example 2: Diisocyanate-added Cardanol Derivative Hexamethylene diisocyanate (HDI) 92.7 g (0.55 mol) was heated to 50 ° C. with stirring, and the water obtained in Synthesis Example 1 was added there. 17.1 g (0.055 mol) of added cardanol (3-pentadecylphenol) was added, and stirring was continued at 80 ° C. for 3 hours. The reaction solution was cooled to 40 ° C., 375 mL of acetonitrile was added, and the mixture was stirred at room temperature for 1 hour, and then allowed to stand at −15 ° C. for 17 hours. Crystals were filtered from the reaction solution after standing (5A, 185 mmφ) and washed with liquid using 125 ml of ice-cooled acetonitrile. The obtained crystals were slurried in 125 ml of acetonitrile and stirred at room temperature for 1 hour. After standing at −15 ° C. overnight, the crystals were filtered (5A, 185 mmφ) and dried under reduced pressure (˜0.4 kPa) at 30 ° C. for 6 hours. As a result, 22.61 g of a white powder (dry crystal) of a diisocyanate-added cardanol derivative in which HDI and hydrogenated cardanol were combined at a molar ratio of 1: 1 was obtained.

  When the obtained diisocyanate-added cardanol derivative was measured with a liquid chromatograph (LC-10ADVP island: manufactured by Tsu Seisakusho), the purity was 91% by mass.

(2-3) Synthesis Example 3: Cardanol-Grafted Cellulose Acetate The diisocyanate-added cardanol derivative obtained in Synthesis Example 2 was converted into cellulose acetate (LM-80: manufactured by Daicel Chemical Industries, Ltd. per cellulose glucose unit). Hydroxy group acetylation rate: DS _Ace = 2.1) to obtain grafted cellulose acetate.

  Specifically, first, 385 mL of dehydrated dioxane was added to 27.5 g (0.11 mol / Glc) of the cellulose acetate and dissolved at a liquid temperature of 80 to 88 ° C. over 1 hour. Next, the solution was cooled to 40 ° C., and 0.276 g (0.437 mmol) of dibutyltin laurate dissolved in 2.8 ml of dehydrated dioxane was added thereto. Subsequently, 11.56 g (purity 91.0%, 0.022 mol) of the diisocyanate-added cardanol derivative synthesized in Synthesis Example 2 was dissolved in 50 ml of dehydrated dioxane after heating and added, and the liquid temperature was 80 ° C. for 3 hours. Stir. Further, with the solution maintained at 80 ° C., 11.05 g (purity 91.0%, 0.022 mol) of a diisocyanate-added cardanol derivative was dissolved in 50 ml of dehydrated dioxane with heating, and the mixture was stirred at 80 ° C. for 18 hours. . After cooling the solution to 30 ° C., 4.5 L of methanol was added with stirring to precipitate the polymer. After the polymer was filtered, the polymer was dried under reduced pressure (˜0.7 kPa) at 105 ° C. for 14 hours to obtain 43.9 g of a dry polymer. To the dried polymer, 600 ml of methyl ethyl ketone was added and stirred at a liquid temperature of 70 to 80 ° C. for 1 hour to dissolve the polymer, and then cooled to 30 ° C. Next, the polymer solution was centrifuged to separate insolubles by sedimentation (3500 rpm × 15 minutes). 1 L of hexane was added to the polymer solution from which unnecessary substances were separated and removed to precipitate the polymer. The polymer was filtered and washed twice (hexane 1 L × 2 times). The obtained polymer was dissolved by heating with ethyl ethyl ketone, cooled, and then the steps of centrifugal separation, sedimentation separation and hexane washing were repeated twice more, followed by drying under reduced pressure (˜0. 8 kPa) to obtain 36.4 g of cardanol grafted cellulose acetate.

(2-4) Synthesis Example 4: Cardanol-Grafted Cellulose Acetate Propionate 36.4 g of cardanol-grafted cellulose acetate obtained in Synthesis Example 3 and 310 ml of dehydrated pyridine were charged at a liquid temperature of 75-80 ° C. Dissolved over minutes. To the solution, 18.3 g (0.15 mol) of N, N-dimethylaminopyridine and 390 ml of propionic anhydride were added at a liquid temperature of 76 ° C., and the mixture was stirred at a liquid temperature of 100 ° C. for 1 hour. And after cooling the said solution to 30 degreeC of liquid temperature, 130 ml of methanol was added over 70 minutes, cooling with ice. Meanwhile, the liquid temperature was kept at 30-40 ° C. Further, 250 ml of methanol was added while stirring the reaction solution to precipitate the polymer. The polymer was filtered and washed twice (methanol 200 ml × 2 times). The obtained polymer was dried and then dissolved in 250 ml of chloroform at a liquid temperature of 60 ° C. After cooling the solution, 1.3 L of methanol was added with stirring to precipitate the polymer. The polymer was filtered and washed twice (100 ml of methanol × 2 times). Then, the polymer was dried under reduced pressure (˜0.7 kPa) at 105 ° C. for 16 hours. Thereby, 35.8 g of cardanol grafted cellulose acetate propionate was obtained as the cellulose resin 3.

The obtained cardanol grafted cellulose acetate propionate (cellulose-based resin 3) was measured by ¹ H-NMR (AV-400, 400 MHz: manufactured by Bruker). DS _Ace : 2.1, DS _Pro : 0 .59, DS _CD : 0.25.

(3) Cellulosic resin 4
Cardanol-grafted cellulose acetate was prepared as the cellulose resin 4 by Synthesis Examples 5 and 6 shown below.

(3-1) Synthesis Example 5: Cardanol derivative 1
As the cardanol derivative 1, a monochloroacetic acid modified cardanol chloride compound was prepared. This is a hydrogenated cardanol in which the unsaturated bond of the linear hydrocarbon moiety in cardanol is hydrogenated as a raw material, mn-pentadecylphenol (3-pentadecylphenol, ACROS) of the above formula (2) : Organics). Then, the phenolic hydroxyl group of the raw material was reacted with monochloroacetic acid to obtain carboxylated hydrogenated cardanol. Next, the carboxyl group of the carboxylated hydrogenated cardanol was converted to an acid chloride group by chlorination with oxalyl chloride to obtain a chloride hydrogenated cardanol. A more specific method for the chlorinated hydrogenated cardanol is shown below.

  First, 80 g (0.26 mol) of hydrogenated cardanol (3-pentadecylphenol) was dissolved in 120 mL of methanol, and an aqueous solution in which 64 g (1.6 mol) of sodium hydroxide was dissolved in 40 mL of distilled water was added thereto. A solution prepared by dissolving 66 g (0.70 mol) of monochloroacetic acid (manufactured by Kanto Chemical Co., Ltd.) in 50 mL of methanol was added dropwise to the solution at room temperature. After completion of the dropwise addition, the reaction solution was refluxed at 73 ° C. for 4 hours while continuing stirring, and then the reaction solution was cooled to room temperature. The reaction solution was acidified with dilute hydrochloric acid until pH = 1, 250 mL of methanol and 500 mL of diethyl ether were added, and 200 mL of distilled water was further added. This mixed solution was put into a separatory funnel, separated into an aqueous layer and an ether layer, the aqueous layer was discarded, and the ether layer was washed twice with 400 mL of distilled water. After anhydrous magnesium was added to the collected ether layer and dried, it was filtered off. The obtained filtrate (ether layer) was concentrated under reduced pressure with an evaporator (90 ° C./3 mmHg) to obtain a yellowish brown powdery crude product as a residue. The crude product was recrystallized from n-hexane and vacuum dried to obtain 46 g (0.12 mol) of a white powder of the desired carboxylated hydrogenated cardanol.

  46 g (0.12 mol) of the obtained carboxylated hydrogenated cardanol was dissolved in 250 mL of dehydrated chloroform, 24 g (0.19 mol) of oxalyl chloride and 0.25 mL (3.2 mmol) of N, N-dimethylformamide were added, and room temperature was added. For 72 hours. Thereafter, chloroform and excess oxalyl chloride were distilled off under reduced pressure to obtain 48 g (0.13 mol) of chlorinated hydrogenated cardanol.

(3-2) Synthesis Example 6: Cardanol-Grafted Cellulose Acetate The chlorinated hydrogenated cardanol (cardanol derivative) obtained in Synthesis Example 5 was converted into cellulose acetate (LM-80: Daicel Chemical Industries, Ltd .: Cellulose). To acetylation rate of hydroxy group per glucose unit: DS _Ace = 2.1) to obtain grafted cellulose acetate.

  Specifically, first, 30 g of the cellulose acetate (hydroxyl amount 0.108 mol) was dissolved in 600 mL of dehydrated dioxane, and 15 mL (0.108 mol) of triethylamine was added as a reaction catalyst and an acid scavenger. To the solution was added 300 mL of a dioxane solution in which 32 g (0.084 mol) of the chlorinated hydrogenated cardanol obtained in Synthesis Example 1 was dissolved, and the mixture was heated to reflux at 100 ° C. for 5 hours. This reaction solution was slowly added dropwise to 4.5 L of methanol while stirring to cause reprecipitation, and the precipitated solid was separated by filtration. The solid separated by filtration was air-dried overnight and further vacuum-dried at 105 ° C. for 5 hours. Thereby, 23 g of grafted cellulose acetate was obtained as the cellulose resin 4.

When the obtained grafted cellulose acetate (cellulose-based resin 4) was measured by 1H-NMR (AV-400, 400 MHz: manufactured by Bruker), the DS _CD was 0.47.

[Polar group-containing rubber]
(1) Carboxyl group-containing rubber As the polar group-containing rubber, an acrylonitrile / butadiene copolymer having carboxyl groups at both ends and a butadiene copolymer having carboxyl groups at both ends, as shown in Formula (3), were used. The polar group-containing rubber was obtained from commercially available Hypro ™ (formerly Hycar ™) CTB, CTBN and CTBNX from CVC Thermoset Specialties (USA) or PTI Japan. The characteristics of these polar group-containing rubbers are shown in Table 1 below.

(2) Maleic anhydride-added rubber A maleic anhydride adduct of isoprene polymer obtained by adding maleic anhydride to the side chain of isoprene rubber was used as the polar group-containing rubber. As the polar group-containing rubber, a commercially available maleic anhydride adduct of isoprene polymer (Kuraray Co., Ltd., LIR-403) was used. The characteristics and structure of the polar group-containing rubber are shown in Table 2 below. In addition, the commercially available isoprene rubber (Kuraray Co., Ltd. product, LIR-30) shown to Formula (5) was used as a polar non-containing rubber of a comparative example. The properties and structure of the non-polar group-containing rubber are shown in Table 2 below.

[Characteristic evaluation]
Various characteristics of the cellulose resin composition described later and a molded body (test piece) molded using the same were evaluated by the following methods.

(1) Evaluation of compatibility About the said molded object, the external appearance was observed visually and compatibility was evaluated on the following reference | standard. In the evaluation of the phase training, ○, ○ to Δ, and Δ were evaluated as acceptable in practical use.
○: Transparent (completely dissolved)
○ to △: Translucent (highly dispersed)
Δ: Cloudy (uniformly dispersed)
×: Unevenly distributed

(2) Evaluation of Izod impact strength The notched Izod impact strength of the molded product was measured in accordance with JIS K7110. The said intensity | strength set 4.0 kJ / m < ² > or more as a pass value in practical use. The strength is preferably 5.4 kJ / m ² or more, more preferably 6.5 kJ / m ² or more, further preferably 7.5 kJ / m ² or more, and particularly preferably 8.0 kJ. / M ² or more.

(3) Bending test The bending test was done about the said molded object based on JISK7171. The bending strength was set to 30 MPa or more as an acceptable value in practical use.

(4) Measurement of melt flow rate (MFR) After the cellulose-based resin composition is dried at 105 ° C. for 7 hours, the measurement apparatus (manufactured by Shimadzu Corporation, Shimadzu Flow Tester CFT-500D) is used in accordance with JIS K7210. Then, the melt flow rate (MFR) was measured under the conditions of 200 ° C. and 500 kgf / cm ² . The said MFR set 1000 g / 10min or more as a pass value in practical use.

(5) Evaluation of water absorption rate The water absorption rate was measured according to JIS K7209. The water absorption rate was set to 3.0% or less as an acceptable value in practical use.

[Examples 1-6 and Comparative Example 1]
The cellulose resin composition of Example 1-6 and the composition of Comparative Example 1 were prepared, molded, and various properties were evaluated.

(1) Kneading Cellulose acetate propionate (cellulose-based resin 1) was used as the cellulose resin, and acrylonitrile / butadiene copolymer having a carboxyl group at the terminal in Table 1 was used as the polar group-containing rubber. These are blended (mass%) shown in Table 3 below, using a biaxial kneader (HAKKE-MiniLab (Micro-Extruder: manufactured by Thermo Electron Corp.)) under the conditions of 180 to 210 ° C. and 60 rpm. The mixture was melt-kneaded for 1 minute to recover the cellulose resin composition.

(2) Injection molding The obtained cellulose resin composition was injected into an injection temperature (HAKKE-MiniJet II: Thermo Scientific) using an injection temperature of 180 to 210 ° C, an injection pressure of 800 bar to 1200 bar, a mold temperature of 100 ° C, Injection molding was performed under the condition of a holding pressure of 400 bar to obtain a test piece having a thickness of 2 mm, a width of 13 mm, and a length of 80 mm. In Comparative Example 1, molding and various characteristics were evaluated in the same manner except that the polar group-containing rubber was not added. These results are shown in Table 3 below. In the following table, the results that did not satisfy the passing score for practical use were shaded (hereinafter the same). Moreover, the compatibility and the surface segregation, which are evaluation items for two or more types of mixing, were excluded from those not added with the polar group-containing rubber (hereinafter the same).

  As shown in the said Table 3, the cellulose resin composition of Example 1-4 satisfy | filled the pass value of practical use about all the items. And it turned out that the cellulose resin composition of the said Example 1-4 is excellent in impact strength and water resistance compared with the cellulose resin 1 of Comparative Example 1 alone.

[Example 5, Comparative Example 2]
The cellulose resin composition and the same as in the above example except that the cardanol grafted cellulose acetate propionate (cellulose resin 3) was used as the cellulose resin and the composition shown in Table 4 below was used. A test piece of a molded body using was prepared. And the various characteristics were evaluated about the said cellulose resin composition and a molded object. In Comparative Example 2, molding and various characteristics were evaluated in the same manner except that the polar group-containing rubber was not added. These results are shown in Table 4 below. Moreover, the item which has not been measured regarding the characteristic was attached with the oblique line (hereinafter the same).

  As shown in the said Table 4, the cellulose resin composition of Example 5 satisfy | filled the pass value of practical use about all the items. And it turned out that the cellulose resin composition of the said Example 5 is excellent in impact strength and water resistance compared with the cellulose resin 3 of Comparative Example 2 alone.

[Example 6-10, Comparative Example 3]
A cellulose resin composition and a molded body using the same in the same manner as in the above example, except that the grafted cellulose acetate (cellulose resin 4) was used as the cellulose resin and the composition shown in Table 5 below was used. A test piece was prepared. And the various characteristics were evaluated about the said cellulose resin composition and a molded object. In Comparative Example 3, molding and various characteristics were evaluated in the same manner except that the polar group-containing rubber was not added. These results are shown in Table 5 below.

  As shown in the said Table 5, the cellulose resin composition of Example 6-10 satisfy | filled the pass value of practical use about all the items. And it turned out that the cellulose resin composition of the said Example 6-10 is excellent in impact strength and water resistance compared with the cellulose resin 4 of Comparative Example 3 alone.

[Example 11, Comparative Examples 4 and 5]
The above examples except that the grafted cellulose acetate (cellulose resin 4) was used as the cellulose resin, the maleic anhydride-modified isoprene rubber was used as the polar group-containing rubber, and the composition shown in Table 6 below was used. In the same manner as above, a cellulose resin composition and a test piece of a molded body using the same were prepared. And the various characteristics were evaluated about the said cellulose resin composition and a molded object. Further, Comparative Example 4 was similarly molded and evaluated for various properties, except that the polar group-containing rubber was not added, and Comparative Example 5 was replaced with the polar group-containing rubber instead of the polar group-containing rubber. A cellulose resin composition and a molded body were prepared and various properties were evaluated in the same manner except that isoprene rubber as a rubber was used. These results are shown in Table 6 below.

  As shown in Table 6, the cellulosic resin composition of Example 10 satisfied the acceptable values for practical use for all items. And it turned out that the cellulose resin composition of the said Example 10 is excellent in impact strength and water resistance compared with the cellulose resin 4 of Comparative Example 4 alone. Further, in the cellulose resin composition of Comparative Example 5 using the polar group-free rubber instead of the polar group-containing rubber, the cellulose resin 4 and the polar group-free rubber are mixed during kneading and injection molding. In addition, surface precipitation (bleeding) was confirmed, and evaluation of each characteristic could not be performed.

  While the present invention has been described with reference to the embodiments, the present invention is not limited to the above embodiments. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.

According to the cellulose resin composition of the present invention, for example, although it is a bioplastic, it can improve impact resistance and can be used for a casing of an electrical device similar to petroleum plastic.

Claims (9)

Including the following cellulose resin (X) and the following polar group-containing rubber (Y),
The cellulose resin composition, wherein the cellulose resin (X) and the polar group-containing rubber (Y) are chemically unbonded.
(X) Cellulose-based resin (Y) having at least one selected from the group consisting of carboxylic acids having 1 to 32 carbon atoms, alcohols and derivatives thereof to at least one of cellulose and derivatives thereof (Y) carboxyl group, carboxylic acid anhydride Polar group-containing rubber having in its structure at least one polar group selected from the group consisting of physical groups, nitrile groups, ester groups, hydroxyl groups, amino groups, halogens, nitro groups, formyl groups and epoxy groups The cellulose resin composition according to claim 1, wherein the polar group-containing rubber (Y) is a polar group-containing rubber having no isocyanate group. The polar group-containing rubber is at least one selected from the group consisting of butadiene rubber, nitrile rubber, isoprene rubber, urethane rubber, ethylene propylene rubber, and silicone rubber, and has the polar group in its structure. Item 3. The cellulose resin composition according to Item 1 or 2. The polar group-containing rubber is at least one of a carboxylic acid-terminated butadiene rubber having a carboxyl group at at least one end and a carboxylic acid-terminated nitrile rubber having a carboxyl group at at least one end, and the polarities in the structure thereof The cellulose resin composition according to any one of claims 1 to 3, which has a group. 5. The method according to claim 1, wherein the polar group-containing rubber is contained in an amount of 0.1% by mass or more and 10% by mass or less based on a total amount of the polar group-containing rubber and the cellulose resin composition. The cellulosic resin composition according to claim 1. The cellulose resin composition according to any one of claims 1 to 5, wherein the cellulose resin is at least one of cellulose acetate propionate and cellulose acetate butyrate. The cellulose resin composition according to any one of claims 1 to 6, wherein the cellulose resin contains at least one of cardanol and a cardanol derivative in its structure. A molding material comprising the cellulose resin composition according to any one of claims 1 to 7. The molded object characterized by including the cellulose resin composition as described in any one of Claim 1 to 8.