WO2014087881A1

WO2014087881A1 - Cellulose-based resin composition

Info

Publication number: WO2014087881A1
Application number: PCT/JP2013/081765
Authority: WO
Inventors: 曽山　誠; 幸浩木内; 位地　正年; 修吉田中; 清彦當山
Original assignee: 日本電気株式会社
Priority date: 2012-12-07
Filing date: 2013-11-26
Publication date: 2014-06-12
Also published as: JPWO2014087881A1

Abstract

Provided is a cellulose-based resin composition which has improved impact resistance, while having improved thermal plasticity, heat resistance, strength, moldability and water resistance. This cellulose-based resin composition contains: a cellulose-based resin that is obtained by having one or more substances selected from among carboxylic acids having 1-32 carbon atoms, alcohols, phenols and derivatives of these substances react with and chemically bonded to a hydroxy group of a cellulose or a derivative thereof; and a polyether-modified polysiloxane which has a polyether group represented by -(CmH2mO)n- (wherein m represents an integer of 2-4 and n represents an integer of 1-80) or the polyether group having a substituent.

Description

Cellulosic resin composition

The present invention relates to a cellulose resin composition, and more particularly to a cellulose resin composition having improved mechanical strength, heat resistance, water resistance, thermoplasticity, impact resistance, and bleed out.

Various bioplastics using cellulose, which is a major component of wood and vegetation, have been developed and commercialized as bioplastics made from non-edible parts among bioplastics made from plants. As this type of bioplastic, there are cellulose derivatives of cellulose derivatives. Specifically, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and the like are used in many fields.
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 it contains many hydroxy groups, its water absorption is high and its water resistance is low. Various studies have been conducted to improve the properties of cellulose.

For example, Patent Document 1 discloses a thermoplastic biodegradable graft polymer 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 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 friction material formed using a base substrate made of aramid fibers and cellulose fibers, a filler made of graphite and cashew dust, and an organic-inorganic composite binder. It is described that this friction material is applied to clutch facing of a power transmission system such as an automobile.

Non-Patent Document 1 describes that the water resistance of paper can be improved by immersing a paper sheet in cardanol and performing a grafting reaction that binds cardanol to cellulose constituting the paper sheet. In this grafting reaction, it is described that the terminal double bond of cardanol and the hydroxy group of cellulose are bonded in the presence of boron trifluoride diethyl ether (BF3-OEt2).
Cellulosic bioplastics are inferior in strength, heat resistance, water resistance, thermoplasticity, and impact resistance compared to petroleum plastics, and these characteristics are improved especially for application to durable products such as exteriors for electronic devices. is required. However, when a plasticizer obtained from a petroleum oil raw material is added to improve the thermoplasticity, the plant utilization rate (plantiness) is lowered, and the heat resistance and strength (particularly rigidity) are lowered. There is a problem of bleed out of the plasticizer (seepage to the surface of the molded product). In addition, when a normal soft component is added to improve impact resistance, the soft component may bleed out during molding, thereby hindering moldability.

Japanese Patent Laid-Open No. 11-255801 Japanese Patent Laid-Open No. 10-8035 JP 2001-32869 A

An object of the present invention is to provide a cellulose-based resin composition having improved impact resistance as well as thermoplasticity, heat resistance, strength, moldability and water resistance.

The present inventors include a cellulose resin in which a carboxylic acid, an alcohol, or a phenol is reacted with a hydroxyl group of cellulose and chemically bonded thereto, and a polyether-modified polysiloxane having an ether group. The dispersibility of the polysiloxane in the cellulosic resin can be improved by a synergistic effect between the formed acyl group, ether group, and the like and the polyether group of the polysiloxane. As a result, mechanical properties, particularly toughness and impact resistance can be improved, water resistance and plasticity can be improved, and the amount of plasticizer added can be reduced or not added. The present inventors have obtained knowledge that heat resistance and strength, particularly rigidity, can be prevented from being lowered, and that additive and polysiloxane bleed-out can be suppressed in the molded product, and the present invention has been completed based on such knowledge.

That is, the present invention relates to a cellulose resin obtained by reacting and chemically bonding one or more selected from carboxylic acids having 1 to 32 carbon atoms, alcohols, phenols and derivatives thereof to the hydroxy group of cellulose or a derivative thereof, A polyether-modified polysiloxane having a polyether group or a substituent-containing polyether group represented by (CmH2mO) n- (m is an integer of 2 to 4, n is an integer of 1 to 80). It is related with the cellulosic resin composition containing.

The cellulose resin composition of the present invention can improve impact resistance as well as thermoplasticity, heat resistance, strength, moldability and water resistance.

The cellulose-based resin composition of the present invention is a cellulose-based resin in which one or more selected from carboxylic acids having 1 to 32 carbon atoms, alcohols, phenols, and derivatives thereof are reacted and chemically bonded to the hydroxy group of cellulose or a derivative thereof. A polyether modified with a polyether group or a substituent represented by a resin and-(CmH2mO) n- (m is an integer of 2 to 4, n is an integer of 1 to 80) It contains polysiloxane.

[Cellulosic resin]
Cellulosic resins are those obtained by reacting and chemically bonding one or more selected from carboxylic acids having 1 to 32 carbon atoms, alcohols, phenols, or derivatives thereof to the hydroxy group of cellulose or a derivative thereof.

The above cellulose is a main component of vegetation and is obtained by separating other components such as lignin from vegetation. In addition to those obtained in this manner, cotton or pulp having a high cellulose content can be purified or used as it is. Cellulose is a linear polymer of β-glucose represented by the following formula (3), and each glucose unit has three hydroxy groups.

The polymerization degree of cellulose and its derivatives is preferably in the range of 50 to 5000, more preferably 100 to 3000, as the glucose polymerization degree. If it is the said range, sufficient intensity | strength and heat resistance will be acquired in the obtained molded object, and it can suppress that the melt viscosity of resin becomes high and causes trouble in shaping | molding.

Examples of the cellulose derivative are those in which a substituent is introduced by a living organism or by chemical synthesis using cellulose as a raw material, and those obtained by acylating, etherifying, or grafting a part of the hydroxy group can be exemplified. Specifically, 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, cellulose acetate butyrate, and cellulose acetate Examples thereof include hybrid esters such as phthalate and cellulose nitrate acetate; etherified celluloses such as methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose. Further, grafted cellulose in which a polymer such as styrene, (meth) acrylic acid, (meth) acrylic ester, ε-caprolactone, lactide, glycolide, etc. is bonded to cellulose can be mentioned.

Among these derivatives, at least one acylated cellulose selected from cellulose acetate, cellulose propionate, and cellulose butyrate in which a part of the hydroxy group of cellulose is acylated can be suitably used.

In the cellulose derivative, the average value of the number of hydroxyl groups reacted and acylated in the glucose unit and the hydroxyl group substitution degree (DSXX) are 2.0 from the viewpoint of water resistance, mechanical properties, heat resistance, and the like. As mentioned above, 2.8 or less is more preferable. In addition, the average value of the number of hydroxy groups remaining in the glucose unit of the cellulose derivative and the hydroxyl group residual degree (DSOH) are preferably 0.9 or less, more preferably 0.7 or less, from the viewpoint of sufficiently securing water resistance. preferable.

The above cellulose or cellulose derivative may be used alone or in combination of two or more.

Further, chitin or chitosan having a similar structure may be mixed with cellulose or a derivative thereof, and when mixed, the content of chitin or chitosan is preferably 30% by mass or less based on the entire mixture, 20 mass% or less is preferable and 10 mass% or less is still more preferable.

The cellulose or derivatives thereof are those in which the hydroxy group is chemically bonded by reacting with a carboxylic acid having 1 to 32 carbon atoms, alcohol, phenol or a derivative thereof. The hydroxy group of cellulose or its derivative reacts with the carboxyl group of carboxylic acid or the hydroxy group of alcohol or phenol to form a glycoside.

Here, the reaction of cellulose or its derivative with the carboxyl group of carboxylic acid or the hydroxy group of alcohol or phenol to form a glycoside is called grafting of cellulose or its derivative.

When carboxylic acid, alcohol, or phenol has an aromatic group or alicyclic group, it is effective for improving rigidity and heat resistance of the molded article by grafting cellulose or a derivative thereof, carboxylic acid, alcohol, When phenol has an aliphatic group, it is effective for improving the toughness of the molded article by grafting cellulose or a derivative thereof.

These carboxylic acids, alcohols or phenols have 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms. When the carbon number is within this range, steric hindrance can be suppressed and the grafting rate of the hydroxy group of cellulose can be increased.

The carboxylic acid may be a linear or branched aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, or carboxylic anhydride. In the alicyclic monocarboxylic acid and aromatic monocarboxylic acid, the carboxyl group may be directly bonded to the alicyclic group or aromatic ring, or may be bonded to the alicyclic group or aromatic ring substituent. .

Specific examples of such carboxylic acids 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. Acid, tridecylic acid, 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, laccelic acid, etc. Carboxylic acids; unsaturated monocarboxylic acids such as butenoic acid, pentenoic acid, hexenoic acid, octenoic acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Furthermore, as alicyclic monocarboxylic acid, cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, cyclohexyl acetic acid, etc., and aromatic carboxylic acid as benzoic acid, toluic acid, phenylacetic acid, phenylpropionic acid, biphenyl, etc. Carboxylic acid, biphenylacetic acid, naphthalene carboxylic acid, tetralin carboxylic acid and the like can be mentioned. Of these, particularly preferred are acetic acid, propionic acid, and butyric acid.

As the carboxylic acid derivative, the carboxylic acid has a substituent. As the substituent, a functional group having reactivity with a hydroxy group of cellulose is preferable. In addition to a carboxylic acid halide group such as a carboxylic acid chloride group and a carboxylic acid anhydride group, a halogen such as an epoxy group, an isocyanate group, and a chlorine atom. Atoms can be mentioned. Among these, carboxylic acid halide groups such as carboxylic acid chloride and isocyanate groups are preferred.

In addition, the alcohol having 1 to 32 carbon atoms bonded to cellulose or a derivative thereof may be either an aliphatic alcohol or an alicyclic alcohol. Examples of the aliphatic alcohol include methanol, ethanol, propanol, etc., examples of the alicyclic alcohol include cyclohexylol and cycloheptalol, and examples of the aromatic alcohol include phenol. In particular, it is preferable to extract and use cardanol contained in the cashew nut shell as the aromatic alcohol. Cardanol is a phenol having a linear hydrocarbon group R as shown in Formula (4). The linear hydrocarbon group R of cardanol has four types of isomers of pentadecyl group, 8-pentadecenyl group, pentadecyl 8,11-diene group, and pentadecyl 8,11,14-triene group having different numbers of unsaturated bonds. Cardanol exists as a mixture of these four isomers.

The linear hydrocarbon group R of cardanol contributes to the improvement of the flexibility and hydrophobicity of the resin, and the hydroxy group forms glucoside with cellulose or its derivatives. When such cardanol is bound to cellulose or its derivative, a cellulose resin in which the cardanol component is bound in a brush shape is formed. As a result, mechanical properties are obtained by the interaction between cardanols glycosylated into cellulose or its derivative. (Especially toughness) can be improved, thermoplasticity can be imparted, and the water resistance can be improved by the hydrophobicity of cardanol. When glycosidating the above cardanol with cellulose or a derivative thereof, a dehydration catalyst such as sulfuric acid, toluenesulfonic acid or hydrogen chloride may be added.

Cardanol is preferably used after the unsaturated bond of the linear hydrocarbon group of cardanol is hydrogenated and converted to a saturated bond. By using a cardanol derivative in which unsaturated bonds of linear hydrocarbon groups are sufficiently converted to saturated bonds by hydrogenation, side reactions can be suppressed and cellulose and cardanol can be bound efficiently. Moreover, the solubility fall to the solvent of a product can be suppressed. The conversion rate (hydrogenation rate) of unsaturated bonds by hydrogenation is preferably 90 mol% or more, and more preferably 95 mol% or more. The residual ratio of unsaturated bonds in cardanol after hydrogenation (average number of unsaturated bonds per molecule of cardanol) is preferably 0.2 or less, more preferably 0.1 or less. .

As a method for hydrogenation, a normal method can be used. As the catalyst, a noble metal such as palladium, ruthenium or rhodium or nickel or a metal selected from these metals supported on a support such as activated carbon, activated alumina or diatomaceous earth is used, and the powdered catalyst is suspended and stirred. A batch method in which the reaction is performed or a continuous method using a reaction tower filled with a molded catalyst can be employed. The solvent for hydrogenation may not be used depending on the method of hydrogenation. However, when a solvent is used, alcohols, ethers, esters, and saturated hydrocarbons can usually be used. The reaction temperature at the time of hydrogenation can be usually set to 20 to 250 ° C., preferably 50 to 200 ° C. in order to appropriately adjust the hydrogenation rate. The hydrogen pressure at the time of hydrogenation is usually 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 4 to 49.0 × 10 5 Pa). ).

Hydrogenation can be performed before the cardanol derivative is formed, after the cardanol derivative is formed, before the bond with the cellulose, and after the bond with the cellulose. From the viewpoint of the hydrogenation and grafting reaction efficiency, etc. Before bonding with cellulose is preferred, and before formation of the cardanol derivative is more preferred.

In addition, the grafting of cellulose or a derivative thereof with alcohol or phenol can be performed using a polyfunctional compound having a functional group that binds to both of these hydroxy groups, and cellulose or a derivative thereof is introduced via the polyfunctional compound. Grafted. In addition, the thing which the polyfunctional compound couple | bonded with the hydroxyl group of cellulose, alcohol, and phenol is the derivative | guide_body of a cellulose, the derivative | guide_body of alcohol, and the derivative | guide_body of phenol, respectively. For example, one functional group of a polyfunctional compound is bonded to the hydroxy group of phenol to form a cardanol derivative, and the functional group of the cardanol derivative is bonded to cellulose. According to such bonding with a polyfunctional compound, the reaction efficiency of the hydroxy group of cellulose can be improved, and side reactions can be suppressed.

In the polyfunctional compound, cellulose and a functional group that is bonded to a hydroxy group of alcohol or phenol are preferably bonded to a hydrocarbon group, and the hydrocarbon group preferably has 1 or more carbon atoms, more preferably 2 or more. The number of carbon atoms is preferably 20 or less, more preferably 14 or less, and even more preferably 8 or less. When the number of carbon atoms is within this range, a decrease in reactivity can be suppressed and grafting can be performed efficiently. As such a hydrocarbon group, a divalent group is preferable, and 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, a dodecamethylene group, Divalent linear aliphatic hydrocarbon groups such as hexadecamethylene group; cycloheptane ring, cyclohexane ring, cyclooctane ring, bicyclopentane ring, tricyclohexane ring, bicyclooctane ring, bicyclononane ring, tricyclodecane ring, etc. Examples thereof include a divalent alicyclic hydrocarbon group; a divalent aromatic hydrocarbon group such as a benzene ring, a naphthalene ring and a biphenylene group, and a divalent group composed of a combination thereof. Of these, a chain alkylene group is preferred.

When the above hydrocarbon group is an aromatic hydrocarbon group or an alicyclic hydrocarbon group, the rigidity of the resin can be improved due to their rigidity. On the other hand, when the hydrocarbon group is a linear aliphatic hydrocarbon group, the toughness of the resin can be improved due to its flexibility.

The functional group of the polyfunctional compound is preferably a group selected from a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid halide group such as a carboxylic acid chloride, an epoxy group, an isocyanate group, and a halogen atom. Of these, carboxyl groups, carboxylic acid anhydride groups, halogen atoms such as chlorine atoms, and isocyanate groups are preferred. The functional group to be reacted with the hydroxyl group of alcohol or phenol is preferably a carboxylic acid anhydride group, a halogen atom such as a chlorine atom, or an isocyanate group. The functional group to be reacted with the hydroxy group of cellulose or a derivative thereof is carboxylic acid chloride. Carboxylic acid halide groups such as groups and isocyanate groups are preferred. The carboxylic acid halide group can be formed by converting a carboxyl group into an acid halide.

Specific examples of such polyfunctional compounds include dicarboxylic acids, carboxylic anhydrides, dicarboxylic acid halides, monochlorocarboxylic acids, and diisocyanates. Examples of the dicarboxylic acid include malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, pentadecanedicarboxylic acid, and hexadecanedicarboxylic acid. The dicarboxylic acid anhydride can be exemplified, and examples of the dicarboxylic acid halide include acid halides of these dicarboxylic acids. Monochlorocarboxylic acids include monochloroacetic acid, 3-chloropropionic acid, 3-fluoropropionic acid, 4-chlorobutyric acid, 4-fluorobutyric acid, 5-chlorovaleric acid, 5-fluorovaleric acid, 6-chlorohexanoic acid, 6 -Fluorohexanoic acid, 8-chlorooctanoic acid, 8-fluorooctanoic acid, 12-chlorododecanoic acid, 12-fluorododecanoic acid, 18-chlorostearic acid, 18-fluorostearic acid. Diisocyanates include 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 triisocyanate 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, dicyclohexylmethane diisocyanate (HMDI: hydrogenated MDI) It can be mentioned. Among these, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI) and 1,6-hexamethylene diisocyanate (HDI) can be preferably used.

The grafting of cellulose or a derivative thereof with alcohol or phenol through these polyfunctional compounds is carried out through an ester bond, an ether bond or a urethane bond.

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

Grafting rate by carboxylic acid, alcohol, phenol or derivatives thereof on cellulose or its derivatives, that is, the number of hydroxyl groups contained in the glucose unit of cellulose or its derivatives reacted with carboxylic acid, alcohol or derivatives thereof Is preferably from 0.1 to 2.9, more preferably from 1.0 to 2.8, in view of water resistance, mechanical properties, heat resistance, and the like. It is. Further, the average value of the number of hydroxy groups remaining in the glucose unit of cellulose or its derivative, and the hydroxyl group residual degree (DSOH) is 0.9 or less from the viewpoint of sufficiently ensuring water resistance, mechanical strength, and plasticity. Preferably, 0.7 or less is more preferable.

The grafting rate of cardanol to cellulose and its derivatives is the average value of the number of hydroxyl groups bonded to cardanol in the glucose unit of cellulose and its derivatives, the degree of hydroxyl substitution (DSCD) is water resistance, mechanical properties From the viewpoint of improving heat resistance, 0.1 or more is preferable, 0.2 or more is more preferable, and 0.4 or more is more preferable. The maximum value of DSCD is theoretically “3”, but is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1.5 or less in order to perform efficient bonding. Further, the DSCD may be 1 or less, and a sufficient improvement effect can be obtained. As DSCD increases, tensile fracture strain (toughness) tends to increase while maximum strength (tensile strength, bending strength) tends to decrease. Therefore, it is preferable to set appropriately according to desired properties. In addition, the average value of the number of hydroxyl groups remaining in the glucose unit of cellulose and its derivatives bound with cardanol, and the residual hydroxyl group (DSOH) are 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.

Grafting cellulose or its derivatives with carboxylic acids, alcohols, phenols or their derivatives heats cellulose or its derivatives, carboxylic acids, alcohols, phenols or their derivatives at a suitable temperature in a solvent that can dissolve them. Can be implemented. Although cellulose is difficult to dissolve in ordinary solvents, it can be dissolved in dimethylsulfoxide-amine solvents, dimethylformamide-chloral-pyridine solvents, dimethylacetamide-lithium chloride solvents, imidazolium ionic liquids, and the like. When grafting in a solvent such as dioxane, chloroform, methylene chloride, acetone, etc., solubility is achieved by preliminarily binding a part of the hydroxy group of cellulose or its derivative with carboxylic acid or alcohol to reduce intermolecular force. It is preferable to use an acylated cellulose such as acetyl cellulose, propionyl cellulose, butyryl cellulose, etc., and particularly preferably acetyl cellulose.

The acylation rate in the acylated cellulose is an average value of the number of hydroxy groups contained in the glucose unit subjected to the acylation reaction, and the degree of hydroxyl group substitution (DSAC), in order to increase the solubility of cellulose. 5 or more is preferable, 1.0 or more is more preferable, 1.5 or more is more preferable, and 2.9 or less is preferable and 2.8 or less is more preferable in order to perform efficient grafting of cellulose or a derivative thereof. preferable.

Thereafter, grafting of cellulose or a derivative thereof can be completed by a reaction between the hydroxy group of acylated cellulose and the hydroxy group of phenol such as cardanol.

[Polyether-modified polysiloxane]
The polyether-modified polysiloxane has a polyether group represented by — (CmH2mO) n— (m is an integer of 2 to 4, n is an integer of 1 to 80) or a polyether group having a substituent. Although it will not specifically limit if it has, The polyether modified polysiloxane represented by Formula (1) is preferable.

In the formula, R ₁ to R ₁₀ independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of R ₁ , R ₄ , R ₆ , and R ₈ is — (CmH 2 mO) n—. A polyether group (m is an integer of 2 to 4, n is an integer of 1 to 80), and a and b are integers having a total of 10 to 1000.

The alkyl group represented by R ₁ to R ₁₀ is preferably a lower alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, and among these, a methyl group is preferable. The aryl group represented by R ₁ to R ₁₀ is preferably an aryl group having 6 to 12 carbon atoms such as a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

The polyether group represented by the above-(CmH2mO) n- represented by at least one of R ₁ , R ₄ , R ₆ and R ₈ is a polymethyl ether group, a polyethyl ether group, a polypropyl ether group or a polybutyl ether group. Even those having one kind of polyether group, those having two or more kinds, or having two or more kinds, alternately, even if the same kind is continuous, Moreover, you may couple | bond together at random. Specific examples include R (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b — and the like. In the formula, the oxyethylene group and the oxypropylene group may be the same or may be bonded alternately or randomly, and R is a hydrogen atom or the above alkyl group or aryl group. Can be mentioned. The polyether group may have a substituent, and examples of the substituent include the above alkyl group and aryl group.

The polyether group may have at least one of R ₁ , R ₄ , R ₆ , and R ₈ , and may have two or more, or all of them. Thus, by having a polyether group at the end of the main chain or side chain, the dispersibility of the polyether-modified polysiloxane in cellulose can be improved, bleed-out is suppressed, and impact resistance is improved. Can be made.

Here, the HLB value is a value indicating a hydrophilic-lipophilic balance, and is defined by the formula (2) based on the Griffin method.

The polyether-modified polysiloxane preferably has an HLB value of 7 or more and 14 or less. When the polyether-modified polysiloxane has a value of 7 or more and 14 or less as the HLB value, the balance between the hydrophilic polyether group and the hydrophobic siloxane structure is such that the hydroxy group of the hydrophilic cellulose is converted to carboxylic acid, alcohol, or It can be matched with the hydrophilic-hydrophobic balance of the cellulose-based resin having a hydrophobic residue bonded to the derivative, and the dispersibility in the resin composition containing these can be improved. The HLB value of the polyether-modified polysiloxane is more preferably 7 or more and 8 or less. In the formula (2), the number average molecular weight can be used as the molecular weight.

In a cellulose resin composition containing these, bleeding out of the polyether-modified polysiloxane can be suppressed, and the impact resistance of the cellulose-based resin composition can be improved by the flexible structure of the polyether-modified polysiloxane.

The number average molecular weight of the polyether-modified polysiloxane is preferably 900 or more, more preferably 1000 or more, and preferably 100,000 or less, more preferably 60000 or less. When the molecular weight of the polyether-modified polysiloxane is sufficiently large, loss due to volatilization can be suppressed during kneading with the molten cellulose resin during the production of the cellulose resin composition. Further, when the molecular weight of the polyether-modified polysiloxane is an appropriate size, a uniform molded article with good dispersibility can be obtained.

As the number average molecular weight, a value measured by GPC of a 0.1% chloroform solution of the sample (calibrated with a polystyrene standard sample) can be adopted.

The content of such a polyether-modified polysiloxane is preferably 0.1% by mass or more and more preferably 1% by mass or more with respect to the whole cellulose resin composition in order to improve the impact resistance of the molded article obtained. . 10 mass% or less is preferable from the point which ensures characteristics, such as an intensity | strength of a cellulose resin, and suppresses bleed-out, and 5 mass% or less is more preferable.

By adding such a polyether-modified polysiloxane to a cellulosic resin, the polyether-modified polysiloxane can be dispersed in the resin with an appropriate particle size, for example, an average particle size of 0.1 to 100 μm. The impact resistance of the composition can be improved.

[Cellulose-based resin composition]
Addition of colorants, antioxidants, heat stabilizers, plasticizers, flame retardants, etc., as necessary, to the cellulose-based resin composition as long as the functions of the cellulose-based resin and the polyether-modified polysiloxane are not impaired. An agent may be added.

Such a cellulose resin composition can be produced by, for example, hand-mixing various additives, a cellulose resin, and a polyether-modified polysiloxane, or a mixer such as a tumbler mixer, a ribbon blender, a single-screw or multi-screw mixing extruder. It can be produced by melting and mixing with a compounding apparatus such as a kneader kneader or a kneading roll, and granulating it into an appropriate shape as necessary. As another preferred production method, various additives and a resin dispersed in a solvent such as an organic solvent are mixed, and if necessary, a coagulation solvent is added to mix the various additives and the resin. And then the solvent is evaporated.

The cellulosic resin can be used as a base resin for molding materials. A molding material using the cellulose-based resin as a base resin is suitable for a molded body such as a casing such as an exterior for an electronic device.

Here, the base resin is contained in a larger amount than the other components contained in the molding material, and allows other components to be contained within a range that does not hinder the function of the base resin. . For example, the base resin includes 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more in the composition.

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

[Cellulosic resin] Base resin 1
As base resin 1, cellulose acetate propionate (CAP482-20: manufactured by Eastman Chemical Co., Ltd .: acetylation rate of hydroxy group per glucose unit of cellulose: DSAce = 0.18, propionyl of hydroxy group per glucose unit of cellulose Conversion rate: DSPro = 2.49).

[Cellulosic resin] Base resin 2
According to Synthesis Examples 1 and 2, cardanol-grafted cellulose acetate was prepared as a base resin.
[Synthesis Example 1] Cardanol derivative 1
Preparation of monochloroacetic acid-modified cardanol chloride compound Hydrogenated cardanol mn-pentadecylphenol (ACROS: manufactured by Organics) in which unsaturated bond of the linear hydrocarbon part of cardanol is hydrogenated is used as a raw material. The hydroxyl group 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.

Specifically, a chlorinated hydrogenated cardanol was obtained according to the following.

First, 80 g (0.26 mol) of hydrogenated cardanol 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. Thereafter, at room temperature, 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 dropped. After completion of the dropwise addition, stirring was continued while refluxing at 73 ° C. for 4 hours. After cooling the reaction solution to room temperature, the reaction mixture was acidified with dilute hydrochloric acid until pH = 1, and methanol (250 mL), diethyl ether (500 mL), and distilled water (200 mL) were added. The aqueous layer was separated and discarded with a separatory funnel, and the ether layer was washed twice with 400 mL of distilled water. After anhydrous magnesium was added to the ether layer and dried, this was filtered off. The filtrate (ether layer) was concentrated under reduced pressure using an evaporator (90 ° C./3 mmHg) to obtain a yellowish brown powdery crude product as a residue. This crude product was recrystallized from n-hexane and vacuum-dried to obtain 46 g (0.12 mol) of the desired carboxylated hydrogenated cardanol white powder.

46 g (0.12 mol) of the obtained carboxylated hydrogenated cardanol was dissolved in 250 mL of dehydrated chloroform, and 24 g (0.19 mol) of oxalyl chloride and 0.25 mL (3.2 mmol) of N, N-dimethylformamide were added at room temperature. Stir for 72 hours. Chloroform and excess oxalyl chloride were distilled off under reduced pressure to obtain 48 g (0.13 mol) of chlorinated hydrogenated cardanol.
[Synthesis Example 2] Cardanol-Grafted Cellulose Acetate The chlorinated hydrogenated cardanol (cardanol derivative) prepared in Synthesis Example 1 was converted into cellulose acetate (LM-80: manufactured by Daicel Chemical Industries, Ltd.): hydroxy per cellulose glucose unit Acetylation rate of the group: DSAce = 2.1) to obtain grafted cellulose acetate.

Specifically, grafted cellulose acetate was obtained according to the following.

30 g of 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 this solution was added 300 mL of a dioxane solution in which 32 g (0.084 mol) of the chlorinated hydrogenated cardanol prepared in Synthesis Example 1 was dissolved, and the mixture was heated to reflux at 100 ° C. for 5 hours. The reaction solution was slowly added dropwise to 4.5 L of methanol while stirring to cause reprecipitation, and the solid was separated by filtration. The solid separated by filtration was air-dried overnight, and further vacuum-dried at 105 ° C. for 5 hours to obtain 23 g of grafted cellulose acetate.

The obtained grafted cellulose acetate was measured by 1H-NMR (AV-400, 400 MHz: manufactured by Bruker), and the DSCD was 0.47.

[Cellulosic resin] Base resin 3
According to Synthesis Examples 3 to 6, cardanol grafted cellulose acetate propionate was prepared as a base resin.
[Synthesis Example 3] Preparation of hydrogenated cardanol 3-pentadecylcyclohexanol In a batch-type autoclave with an internal volume of 1.0 liter, 20 g of cardanol obtained by distillation purification from heat-treated cashew nut oil, ruthenium / carbon catalyst (Ru : 5% by mass) and 20 ml of tetrahydrofuran were charged, 20 kgf / cm 2 (1.96 × 10 6 Pa) of hydrogen was injected at room temperature, and the mixture was stirred at 80 ° C. for 3 hours to carry out a hydrogenation reaction. Then, the ruthenium / carbon catalyst was removed by filtering the solution taken out from 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 to obtain 20.6 g of hydrogenated cardanol which was a white solid at room temperature.

The purity of the obtained hydrogenated cardanol was measured by a liquid chromatograph (LC-10ADVP: manufactured by Shimadzu Corporation), and the purity was 99% by mass.

The hydrogenated cardanol obtained was measured by 1H-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.
[Synthesis Example 4] Diisocyanate-added cardanol derivative 92.7 g (0.55 mol) of hexamethylene diisocyanate (HDI) was heated to 50 ° C. while stirring, and 17.1 g of hydrogenated cardanol obtained in Synthesis Example 3 ( 0.055 mol) 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. Thereafter, the crystals were filtered (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), dried under reduced pressure (˜0.4 kPa) at 30 ° C. for 6 hours, and diisocyanate addition in which HDI and hydrogenated cardanol were combined at 1: 1. 22.61 g of a white powder (dry crystal) of a cardanol derivative was obtained. The obtained diisocyanate-added cardanol derivative was measured by liquid chromatography (LC-10ADVP island: manufactured by Tsu Seisakusho), and the purity was 91% by mass.
[Synthesis Example 5] Cardanol-Grafted Cellulose Acetate The diisocyanate-added cardanol derivative obtained in Synthesis Example 4 was converted into cellulose acetate (LM-80: manufactured by Daicel Chemical Industries, Ltd.): acetylation of hydroxy groups per glucose unit of cellulose. Ratio: DSAce = 2.1) to obtain grafted cellulose acetate.

Specifically, grafted cellulose acetate was prepared according to the following.

27.5 g (0.11 mol / Glc) of cellulose acetate and 385 mL of dehydrated dioxane were added and dissolved at a liquid temperature of 80 to 88 ° C. over 1 hour. After cooling to 40 ° C., 0.276 g (0.437 mmol) of dibutyltin laurate was dissolved in 2.8 ml of dehydrated dioxane and added. Subsequently, 11.56 g (purity 91.0%, 0.022 mol) of the diisocyanate-added cardanol derivative synthesized in Synthesis Example 4 was dissolved in 50 ml of dehydrated dioxane after heating and added, and the mixture was stirred at a liquid temperature of 80 ° C. for 3 hours. Further, 11.05 g (purity 91.0%, 0.022 mol) of a diisocyanate-added cardanol derivative was heated and dissolved in 50 ml of dehydrated dioxane, and the mixture was stirred at 80 ° C. for 18 hours. After cooling to 30 ° C., 4.5 L of methanol was added with stirring to precipitate the polymer. After the polymer was filtered, it was dried under reduced pressure (˜0.7 kPa) at 105 ° C. for 14 hours to obtain 43.9 g of a dry polymer. This dry polymer and 600 ml of methyl ethyl ketone were stirred at a liquid temperature of 70 to 80 ° C. for 1 hour to dissolve the polymer. Thereafter, it was cooled to 30 ° C. The polymer solution was centrifuged to separate the insoluble matter by sedimentation (3500 rpm × 15 minutes). Further, 1 L of hexane was added to the polymer solution to precipitate the polymer. The polymer was filtered and washed twice with 1 L of hexane. The same operation was further repeated twice, followed by drying under reduced pressure (˜0.8 kPa) at 50 ° C. for 14 hours to obtain 36.4 g of cardanol-grafted cellulose acetate.
[Synthesis Example 6] Cardanol-grafted cellulose acetate propionate 36.4 g of cardanol-grafted cellulose acetate obtained in Synthesis Example 5 and 310 ml of dehydrated pyridine were charged and dissolved at a liquid temperature of 75 to 80 ° C. over 20 minutes. . At a liquid temperature of 76 ° C., 18.3 g (0.15 mol) of N, N-dimethylaminopyridine and 390 ml of propionic anhydride were added, and the mixture was stirred at a liquid temperature of 100 ° C. for 1 hour. After cooling to a liquid temperature of 30 ° C., 130 ml of methanol was added over 70 minutes while cooling with ice. Meanwhile, the liquid temperature was kept at 30-40 ° C. While stirring the reaction solution, 250 ml of methanol was added to precipitate the polymer. The polymer was filtered and washed twice with 200 ml of methanol. The obtained polymer was dried and then dissolved in 250 ml of chloroform at a liquid temperature of 60 ° C. After cooling, 1.3 L of methanol was added with stirring to precipitate the polymer. The polymer was filtered and washed twice with 100 ml of methanol. The polymer was dried in vacuo (˜0.7 kPa) at 105 ° C. for 16 hours to give 35.8 g of cardanol grafted cellulose acetate propionate.

The obtained cardanol grafted cellulose acetate propionate was measured by 1H-NMR (AV-400, 400 MHz: manufactured by Bruker). DSAce: 2.1, DSPro: 0.59, DSCD: 0.25 there were.

[Polyether-modified silicone compound]
The polyether-modified polysiloxane shown in Table 1 was used.

[Example 1]
[Kneading]
Cellulose acetate propionate (base resin 1) and SH8700 (Toray Dow Corning Co., Ltd.) were blended as shown in Table 1 using a twin-screw kneader (HAKE-MiniLab (Micro-Extruder: manufactured by Thermo Electron Corp.)). Then, the mixture was melt-kneaded for 7 minutes under the conditions of 200 to 210 ° C. and a rotational speed of 60 rpm to recover the cellulose resin composition.
[injection molding]
The obtained cellulose resin composition was injection-molded by injection molding (HAKKE-MiniJetII: manufactured by Thermo Scientific) under the conditions of an injection temperature of 200 to 210 ° C., an injection pressure of 800 bar to 1200 bar, a mold temperature of 100 ° C., and a holding pressure of 400 bar. A test piece having a thickness of 2 mm, a width of 13 mm, and a length of 80 mm was obtained. Moreover, this molded body was evaluated according to the following. The results are shown in Table 2.
[Compatibility evaluation]
About the molded object obtained by said shaping | molding, the external appearance was observed visually and compatibility was evaluated on the following reference | standard.

A: Transparent B: Cloudiness (uniformly dispersed)
C: Unevenly distributed [Evaluation of Izod impact strength]
About the molded object obtained by said shaping | molding, the Izod impact strength with a notch was measured based on JISK7110.
[Bending test]
About the molded object obtained by said shaping | molding, the bending test was done based on JISK7171.
[Measurement of water absorption rate]
The water absorption was measured according to JIS K7209.

[Comparative Example 1]
A test piece was prepared and tested in the same manner as in Example 1 except that the polyether-modified polysiloxane was not used. The results are shown in Table 2.

From the results, it can be seen that in Example 1, the impact strength was improved while maintaining good strength and water resistance.

[Examples 2 to 21, Comparative Example 3]
Test pieces were prepared and tested in the same manner as in Example 1 except that the base resins and polyether-modified polysiloxanes shown in Tables 3 to 6 were used. The results are shown in Tables 3-6.

[Comparative Examples 2 and 4]
Test pieces were prepared and tested in the same manner as in Example 1 except that the polyether-modified polysiloxane was not used and the base resins shown in Tables 3 to 6 were used. The results are shown in Tables 3-6.

As shown in Examples 2 to 12, the cellulose resin composition in which the polyether-modified polysiloxane having an HLB value of 7 to 8 is added to the base resin 2 has a large impact strength while maintaining good strength and water resistance. It can be seen that there is an improvement. Since the polyether-modified polysiloxane having an HLB value of 7 to 8 is moderately dispersed in the base resin 2, shear deformation due to the plasticizing effect of the base resin 2 and the low-elasticity region of the polyether-modified polysiloxane at the time of failure It is thought that stress concentration on the surface causes impact energy to be absorbed efficiently. As shown in Examples 13 to 15, the cellulose resin composition in which the polyether-modified polysiloxane having an HLB value of 10 to 14 is added to the base resin 2 has an impact strength while maintaining good strength and water resistance. It turns out that it is improving. Since the polyether-modified polysiloxane having an HLB value of 10 to 14 is highly dispersed in the base resin 2, it is considered that the plasticity of the base resin 2 is promoted at the time of breakage and energy absorption occurs due to shear deformation.

On the other hand, as shown in Examples 16 and 17, the cellulose resin composition in which the polyether-modified polysiloxane having an HLB value of 6 or less was added to the base resin 2, although the compatibility with the base resin 2 was poor, the water absorption rate It can be seen that the difference between the HLB values of 7 and 8 is small. Furthermore, in the cellulose resin composition to which dimethyl silicone is added as shown in Comparative Example 3, the compatibility with the base resin 2 is remarkably poor, and the phenomenon that dimethyl silicone oozes out on the surface of the molded product, bleeding occurs.

As shown in Examples 13 to 15, the cellulose resin composition in which the polyether-modified polysiloxane having an HLB value of 10 to 14 is added to the base resin 2 has an impact strength while maintaining good strength and water resistance. You can see that it has improved. Since the polyether-modified polysiloxane having an HLB value of 10 to 14 is highly dispersed in the base resin 2, it is considered that the plasticity of the base resin 2 is promoted at the time of breakage and energy absorption occurs due to shear deformation.

As shown in Example 19, the impact strength of the cellulosic resin composition obtained by adding the polyether-modified polysiloxane having an HLB value of 8 to the base resin 3 is improved while maintaining good strength and water resistance. I understand. It is considered that the polyether-modified polysiloxane having an HLB value of 8 is moderately dispersed in the base resin 3 and absorbs impact energy by stress concentration in the low elasticity region of the polysiloxane when broken.
On the other hand, as shown in Example 18, in the cellulose resin composition in which the polyether-modified polysiloxane having an HLB value of 6 is added to the base resin 3, the water absorption is HLB value although the compatibility with the base resin 3 is poor. It can be seen that the difference from 7 and 8 is small. Furthermore, it can be seen that the cellulose resin composition to which the polyether-modified polysiloxane having an HLB value of 10 to 13 shown in Examples 20 and 21 is added has good compatibility between the base resin 3 and the polysiloxane.

This application includes all matters described in Japanese Patent Application No. 2012-268140 filed on Dec. 7, 2012 as its contents.

Although the cellulose resin composition of the present invention is a bioplastic, it can improve mechanical properties, impact resistance, plasticity, and water resistance, and can be used for the casing of electrical equipment similar to petroleum plastic.

The present invention can be used in all industrial fields that require a power source, as well as industrial fields related to the transportation, storage and supply of electrical energy. Specifically, it can be used as a power source for mobile devices such as mobile phones and notebook computers.

Claims

A cellulose resin in which one or more selected from carboxylic acids having 1 to 32 carbon atoms, alcohols, phenols and derivatives thereof are chemically bonded to a hydroxy group of cellulose or a derivative thereof; and-(CmH2mO) n- ( m represents an integer of 2 to 4, and n represents an integer of 1 to 80.) and a polyether-modified polysiloxane having a polyether group having a substituent. Cellulosic resin composition.
The polyether-modified polysiloxane has the formula (1)

(Wherein R 1 to R 10 independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of R 1 , R 4 , R 6 , and R 8 is the polyether group or The cellulose-based resin composition according to claim 1, wherein the polyether group has a group, and a and b are integers having a total of 10 to 1,000.
The cellulose-based resin composition according to claim 1 or 2, wherein the polyether-modified polysiloxane has an HLB value represented by the formula (2) of 7 or more and 14 or less.
The polyether-modified polysiloxane is contained in an amount of 0.1% by mass or more and 10% by mass or less based on the total amount of the polyether-modified polysiloxane and the cellulose resin. Cellulosic resin composition as described in 2.
A molding material comprising the cellulose resin composition according to any one of claims 1 to 4.